---
_id: '14001'
abstract:
- lang: eng
text: Chiral molecules interact and react differently with other chiral objects,
depending on their handedness. Therefore, it is essential to understand and ultimately
control the evolution of molecular chirality during chemical reactions. Although
highly sophisticated techniques for the controlled synthesis of chiral molecules
have been developed, the observation of chirality on the natural femtosecond time
scale of a chemical reaction has so far remained out of reach in the gas phase.
Here, we demonstrate a general experimental technique, based on high-harmonic
generation in tailored laser fields, and apply it to probe the time evolution
of molecular chirality during the photodissociation of 2-iodobutane. These measurements
show a change in sign and a pronounced increase in the magnitude of the chiral
response over the first 100 fs, followed by its decay within less than 500 fs,
revealing the photodissociation to achiral products. The observed time evolution
is explained in terms of the variation of the electric and magnetic transition-dipole
moments between the lowest electronic states of the cation as a function of the
reaction coordinate. These results open the path to investigations of the chirality
of molecular-reaction pathways, light-induced chirality in chemical processes,
and the control of molecular chirality through tailored laser pulses.
article_processing_charge: No
article_type: original
arxiv: 1
author:
- first_name: Denitsa Rangelova
full_name: Baykusheva, Denitsa Rangelova
id: 71b4d059-2a03-11ee-914d-dfa3beed6530
last_name: Baykusheva
- first_name: Daniel
full_name: Zindel, Daniel
last_name: Zindel
- first_name: Vít
full_name: Svoboda, Vít
last_name: Svoboda
- first_name: Elias
full_name: Bommeli, Elias
last_name: Bommeli
- first_name: Manuel
full_name: Ochsner, Manuel
last_name: Ochsner
- first_name: Andres
full_name: Tehlar, Andres
last_name: Tehlar
- first_name: Hans Jakob
full_name: Wörner, Hans Jakob
last_name: Wörner
citation:
ama: Baykusheva DR, Zindel D, Svoboda V, et al. Real-time probing of chirality during
a chemical reaction. Proceedings of the National Academy of Sciences. 2019;116(48):23923-23929.
doi:10.1073/pnas.1907189116
apa: Baykusheva, D. R., Zindel, D., Svoboda, V., Bommeli, E., Ochsner, M., Tehlar,
A., & Wörner, H. J. (2019). Real-time probing of chirality during a chemical
reaction. Proceedings of the National Academy of Sciences. Proceedings
of the National Academy of Sciences. https://doi.org/10.1073/pnas.1907189116
chicago: Baykusheva, Denitsa Rangelova, Daniel Zindel, Vít Svoboda, Elias Bommeli,
Manuel Ochsner, Andres Tehlar, and Hans Jakob Wörner. “Real-Time Probing of Chirality
during a Chemical Reaction.” Proceedings of the National Academy of Sciences.
Proceedings of the National Academy of Sciences, 2019. https://doi.org/10.1073/pnas.1907189116.
ieee: D. R. Baykusheva et al., “Real-time probing of chirality during a chemical
reaction,” Proceedings of the National Academy of Sciences, vol. 116, no.
48. Proceedings of the National Academy of Sciences, pp. 23923–23929, 2019.
ista: Baykusheva DR, Zindel D, Svoboda V, Bommeli E, Ochsner M, Tehlar A, Wörner
HJ. 2019. Real-time probing of chirality during a chemical reaction. Proceedings
of the National Academy of Sciences. 116(48), 23923–23929.
mla: Baykusheva, Denitsa Rangelova, et al. “Real-Time Probing of Chirality during
a Chemical Reaction.” Proceedings of the National Academy of Sciences,
vol. 116, no. 48, Proceedings of the National Academy of Sciences, 2019, pp. 23923–29,
doi:10.1073/pnas.1907189116.
short: D.R. Baykusheva, D. Zindel, V. Svoboda, E. Bommeli, M. Ochsner, A. Tehlar,
H.J. Wörner, Proceedings of the National Academy of Sciences 116 (2019) 23923–23929.
date_created: 2023-08-09T13:10:36Z
date_published: 2019-11-13T00:00:00Z
date_updated: 2023-08-22T07:40:05Z
day: '13'
doi: 10.1073/pnas.1907189116
extern: '1'
external_id:
arxiv:
- '1906.10818'
pmid:
- '31723044'
intvolume: ' 116'
issue: '48'
keyword:
- Multidisciplinary
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.1073/pnas.1907189116
month: '11'
oa: 1
oa_version: Published Version
page: 23923-23929
pmid: 1
publication: Proceedings of the National Academy of Sciences
publication_identifier:
eissn:
- 1091-6490
issn:
- 0027-8424
publication_status: published
publisher: Proceedings of the National Academy of Sciences
quality_controlled: '1'
scopus_import: '1'
status: public
title: Real-time probing of chirality during a chemical reaction
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 116
year: '2019'
...
---
_id: '14002'
abstract:
- lang: eng
text: The advancement of attosecond chronoscopy has made it possible to reveal ultrashort
time dynamics of photoionization [1]. Ionization delay measurements in atomic
targets provide a wealth of information about the timing of the photoelectric
effect [2], resonances, electron correlations and transport. The extension of
this approach to molecules, however, presents great challenges. In addition to
the difficulty of identifying correct ionization channels, it is hard to disentangle
the role of the anisotropic molecular landscape from the delays inherent to the
excitation process itself. Here, we present the measurements of ionization delays
from ethyl iodide around the 4d giant dipole resonance of iodine. We employ attosecond
streaking spectroscopy, which enables to disentangle the contribution to the delay
from the functional ethyl group, being responsible for the characteristic chemical
reactivity of the molecule. An attosecond extreme ultraviolet (XUV) pulse ionizes
the molecule around the energy of the giant resonance and the released electron
is exposed to the ponderomotive force of a synchronized near-infrared (NIR) field,
which yields a streaking spectrogram (see figure). Comparative phase analysis
of the spectrograms corresponding to iodine 4d and neon 2p emission permits extracting
overall photoemission delays for ethyl iodide. The data is recorded for multiple
photon energies around the iodine 4d resonance and compared to classical Wigner
propagation [3] and quantum scattering [4] calculations. Here the outgoing electron,
produced via inner shell ionization of the iodine atom in ethyl iodide, and thereby
hardly influenced by the molecular potential during the birth process, acquires
the necessary information about the influence of the functional ethyl group during
its propagation. We find significant delay contributions that can distinguish
between different functional groups, providing a sensitive probe of the local
molecular environment [5]. This would stimulate to perform further angle resolved
measurements in molecules to probe the potential landscape in three dimension.
article_number: '8871819'
article_processing_charge: No
author:
- first_name: Shubhadeep
full_name: Biswas, Shubhadeep
last_name: Biswas
- first_name: I.
full_name: Liontos, I.
last_name: Liontos
- first_name: A. M.
full_name: Kamal, A. M.
last_name: Kamal
- first_name: N. G.
full_name: Kling, N. G.
last_name: Kling
- first_name: A. F.
full_name: Alharbi, A. F.
last_name: Alharbi
- first_name: M.
full_name: Alharbi, M.
last_name: Alharbi
- first_name: A. M.
full_name: Azzeer, A. M.
last_name: Azzeer
- first_name: H. J.
full_name: Worner, H. J.
last_name: Worner
- first_name: A. S.
full_name: Landsman, A. S.
last_name: Landsman
- first_name: M. F.
full_name: Kling, M. F.
last_name: Kling
- first_name: B.
full_name: Forg, B.
last_name: Forg
- first_name: J.
full_name: Schotz, J.
last_name: Schotz
- first_name: W.
full_name: Schweinberger, W.
last_name: Schweinberger
- first_name: L.
full_name: Ortmann, L.
last_name: Ortmann
- first_name: T.
full_name: Zimmermann, T.
last_name: Zimmermann
- first_name: L.-W.
full_name: Pi, L.-W.
last_name: Pi
- first_name: Denitsa Rangelova
full_name: Baykusheva, Denitsa Rangelova
id: 71b4d059-2a03-11ee-914d-dfa3beed6530
last_name: Baykusheva
- first_name: H. A.
full_name: Masood, H. A.
last_name: Masood
citation:
ama: 'Biswas S, Liontos I, Kamal AM, et al. Probing molecular influence on photoemission
delays. In: 2019 Conference on Lasers and Electro-Optics Europe & European
Quantum Electronics Conference. Institute of Electrical and Electronics Engineers;
2019. doi:10.1109/cleoe-eqec.2019.8871819'
apa: 'Biswas, S., Liontos, I., Kamal, A. M., Kling, N. G., Alharbi, A. F., Alharbi,
M., … Masood, H. A. (2019). Probing molecular influence on photoemission delays.
In 2019 Conference on Lasers and Electro-Optics Europe & European Quantum
Electronics Conference. Munich, Germany: Institute of Electrical and Electronics
Engineers. https://doi.org/10.1109/cleoe-eqec.2019.8871819'
chicago: Biswas, Shubhadeep, I. Liontos, A. M. Kamal, N. G. Kling, A. F. Alharbi,
M. Alharbi, A. M. Azzeer, et al. “Probing Molecular Influence on Photoemission
Delays.” In 2019 Conference on Lasers and Electro-Optics Europe & European
Quantum Electronics Conference. Institute of Electrical and Electronics Engineers,
2019. https://doi.org/10.1109/cleoe-eqec.2019.8871819.
ieee: S. Biswas et al., “Probing molecular influence on photoemission delays,”
in 2019 Conference on Lasers and Electro-Optics Europe & European Quantum
Electronics Conference, Munich, Germany, 2019.
ista: 'Biswas S, Liontos I, Kamal AM, Kling NG, Alharbi AF, Alharbi M, Azzeer AM,
Worner HJ, Landsman AS, Kling MF, Forg B, Schotz J, Schweinberger W, Ortmann L,
Zimmermann T, Pi L-W, Baykusheva DR, Masood HA. 2019. Probing molecular influence
on photoemission delays. 2019 Conference on Lasers and Electro-Optics Europe &
European Quantum Electronics Conference. CLEO: European Conference on Lasers and
Electro-Optics, 8871819.'
mla: Biswas, Shubhadeep, et al. “Probing Molecular Influence on Photoemission Delays.”
2019 Conference on Lasers and Electro-Optics Europe & European Quantum
Electronics Conference, 8871819, Institute of Electrical and Electronics Engineers,
2019, doi:10.1109/cleoe-eqec.2019.8871819.
short: S. Biswas, I. Liontos, A.M. Kamal, N.G. Kling, A.F. Alharbi, M. Alharbi,
A.M. Azzeer, H.J. Worner, A.S. Landsman, M.F. Kling, B. Forg, J. Schotz, W. Schweinberger,
L. Ortmann, T. Zimmermann, L.-W. Pi, D.R. Baykusheva, H.A. Masood, in:, 2019 Conference
on Lasers and Electro-Optics Europe & European Quantum Electronics Conference,
Institute of Electrical and Electronics Engineers, 2019.
conference:
end_date: 2019-06-27
location: Munich, Germany
name: 'CLEO: European Conference on Lasers and Electro-Optics'
start_date: 2019-06-23
date_created: 2023-08-09T13:10:49Z
date_published: 2019-10-17T00:00:00Z
date_updated: 2023-08-22T09:32:56Z
day: '17'
doi: 10.1109/cleoe-eqec.2019.8871819
extern: '1'
language:
- iso: eng
month: '10'
oa_version: None
publication: 2019 Conference on Lasers and Electro-Optics Europe & European Quantum
Electronics Conference
publication_identifier:
eisbn:
- '9781728104690'
isbn:
- '9781728104706'
publication_status: published
publisher: Institute of Electrical and Electronics Engineers
quality_controlled: '1'
scopus_import: '1'
status: public
title: Probing molecular influence on photoemission delays
type: conference
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
year: '2019'
...
---
_id: '14184'
abstract:
- lang: eng
text: "Learning disentangled representations is considered a cornerstone problem
in\r\nrepresentation learning. Recently, Locatello et al. (2019) demonstrated
that\r\nunsupervised disentanglement learning without inductive biases is theoretically\r\nimpossible
and that existing inductive biases and unsupervised methods do not\r\nallow to
consistently learn disentangled representations. However, in many\r\npractical
settings, one might have access to a limited amount of supervision,\r\nfor example
through manual labeling of (some) factors of variation in a few\r\ntraining examples.
In this paper, we investigate the impact of such supervision\r\non state-of-the-art
disentanglement methods and perform a large scale study,\r\ntraining over 52000
models under well-defined and reproducible experimental\r\nconditions. We observe
that a small number of labeled examples (0.01--0.5\\% of\r\nthe data set), with
potentially imprecise and incomplete labels, is sufficient\r\nto perform model
selection on state-of-the-art unsupervised models. Further, we\r\ninvestigate
the benefit of incorporating supervision into the training process.\r\nOverall,
we empirically validate that with little and imprecise supervision it\r\nis possible
to reliably learn disentangled representations."
article_processing_charge: No
arxiv: 1
author:
- first_name: Francesco
full_name: Locatello, Francesco
id: 26cfd52f-2483-11ee-8040-88983bcc06d4
last_name: Locatello
orcid: 0000-0002-4850-0683
- first_name: Michael
full_name: Tschannen, Michael
last_name: Tschannen
- first_name: Stefan
full_name: Bauer, Stefan
last_name: Bauer
- first_name: Gunnar
full_name: Rätsch, Gunnar
last_name: Rätsch
- first_name: Bernhard
full_name: Schölkopf, Bernhard
last_name: Schölkopf
- first_name: Olivier
full_name: Bachem, Olivier
last_name: Bachem
citation:
ama: 'Locatello F, Tschannen M, Bauer S, Rätsch G, Schölkopf B, Bachem O. Disentangling
factors of variation using few labels. In: 8th International Conference on
Learning Representations. ; 2019.'
apa: Locatello, F., Tschannen, M., Bauer, S., Rätsch, G., Schölkopf, B., & Bachem,
O. (2019). Disentangling factors of variation using few labels. In 8th International
Conference on Learning Representations. Virtual.
chicago: Locatello, Francesco, Michael Tschannen, Stefan Bauer, Gunnar Rätsch, Bernhard
Schölkopf, and Olivier Bachem. “Disentangling Factors of Variation Using Few Labels.”
In 8th International Conference on Learning Representations, 2019.
ieee: F. Locatello, M. Tschannen, S. Bauer, G. Rätsch, B. Schölkopf, and O. Bachem,
“Disentangling factors of variation using few labels,” in 8th International
Conference on Learning Representations, Virtual, 2019.
ista: 'Locatello F, Tschannen M, Bauer S, Rätsch G, Schölkopf B, Bachem O. 2019.
Disentangling factors of variation using few labels. 8th International Conference
on Learning Representations. ICLR: International Conference on Learning Representations.'
mla: Locatello, Francesco, et al. “Disentangling Factors of Variation Using Few
Labels.” 8th International Conference on Learning Representations, 2019.
short: F. Locatello, M. Tschannen, S. Bauer, G. Rätsch, B. Schölkopf, O. Bachem,
in:, 8th International Conference on Learning Representations, 2019.
conference:
end_date: 2020-05-01
location: Virtual
name: 'ICLR: International Conference on Learning Representations'
start_date: 2020-04-26
date_created: 2023-08-22T14:06:37Z
date_published: 2019-12-20T00:00:00Z
date_updated: 2023-09-12T07:01:34Z
day: '20'
department:
- _id: FrLo
extern: '1'
external_id:
arxiv:
- '1905.01258'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://arxiv.org/abs/1905.01258
month: '12'
oa: 1
oa_version: Preprint
publication: 8th International Conference on Learning Representations
publication_status: published
quality_controlled: '1'
scopus_import: '1'
status: public
title: Disentangling factors of variation using few labels
type: conference
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
year: '2019'
...
---
_id: '14189'
abstract:
- lang: eng
text: "We consider the problem of recovering a common latent source with independent\r\ncomponents
from multiple views. This applies to settings in which a variable is\r\nmeasured
with multiple experimental modalities, and where the goal is to\r\nsynthesize
the disparate measurements into a single unified representation. We\r\nconsider
the case that the observed views are a nonlinear mixing of\r\ncomponent-wise corruptions
of the sources. When the views are considered\r\nseparately, this reduces to nonlinear
Independent Component Analysis (ICA) for\r\nwhich it is provably impossible to
undo the mixing. We present novel\r\nidentifiability proofs that this is possible
when the multiple views are\r\nconsidered jointly, showing that the mixing can
theoretically be undone using\r\nfunction approximators such as deep neural networks.
In contrast to known\r\nidentifiability results for nonlinear ICA, we prove that
independent latent\r\nsources with arbitrary mixing can be recovered as long as
multiple,\r\nsufficiently different noisy views are available."
alternative_title:
- PMLR
article_processing_charge: No
arxiv: 1
author:
- first_name: Luigi
full_name: Gresele, Luigi
last_name: Gresele
- first_name: Paul K.
full_name: Rubenstein, Paul K.
last_name: Rubenstein
- first_name: Arash
full_name: Mehrjou, Arash
last_name: Mehrjou
- first_name: Francesco
full_name: Locatello, Francesco
id: 26cfd52f-2483-11ee-8040-88983bcc06d4
last_name: Locatello
orcid: 0000-0002-4850-0683
- first_name: Bernhard
full_name: Schölkopf, Bernhard
last_name: Schölkopf
citation:
ama: 'Gresele L, Rubenstein PK, Mehrjou A, Locatello F, Schölkopf B. The incomplete
Rosetta Stone problem: Identifiability results for multi-view nonlinear ICA. In:
Proceedings of the 35th Conference on Uncertainty in Artificial Intelligence.
Vol 115. ML Research Press; 2019:217-227.'
apa: 'Gresele, L., Rubenstein, P. K., Mehrjou, A., Locatello, F., & Schölkopf,
B. (2019). The incomplete Rosetta Stone problem: Identifiability results for multi-view
nonlinear ICA. In Proceedings of the 35th Conference on Uncertainty in Artificial
Intelligence (Vol. 115, pp. 217–227). Tel Aviv, Israel: ML Research Press.'
chicago: 'Gresele, Luigi, Paul K. Rubenstein, Arash Mehrjou, Francesco Locatello,
and Bernhard Schölkopf. “The Incomplete Rosetta Stone Problem: Identifiability
Results for Multi-View Nonlinear ICA.” In Proceedings of the 35th Conference
on Uncertainty in Artificial Intelligence, 115:217–27. ML Research Press,
2019.'
ieee: 'L. Gresele, P. K. Rubenstein, A. Mehrjou, F. Locatello, and B. Schölkopf,
“The incomplete Rosetta Stone problem: Identifiability results for multi-view
nonlinear ICA,” in Proceedings of the 35th Conference on Uncertainty in Artificial
Intelligence, Tel Aviv, Israel, 2019, vol. 115, pp. 217–227.'
ista: 'Gresele L, Rubenstein PK, Mehrjou A, Locatello F, Schölkopf B. 2019. The
incomplete Rosetta Stone problem: Identifiability results for multi-view nonlinear
ICA. Proceedings of the 35th Conference on Uncertainty in Artificial Intelligence.
UAI: Uncertainty in Artificial Intelligence, PMLR, vol. 115, 217–227.'
mla: 'Gresele, Luigi, et al. “The Incomplete Rosetta Stone Problem: Identifiability
Results for Multi-View Nonlinear ICA.” Proceedings of the 35th Conference on
Uncertainty in Artificial Intelligence, vol. 115, ML Research Press, 2019,
pp. 217–27.'
short: L. Gresele, P.K. Rubenstein, A. Mehrjou, F. Locatello, B. Schölkopf, in:,
Proceedings of the 35th Conference on Uncertainty in Artificial Intelligence,
ML Research Press, 2019, pp. 217–227.
conference:
end_date: 2019-07-25
location: Tel Aviv, Israel
name: 'UAI: Uncertainty in Artificial Intelligence'
start_date: 2019-07-22
date_created: 2023-08-22T14:08:35Z
date_published: 2019-05-16T00:00:00Z
date_updated: 2023-09-12T08:07:38Z
day: '16'
department:
- _id: FrLo
extern: '1'
external_id:
arxiv:
- '1905.06642'
intvolume: ' 115'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://arxiv.org/abs/1905.06642
month: '05'
oa: 1
oa_version: Preprint
page: 217-227
publication: Proceedings of the 35th Conference on Uncertainty in Artificial Intelligence
publication_status: published
publisher: ML Research Press
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'The incomplete Rosetta Stone problem: Identifiability results for multi-view
nonlinear ICA'
type: conference
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 115
year: '2019'
...
---
_id: '14190'
abstract:
- lang: eng
text: "Learning meaningful and compact representations with disentangled semantic\r\naspects
is considered to be of key importance in representation learning. Since\r\nreal-world
data is notoriously costly to collect, many recent state-of-the-art\r\ndisentanglement
models have heavily relied on synthetic toy data-sets. In this\r\npaper, we propose
a novel data-set which consists of over one million images of\r\nphysical 3D objects
with seven factors of variation, such as object color,\r\nshape, size and position.
In order to be able to control all the factors of\r\nvariation precisely, we built
an experimental platform where the objects are\r\nbeing moved by a robotic arm.
In addition, we provide two more datasets which\r\nconsist of simulations of the
experimental setup. These datasets provide for\r\nthe first time the possibility
to systematically investigate how well different\r\ndisentanglement methods perform
on real data in comparison to simulation, and\r\nhow simulated data can be leveraged
to build better representations of the real\r\nworld. We provide a first experimental
study of these questions and our results\r\nindicate that learned models transfer
poorly, but that model and hyperparameter\r\nselection is an effective means of
transferring information to the real world."
article_processing_charge: No
arxiv: 1
author:
- first_name: Muhammad Waleed
full_name: Gondal, Muhammad Waleed
last_name: Gondal
- first_name: Manuel
full_name: Wüthrich, Manuel
last_name: Wüthrich
- first_name: Đorđe
full_name: Miladinović, Đorđe
last_name: Miladinović
- first_name: Francesco
full_name: Locatello, Francesco
id: 26cfd52f-2483-11ee-8040-88983bcc06d4
last_name: Locatello
orcid: 0000-0002-4850-0683
- first_name: Martin
full_name: Breidt, Martin
last_name: Breidt
- first_name: Valentin
full_name: Volchkov, Valentin
last_name: Volchkov
- first_name: Joel
full_name: Akpo, Joel
last_name: Akpo
- first_name: Olivier
full_name: Bachem, Olivier
last_name: Bachem
- first_name: Bernhard
full_name: Schölkopf, Bernhard
last_name: Schölkopf
- first_name: Stefan
full_name: Bauer, Stefan
last_name: Bauer
citation:
ama: 'Gondal MW, Wüthrich M, Miladinović Đ, et al. On the transfer of inductive
bias from simulation to the real world: a new disentanglement dataset. In: Advances
in Neural Information Processing Systems. Vol 32. ; 2019.'
apa: 'Gondal, M. W., Wüthrich, M., Miladinović, Đ., Locatello, F., Breidt, M., Volchkov,
V., … Bauer, S. (2019). On the transfer of inductive bias from simulation to the
real world: a new disentanglement dataset. In Advances in Neural Information
Processing Systems (Vol. 32). Vancouver, Canada.'
chicago: 'Gondal, Muhammad Waleed, Manuel Wüthrich, Đorđe Miladinović, Francesco
Locatello, Martin Breidt, Valentin Volchkov, Joel Akpo, Olivier Bachem, Bernhard
Schölkopf, and Stefan Bauer. “On the Transfer of Inductive Bias from Simulation
to the Real World: A New Disentanglement Dataset.” In Advances in Neural Information
Processing Systems, Vol. 32, 2019.'
ieee: 'M. W. Gondal et al., “On the transfer of inductive bias from simulation
to the real world: a new disentanglement dataset,” in Advances in Neural Information
Processing Systems, Vancouver, Canada, 2019, vol. 32.'
ista: 'Gondal MW, Wüthrich M, Miladinović Đ, Locatello F, Breidt M, Volchkov V,
Akpo J, Bachem O, Schölkopf B, Bauer S. 2019. On the transfer of inductive bias
from simulation to the real world: a new disentanglement dataset. Advances in
Neural Information Processing Systems. NeurIPS: Neural Information Processing
Systems vol. 32.'
mla: 'Gondal, Muhammad Waleed, et al. “On the Transfer of Inductive Bias from Simulation
to the Real World: A New Disentanglement Dataset.” Advances in Neural Information
Processing Systems, vol. 32, 2019.'
short: M.W. Gondal, M. Wüthrich, Đ. Miladinović, F. Locatello, M. Breidt, V. Volchkov,
J. Akpo, O. Bachem, B. Schölkopf, S. Bauer, in:, Advances in Neural Information
Processing Systems, 2019.
conference:
end_date: 2019-12-14
location: Vancouver, Canada
name: 'NeurIPS: Neural Information Processing Systems'
start_date: 2019-12-08
date_created: 2023-08-22T14:09:13Z
date_published: 2019-06-07T00:00:00Z
date_updated: 2023-09-13T09:46:38Z
day: '07'
department:
- _id: FrLo
extern: '1'
external_id:
arxiv:
- '1906.03292'
intvolume: ' 32'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://arxiv.org/abs/1906.03292
month: '06'
oa: 1
oa_version: Preprint
publication: Advances in Neural Information Processing Systems
publication_identifier:
isbn:
- '9781713807933'
publication_status: published
quality_controlled: '1'
status: public
title: 'On the transfer of inductive bias from simulation to the real world: a new
disentanglement dataset'
type: conference
user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1
volume: 32
year: '2019'
...
---
_id: '14191'
abstract:
- lang: eng
text: A broad class of convex optimization problems can be formulated as a semidefinite
program (SDP), minimization of a convex function over the positive-semidefinite
cone subject to some affine constraints. The majority of classical SDP solvers
are designed for the deterministic setting where problem data is readily available.
In this setting, generalized conditional gradient methods (aka Frank-Wolfe-type
methods) provide scalable solutions by leveraging the so-called linear minimization
oracle instead of the projection onto the semidefinite cone. Most problems in
machine learning and modern engineering applications, however, contain some degree
of stochasticity. In this work, we propose the first conditional-gradient-type
method for solving stochastic optimization problems under affine constraints.
Our method guarantees O(k−1/3) convergence rate in expectation on the objective
residual and O(k−5/12) on the feasibility gap.
article_processing_charge: No
arxiv: 1
author:
- first_name: Francesco
full_name: Locatello, Francesco
id: 26cfd52f-2483-11ee-8040-88983bcc06d4
last_name: Locatello
orcid: 0000-0002-4850-0683
- first_name: Alp
full_name: Yurtsever, Alp
last_name: Yurtsever
- first_name: Olivier
full_name: Fercoq, Olivier
last_name: Fercoq
- first_name: Volkan
full_name: Cevher, Volkan
last_name: Cevher
citation:
ama: 'Locatello F, Yurtsever A, Fercoq O, Cevher V. Stochastic Frank-Wolfe for composite
convex minimization. In: Advances in Neural Information Processing Systems.
Vol 32. ; 2019:14291–14301.'
apa: Locatello, F., Yurtsever, A., Fercoq, O., & Cevher, V. (2019). Stochastic
Frank-Wolfe for composite convex minimization. In Advances in Neural Information
Processing Systems (Vol. 32, pp. 14291–14301). Vancouver, Canada.
chicago: Locatello, Francesco, Alp Yurtsever, Olivier Fercoq, and Volkan Cevher.
“Stochastic Frank-Wolfe for Composite Convex Minimization.” In Advances in
Neural Information Processing Systems, 32:14291–14301, 2019.
ieee: F. Locatello, A. Yurtsever, O. Fercoq, and V. Cevher, “Stochastic Frank-Wolfe
for composite convex minimization,” in Advances in Neural Information Processing
Systems, Vancouver, Canada, 2019, vol. 32, pp. 14291–14301.
ista: 'Locatello F, Yurtsever A, Fercoq O, Cevher V. 2019. Stochastic Frank-Wolfe
for composite convex minimization. Advances in Neural Information Processing Systems.
NeurIPS: Neural Information Processing Systems vol. 32, 14291–14301.'
mla: Locatello, Francesco, et al. “Stochastic Frank-Wolfe for Composite Convex Minimization.”
Advances in Neural Information Processing Systems, vol. 32, 2019, pp. 14291–14301.
short: F. Locatello, A. Yurtsever, O. Fercoq, V. Cevher, in:, Advances in Neural
Information Processing Systems, 2019, pp. 14291–14301.
conference:
end_date: 2019-12-14
location: Vancouver, Canada
name: 'NeurIPS: Neural Information Processing Systems'
start_date: 2019-12-08
date_created: 2023-08-22T14:09:35Z
date_published: 2019-12-29T00:00:00Z
date_updated: 2023-09-12T08:48:45Z
day: '29'
department:
- _id: FrLo
extern: '1'
external_id:
arxiv:
- '1901.10348'
intvolume: ' 32'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://arxiv.org/abs/1901.10348
month: '12'
oa: 1
oa_version: Preprint
page: 14291–14301
publication: Advances in Neural Information Processing Systems
publication_identifier:
isbn:
- '9781713807933'
publication_status: published
quality_controlled: '1'
scopus_import: '1'
status: public
title: Stochastic Frank-Wolfe for composite convex minimization
type: conference
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 32
year: '2019'
...
---
_id: '14193'
abstract:
- lang: eng
text: "A disentangled representation encodes information about the salient factors\r\nof
variation in the data independently. Although it is often argued that this\r\nrepresentational
format is useful in learning to solve many real-world\r\ndown-stream tasks, there
is little empirical evidence that supports this claim.\r\nIn this paper, we conduct
a large-scale study that investigates whether\r\ndisentangled representations
are more suitable for abstract reasoning tasks.\r\nUsing two new tasks similar
to Raven's Progressive Matrices, we evaluate the\r\nusefulness of the representations
learned by 360 state-of-the-art unsupervised\r\ndisentanglement models. Based
on these representations, we train 3600 abstract\r\nreasoning models and observe
that disentangled representations do in fact lead\r\nto better down-stream performance.
In particular, they enable quicker learning\r\nusing fewer samples."
article_processing_charge: No
arxiv: 1
author:
- first_name: Sjoerd van
full_name: Steenkiste, Sjoerd van
last_name: Steenkiste
- first_name: Francesco
full_name: Locatello, Francesco
id: 26cfd52f-2483-11ee-8040-88983bcc06d4
last_name: Locatello
orcid: 0000-0002-4850-0683
- first_name: Jürgen
full_name: Schmidhuber, Jürgen
last_name: Schmidhuber
- first_name: Olivier
full_name: Bachem, Olivier
last_name: Bachem
citation:
ama: 'Steenkiste S van, Locatello F, Schmidhuber J, Bachem O. Are disentangled representations
helpful for abstract visual reasoning? In: Advances in Neural Information Processing
Systems. Vol 32. ; 2019.'
apa: Steenkiste, S. van, Locatello, F., Schmidhuber, J., & Bachem, O. (2019).
Are disentangled representations helpful for abstract visual reasoning? In Advances
in Neural Information Processing Systems (Vol. 32). Vancouver, Canada.
chicago: Steenkiste, Sjoerd van, Francesco Locatello, Jürgen Schmidhuber, and Olivier
Bachem. “Are Disentangled Representations Helpful for Abstract Visual Reasoning?”
In Advances in Neural Information Processing Systems, Vol. 32, 2019.
ieee: S. van Steenkiste, F. Locatello, J. Schmidhuber, and O. Bachem, “Are disentangled
representations helpful for abstract visual reasoning?,” in Advances in Neural
Information Processing Systems, Vancouver, Canada, 2019, vol. 32.
ista: 'Steenkiste S van, Locatello F, Schmidhuber J, Bachem O. 2019. Are disentangled
representations helpful for abstract visual reasoning? Advances in Neural Information
Processing Systems. NeurIPS: Neural Information Processing Systems vol. 32.'
mla: Steenkiste, Sjoerd van, et al. “Are Disentangled Representations Helpful for
Abstract Visual Reasoning?” Advances in Neural Information Processing Systems,
vol. 32, 2019.
short: S. van Steenkiste, F. Locatello, J. Schmidhuber, O. Bachem, in:, Advances
in Neural Information Processing Systems, 2019.
conference:
end_date: 2019-12-14
location: Vancouver, Canada
name: 'NeurIPS: Neural Information Processing Systems'
start_date: 2019-12-08
date_created: 2023-08-22T14:09:53Z
date_published: 2019-05-29T00:00:00Z
date_updated: 2024-10-14T12:28:15Z
day: '29'
department:
- _id: FrLo
extern: '1'
external_id:
arxiv:
- '1905.12506'
intvolume: ' 32'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.48550/arXiv.1905.12506
month: '05'
oa: 1
oa_version: Preprint
publication: Advances in Neural Information Processing Systems
publication_identifier:
isbn:
- '9781713807933'
publication_status: published
quality_controlled: '1'
status: public
title: Are disentangled representations helpful for abstract visual reasoning?
type: conference
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 32
year: '2019'
...
---
_id: '14197'
abstract:
- lang: eng
text: "Recently there has been a significant interest in learning disentangled\r\nrepresentations,
as they promise increased interpretability, generalization to\r\nunseen scenarios
and faster learning on downstream tasks. In this paper, we\r\ninvestigate the
usefulness of different notions of disentanglement for\r\nimproving the fairness
of downstream prediction tasks based on representations.\r\nWe consider the setting
where the goal is to predict a target variable based on\r\nthe learned representation
of high-dimensional observations (such as images)\r\nthat depend on both the target
variable and an \\emph{unobserved} sensitive\r\nvariable. We show that in this
setting both the optimal and empirical\r\npredictions can be unfair, even if the
target variable and the sensitive\r\nvariable are independent. Analyzing the representations
of more than\r\n\\num{12600} trained state-of-the-art disentangled models, we
observe that\r\nseveral disentanglement scores are consistently correlated with
increased\r\nfairness, suggesting that disentanglement may be a useful property
to encourage\r\nfairness when sensitive variables are not observed."
article_processing_charge: No
arxiv: 1
author:
- first_name: Francesco
full_name: Locatello, Francesco
id: 26cfd52f-2483-11ee-8040-88983bcc06d4
last_name: Locatello
orcid: 0000-0002-4850-0683
- first_name: Gabriele
full_name: Abbati, Gabriele
last_name: Abbati
- first_name: Tom
full_name: Rainforth, Tom
last_name: Rainforth
- first_name: Stefan
full_name: Bauer, Stefan
last_name: Bauer
- first_name: Bernhard
full_name: Schölkopf, Bernhard
last_name: Schölkopf
- first_name: Olivier
full_name: Bachem, Olivier
last_name: Bachem
citation:
ama: 'Locatello F, Abbati G, Rainforth T, Bauer S, Schölkopf B, Bachem O. On the
fairness of disentangled representations. In: Advances in Neural Information
Processing Systems. Vol 32. ; 2019:14611–14624.'
apa: Locatello, F., Abbati, G., Rainforth, T., Bauer, S., Schölkopf, B., & Bachem,
O. (2019). On the fairness of disentangled representations. In Advances in
Neural Information Processing Systems (Vol. 32, pp. 14611–14624). Vancouver,
Canada.
chicago: Locatello, Francesco, Gabriele Abbati, Tom Rainforth, Stefan Bauer, Bernhard
Schölkopf, and Olivier Bachem. “On the Fairness of Disentangled Representations.”
In Advances in Neural Information Processing Systems, 32:14611–14624, 2019.
ieee: F. Locatello, G. Abbati, T. Rainforth, S. Bauer, B. Schölkopf, and O. Bachem,
“On the fairness of disentangled representations,” in Advances in Neural Information
Processing Systems, Vancouver, Canada, 2019, vol. 32, pp. 14611–14624.
ista: 'Locatello F, Abbati G, Rainforth T, Bauer S, Schölkopf B, Bachem O. 2019.
On the fairness of disentangled representations. Advances in Neural Information
Processing Systems. NeurIPS: Neural Information Processing Systems vol. 32, 14611–14624.'
mla: Locatello, Francesco, et al. “On the Fairness of Disentangled Representations.”
Advances in Neural Information Processing Systems, vol. 32, 2019, pp. 14611–14624.
short: F. Locatello, G. Abbati, T. Rainforth, S. Bauer, B. Schölkopf, O. Bachem,
in:, Advances in Neural Information Processing Systems, 2019, pp. 14611–14624.
conference:
end_date: 2019-12-14
location: Vancouver, Canada
name: 'NeurIPS: Neural Information Processing Systems'
start_date: 2019-12-08
date_created: 2023-08-22T14:12:28Z
date_published: 2019-12-08T00:00:00Z
date_updated: 2024-10-14T12:29:05Z
day: '08'
department:
- _id: FrLo
extern: '1'
external_id:
arxiv:
- '1905.13662'
intvolume: ' 32'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://arxiv.org/abs/1905.13662
month: '12'
oa: 1
oa_version: Preprint
page: 14611–14624
publication: Advances in Neural Information Processing Systems
publication_identifier:
isbn:
- '9781713807933'
publication_status: published
quality_controlled: '1'
scopus_import: '1'
status: public
title: On the fairness of disentangled representations
type: conference
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 32
year: '2019'
...
---
_id: '14200'
abstract:
- lang: eng
text: "The key idea behind the unsupervised learning of disentangled representations\r\nis
that real-world data is generated by a few explanatory factors of variation\r\nwhich
can be recovered by unsupervised learning algorithms. In this paper, we\r\nprovide
a sober look at recent progress in the field and challenge some common\r\nassumptions.
We first theoretically show that the unsupervised learning of\r\ndisentangled
representations is fundamentally impossible without inductive\r\nbiases on both
the models and the data. Then, we train more than 12000 models\r\ncovering most
prominent methods and evaluation metrics in a reproducible\r\nlarge-scale experimental
study on seven different data sets. We observe that\r\nwhile the different methods
successfully enforce properties ``encouraged'' by\r\nthe corresponding losses,
well-disentangled models seemingly cannot be\r\nidentified without supervision.
Furthermore, increased disentanglement does not\r\nseem to lead to a decreased
sample complexity of learning for downstream tasks.\r\nOur results suggest that
future work on disentanglement learning should be\r\nexplicit about the role of
inductive biases and (implicit) supervision,\r\ninvestigate concrete benefits
of enforcing disentanglement of the learned\r\nrepresentations, and consider a
reproducible experimental setup covering\r\nseveral data sets."
article_processing_charge: No
arxiv: 1
author:
- first_name: Francesco
full_name: Locatello, Francesco
id: 26cfd52f-2483-11ee-8040-88983bcc06d4
last_name: Locatello
orcid: 0000-0002-4850-0683
- first_name: Stefan
full_name: Bauer, Stefan
last_name: Bauer
- first_name: Mario
full_name: Lucic, Mario
last_name: Lucic
- first_name: Gunnar
full_name: Rätsch, Gunnar
last_name: Rätsch
- first_name: Sylvain
full_name: Gelly, Sylvain
last_name: Gelly
- first_name: Bernhard
full_name: Schölkopf, Bernhard
last_name: Schölkopf
- first_name: Olivier
full_name: Bachem, Olivier
last_name: Bachem
citation:
ama: 'Locatello F, Bauer S, Lucic M, et al. Challenging common assumptions in the
unsupervised learning of disentangled representations. In: Proceedings of the
36th International Conference on Machine Learning. Vol 97. ML Research Press;
2019:4114-4124.'
apa: 'Locatello, F., Bauer, S., Lucic, M., Rätsch, G., Gelly, S., Schölkopf, B.,
& Bachem, O. (2019). Challenging common assumptions in the unsupervised learning
of disentangled representations. In Proceedings of the 36th International Conference
on Machine Learning (Vol. 97, pp. 4114–4124). Long Beach, CA, United States:
ML Research Press.'
chicago: Locatello, Francesco, Stefan Bauer, Mario Lucic, Gunnar Rätsch, Sylvain
Gelly, Bernhard Schölkopf, and Olivier Bachem. “Challenging Common Assumptions
in the Unsupervised Learning of Disentangled Representations.” In Proceedings
of the 36th International Conference on Machine Learning, 97:4114–24. ML Research
Press, 2019.
ieee: F. Locatello et al., “Challenging common assumptions in the unsupervised
learning of disentangled representations,” in Proceedings of the 36th International
Conference on Machine Learning, Long Beach, CA, United States, 2019, vol.
97, pp. 4114–4124.
ista: Locatello F, Bauer S, Lucic M, Rätsch G, Gelly S, Schölkopf B, Bachem O. 2019.
Challenging common assumptions in the unsupervised learning of disentangled representations.
Proceedings of the 36th International Conference on Machine Learning. International
Conference on Machine Learning vol. 97, 4114–4124.
mla: Locatello, Francesco, et al. “Challenging Common Assumptions in the Unsupervised
Learning of Disentangled Representations.” Proceedings of the 36th International
Conference on Machine Learning, vol. 97, ML Research Press, 2019, pp. 4114–24.
short: F. Locatello, S. Bauer, M. Lucic, G. Rätsch, S. Gelly, B. Schölkopf, O. Bachem,
in:, Proceedings of the 36th International Conference on Machine Learning, ML
Research Press, 2019, pp. 4114–4124.
conference:
end_date: 2019-06-15
location: Long Beach, CA, United States
name: International Conference on Machine Learning
start_date: 2019-06-10
date_created: 2023-08-22T14:13:08Z
date_published: 2019-06-09T00:00:00Z
date_updated: 2024-10-14T12:29:16Z
day: '09'
department:
- _id: FrLo
extern: '1'
external_id:
arxiv:
- '1811.12359'
intvolume: ' 97'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://arxiv.org/abs/1811.12359
month: '06'
oa: 1
oa_version: Preprint
page: 4114-4124
publication: Proceedings of the 36th International Conference on Machine Learning
publication_status: published
publisher: ML Research Press
quality_controlled: '1'
scopus_import: '1'
status: public
title: Challenging common assumptions in the unsupervised learning of disentangled
representations
type: conference
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 97
year: '2019'
...
---
_id: '14299'
abstract:
- lang: eng
text: DNA origami nano-objects are usually designed around generic single-stranded
“scaffolds”. Many properties of the target object are determined by details of
those generic scaffold sequences. Here, we enable designers to fully specify the
target structure not only in terms of desired 3D shape but also in terms of the
sequences used. To this end, we built design tools to construct scaffold sequences
de novo based on strand diagrams, and we developed scalable production methods
for creating design-specific scaffold strands with fully user-defined sequences.
We used 17 custom scaffolds having different lengths and sequence properties to
study the influence of sequence redundancy and sequence composition on multilayer
DNA origami assembly and to realize efficient one-pot assembly of multiscaffold
DNA origami objects. Furthermore, as examples for functionalized scaffolds, we
created a scaffold that enables direct, covalent cross-linking of DNA origami
via UV irradiation, and we built DNAzyme-containing scaffolds that allow postfolding
DNA origami domain separation.
article_processing_charge: No
article_type: original
author:
- first_name: Engelhardt
full_name: FAS, Engelhardt
last_name: FAS
- first_name: Florian M
full_name: Praetorius, Florian M
id: dfec9381-4341-11ee-8fd8-faa02bba7d62
last_name: Praetorius
- first_name: CH
full_name: Wachauf, CH
last_name: Wachauf
- first_name: G
full_name: Brüggenthies, G
last_name: Brüggenthies
- first_name: F
full_name: Kohler, F
last_name: Kohler
- first_name: B
full_name: Kick, B
last_name: Kick
- first_name: KL
full_name: Kadletz, KL
last_name: Kadletz
- first_name: PN
full_name: Pham, PN
last_name: Pham
- first_name: KL
full_name: Behler, KL
last_name: Behler
- first_name: T
full_name: Gerling, T
last_name: Gerling
- first_name: H
full_name: Dietz, H
last_name: Dietz
citation:
ama: FAS E, Praetorius FM, Wachauf C, et al. Custom-size, functional, and durable
DNA origami with design-specific scaffolds. ACS Nano. 2019;13(5):5015-5027.
doi:10.1021/acsnano.9b01025
apa: FAS, E., Praetorius, F. M., Wachauf, C., Brüggenthies, G., Kohler, F., Kick,
B., … Dietz, H. (2019). Custom-size, functional, and durable DNA origami with
design-specific scaffolds. ACS Nano. ACS Publications. https://doi.org/10.1021/acsnano.9b01025
chicago: FAS, Engelhardt, Florian M Praetorius, CH Wachauf, G Brüggenthies, F Kohler,
B Kick, KL Kadletz, et al. “Custom-Size, Functional, and Durable DNA Origami with
Design-Specific Scaffolds.” ACS Nano. ACS Publications, 2019. https://doi.org/10.1021/acsnano.9b01025.
ieee: E. FAS et al., “Custom-size, functional, and durable DNA origami with
design-specific scaffolds,” ACS Nano, vol. 13, no. 5. ACS Publications,
pp. 5015–5027, 2019.
ista: FAS E, Praetorius FM, Wachauf C, Brüggenthies G, Kohler F, Kick B, Kadletz
K, Pham P, Behler K, Gerling T, Dietz H. 2019. Custom-size, functional, and durable
DNA origami with design-specific scaffolds. ACS Nano. 13(5), 5015–5027.
mla: FAS, Engelhardt, et al. “Custom-Size, Functional, and Durable DNA Origami with
Design-Specific Scaffolds.” ACS Nano, vol. 13, no. 5, ACS Publications,
2019, pp. 5015–27, doi:10.1021/acsnano.9b01025.
short: E. FAS, F.M. Praetorius, C. Wachauf, G. Brüggenthies, F. Kohler, B. Kick,
K. Kadletz, P. Pham, K. Behler, T. Gerling, H. Dietz, ACS Nano 13 (2019) 5015–5027.
date_created: 2023-09-06T12:48:47Z
date_published: 2019-04-16T00:00:00Z
date_updated: 2023-11-07T12:17:31Z
day: '16'
doi: 10.1021/acsnano.9b01025
extern: '1'
external_id:
pmid:
- '30990672'
intvolume: ' 13'
issue: '5'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.1021/acsnano.9b01025
month: '04'
oa: 1
oa_version: Published Version
page: 5015-5027
pmid: 1
publication: ACS Nano
publication_identifier:
eissn:
- 1936-086x
issn:
- 1936-0851
publication_status: published
publisher: ACS Publications
quality_controlled: '1'
scopus_import: '1'
status: public
title: Custom-size, functional, and durable DNA origami with design-specific scaffolds
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 13
year: '2019'
...
---
OA_type: closed access
_id: '17915'
abstract:
- lang: eng
text: The construction of self-assembled iron phthalocyanine (FePc) systems on gold
electrodes modified by self-assembled monolayers (SAMs) is becoming an interesting
strategy for obtaining electrocatalytic molecular building blocks for the oxygen
reduction reaction (ORR). In this work, we have measured the conductance of pyridiniums
axial ligands at the single molecule level using the scanning tunneling microscope-based
break-junction method (STM-Break Junction) to study the role of the axial ligand
on the activity of the self-assembled FePc systems on a gold electrode surface.
The electron-pulling effect of pyridinium axial ligands is known to increase the
electrocatalytic activity of FePc for the oxygen reduction reaction (ORR). We
have used these systems as a platform for carrying out a comparative study for
understanding the real influence of the proximal axial ligands. Further, these
ligands act as molecular wires between the gold electrode surface and the FePc
molecule. The pyridinium molecules were synthesized following a series of structural
variations using a basic molecular backbone. From conductance measurements obtained
for each pyridinium molecule, it was possible to establish that electron transport
through each pyridinium does not influence the activity of FePc for ORR in alkaline
media. In addition, the DFT calculations shows that the axial ligand in FePc modifies
its catalytic activity by decreasing the binding energy of O2 to the Fe site.
article_number: '134996'
article_processing_charge: No
article_type: original
author:
- first_name: Cristian
full_name: Gutiérrez-Ceron, Cristian
last_name: Gutiérrez-Ceron
- first_name: Rubén
full_name: Oñate, Rubén
last_name: Oñate
- first_name: José H.
full_name: Zagal, José H.
last_name: Zagal
- first_name: Ana
full_name: Pizarro, Ana
last_name: Pizarro
- first_name: J. Francisco
full_name: Silva, J. Francisco
last_name: Silva
- first_name: Carmen
full_name: Castro-Castillo, Carmen
last_name: Castro-Castillo
- first_name: Marcos Caroli
full_name: Rezende, Marcos Caroli
last_name: Rezende
- first_name: Marcos
full_name: Flores, Marcos
last_name: Flores
- first_name: Diego
full_name: Cortés-Arriagada, Diego
last_name: Cortés-Arriagada
- first_name: Alejandro
full_name: Toro-Labbé, Alejandro
last_name: Toro-Labbé
- first_name: Luis M.
full_name: Campos, Luis M.
last_name: Campos
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
- first_name: Ingrid
full_name: Ponce, Ingrid
last_name: Ponce
citation:
ama: 'Gutiérrez-Ceron C, Oñate R, Zagal JH, et al. Molecular conductance versus
inductive effects of axial ligands on the electrocatalytic activity of self-assembled
iron phthalocyanines: The oxygen reduction reaction. Electrochimica Acta.
2019;327. doi:10.1016/j.electacta.2019.134996'
apa: 'Gutiérrez-Ceron, C., Oñate, R., Zagal, J. H., Pizarro, A., Silva, J. F., Castro-Castillo,
C., … Ponce, I. (2019). Molecular conductance versus inductive effects of axial
ligands on the electrocatalytic activity of self-assembled iron phthalocyanines:
The oxygen reduction reaction. Electrochimica Acta. Elsevier. https://doi.org/10.1016/j.electacta.2019.134996'
chicago: 'Gutiérrez-Ceron, Cristian, Rubén Oñate, José H. Zagal, Ana Pizarro, J.
Francisco Silva, Carmen Castro-Castillo, Marcos Caroli Rezende, et al. “Molecular
Conductance versus Inductive Effects of Axial Ligands on the Electrocatalytic
Activity of Self-Assembled Iron Phthalocyanines: The Oxygen Reduction Reaction.”
Electrochimica Acta. Elsevier, 2019. https://doi.org/10.1016/j.electacta.2019.134996.'
ieee: 'C. Gutiérrez-Ceron et al., “Molecular conductance versus inductive
effects of axial ligands on the electrocatalytic activity of self-assembled iron
phthalocyanines: The oxygen reduction reaction,” Electrochimica Acta, vol.
327. Elsevier, 2019.'
ista: 'Gutiérrez-Ceron C, Oñate R, Zagal JH, Pizarro A, Silva JF, Castro-Castillo
C, Rezende MC, Flores M, Cortés-Arriagada D, Toro-Labbé A, Campos LM, Venkataraman
L, Ponce I. 2019. Molecular conductance versus inductive effects of axial ligands
on the electrocatalytic activity of self-assembled iron phthalocyanines: The oxygen
reduction reaction. Electrochimica Acta. 327, 134996.'
mla: 'Gutiérrez-Ceron, Cristian, et al. “Molecular Conductance versus Inductive
Effects of Axial Ligands on the Electrocatalytic Activity of Self-Assembled Iron
Phthalocyanines: The Oxygen Reduction Reaction.” Electrochimica Acta, vol.
327, 134996, Elsevier, 2019, doi:10.1016/j.electacta.2019.134996.'
short: C. Gutiérrez-Ceron, R. Oñate, J.H. Zagal, A. Pizarro, J.F. Silva, C. Castro-Castillo,
M.C. Rezende, M. Flores, D. Cortés-Arriagada, A. Toro-Labbé, L.M. Campos, L. Venkataraman,
I. Ponce, Electrochimica Acta 327 (2019).
date_created: 2024-09-09T07:39:29Z
date_published: 2019-12-10T00:00:00Z
date_updated: 2024-12-10T12:30:09Z
day: '10'
doi: 10.1016/j.electacta.2019.134996
extern: '1'
intvolume: ' 327'
language:
- iso: eng
month: '12'
oa_version: None
publication: Electrochimica Acta
publication_identifier:
issn:
- 0013-4686
publication_status: published
publisher: Elsevier
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'Molecular conductance versus inductive effects of axial ligands on the electrocatalytic
activity of self-assembled iron phthalocyanines: The oxygen reduction reaction'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 327
year: '2019'
...
---
DOAJ_listed: '1'
OA_place: publisher
OA_type: gold
_id: '17916'
abstract:
- lang: eng
text: Electric fields have been proposed as having a distinct ability to catalyze
chemical reactions through the stabilization of polar or ionic intermediate transition
states. Although field-assisted catalysis is being researched, the ability to
catalyze reactions in solution using electric fields remains elusive and the understanding
of mechanisms of such catalysis is sparse. Here we show that an electric field
can catalyze the cis-to-trans isomerization of [3]cumulene derivatives in solution,
in a scanning tunneling microscope. We further show that the external electric
field can alter the thermodynamics inhibiting the trans-to-cis reverse reaction,
endowing the selectivity toward trans isomer. Using density functional theory-based
calculations, we find that the applied electric field promotes a zwitterionic
resonance form, which ensures a lower energy transition state for the isomerization
reaction. The field also stabilizes the trans form, relative to the cis, dictating
the cis/trans thermodynamics, driving the equilibrium product exclusively toward
the trans.
article_number: '4482'
article_processing_charge: Yes
article_type: original
author:
- first_name: Yaping
full_name: Zang, Yaping
last_name: Zang
- first_name: Qi
full_name: Zou, Qi
last_name: Zou
- first_name: Tianren
full_name: Fu, Tianren
last_name: Fu
- first_name: Fay
full_name: Ng, Fay
last_name: Ng
- first_name: Brandon
full_name: Fowler, Brandon
last_name: Fowler
- first_name: Jingjing
full_name: Yang, Jingjing
last_name: Yang
- first_name: Hexing
full_name: Li, Hexing
last_name: Li
- first_name: Michael L.
full_name: Steigerwald, Michael L.
last_name: Steigerwald
- first_name: Colin
full_name: Nuckolls, Colin
last_name: Nuckolls
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
citation:
ama: Zang Y, Zou Q, Fu T, et al. Directing isomerization reactions of cumulenes
with electric fields. Nature Communications. 2019;10. doi:10.1038/s41467-019-12487-w
apa: Zang, Y., Zou, Q., Fu, T., Ng, F., Fowler, B., Yang, J., … Venkataraman, L.
(2019). Directing isomerization reactions of cumulenes with electric fields. Nature
Communications. Springer Nature. https://doi.org/10.1038/s41467-019-12487-w
chicago: Zang, Yaping, Qi Zou, Tianren Fu, Fay Ng, Brandon Fowler, Jingjing Yang,
Hexing Li, Michael L. Steigerwald, Colin Nuckolls, and Latha Venkataraman. “Directing
Isomerization Reactions of Cumulenes with Electric Fields.” Nature Communications.
Springer Nature, 2019. https://doi.org/10.1038/s41467-019-12487-w.
ieee: Y. Zang et al., “Directing isomerization reactions of cumulenes with
electric fields,” Nature Communications, vol. 10. Springer Nature, 2019.
ista: Zang Y, Zou Q, Fu T, Ng F, Fowler B, Yang J, Li H, Steigerwald ML, Nuckolls
C, Venkataraman L. 2019. Directing isomerization reactions of cumulenes with electric
fields. Nature Communications. 10, 4482.
mla: Zang, Yaping, et al. “Directing Isomerization Reactions of Cumulenes with Electric
Fields.” Nature Communications, vol. 10, 4482, Springer Nature, 2019, doi:10.1038/s41467-019-12487-w.
short: Y. Zang, Q. Zou, T. Fu, F. Ng, B. Fowler, J. Yang, H. Li, M.L. Steigerwald,
C. Nuckolls, L. Venkataraman, Nature Communications 10 (2019).
date_created: 2024-09-09T07:40:44Z
date_published: 2019-10-02T00:00:00Z
date_updated: 2024-12-10T12:32:33Z
day: '02'
doi: 10.1038/s41467-019-12487-w
extern: '1'
external_id:
pmid:
- '31578333'
intvolume: ' 10'
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.1038/s41467-019-12487-w
month: '10'
oa: 1
oa_version: Published Version
pmid: 1
publication: Nature Communications
publication_identifier:
issn:
- 2041-1723
publication_status: published
publisher: Springer Nature
quality_controlled: '1'
scopus_import: '1'
status: public
title: Directing isomerization reactions of cumulenes with electric fields
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 10
year: '2019'
...
---
OA_type: closed access
_id: '17917'
abstract:
- lang: eng
text: A single-molecule method has been developed based on the scanning tunneling
microscope (STM) to selectively couple a series of aniline derivatives and create
azobenzenes. The Au-catalyzed oxidative coupling is driven by the local electrochemical
potential at the nanostructured Au STM tip. The products are detected in situ
by measuring the conductance and molecular junction elongation and compared with
analogous measurements of the expected azobenzene derivatives prepared ex situ.
This single-molecule approach is robust, and it can quickly and reproducibly create
reactions for a variety of anilines. We further demonstrate the selective synthesis
of geometric isomers and the assembly of complex molecular architectures by sequential
coupling of complementary anilines, demonstrating unprecedented control over bond
formation at the nanoscale.
article_processing_charge: No
article_type: original
author:
- first_name: Yaping
full_name: Zang, Yaping
last_name: Zang
- first_name: Ilana
full_name: Stone, Ilana
last_name: Stone
- first_name: Michael S.
full_name: Inkpen, Michael S.
last_name: Inkpen
- first_name: Fay
full_name: Ng, Fay
last_name: Ng
- first_name: Tristan H.
full_name: Lambert, Tristan H.
last_name: Lambert
- first_name: Colin
full_name: Nuckolls, Colin
last_name: Nuckolls
- first_name: Michael L.
full_name: Steigerwald, Michael L.
last_name: Steigerwald
- first_name: Xavier
full_name: Roy, Xavier
last_name: Roy
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
citation:
ama: Zang Y, Stone I, Inkpen MS, et al. In situ coupling of single molecules driven
by gold‐catalyzed electrooxidation. Angewandte Chemie International Edition.
2019;58(45):16008-16012. doi:10.1002/anie.201906215
apa: Zang, Y., Stone, I., Inkpen, M. S., Ng, F., Lambert, T. H., Nuckolls, C., …
Venkataraman, L. (2019). In situ coupling of single molecules driven by gold‐catalyzed
electrooxidation. Angewandte Chemie International Edition. Wiley. https://doi.org/10.1002/anie.201906215
chicago: Zang, Yaping, Ilana Stone, Michael S. Inkpen, Fay Ng, Tristan H. Lambert,
Colin Nuckolls, Michael L. Steigerwald, Xavier Roy, and Latha Venkataraman. “In
Situ Coupling of Single Molecules Driven by Gold‐catalyzed Electrooxidation.”
Angewandte Chemie International Edition. Wiley, 2019. https://doi.org/10.1002/anie.201906215.
ieee: Y. Zang et al., “In situ coupling of single molecules driven by gold‐catalyzed
electrooxidation,” Angewandte Chemie International Edition, vol. 58, no.
45. Wiley, pp. 16008–16012, 2019.
ista: Zang Y, Stone I, Inkpen MS, Ng F, Lambert TH, Nuckolls C, Steigerwald ML,
Roy X, Venkataraman L. 2019. In situ coupling of single molecules driven by gold‐catalyzed
electrooxidation. Angewandte Chemie International Edition. 58(45), 16008–16012.
mla: Zang, Yaping, et al. “In Situ Coupling of Single Molecules Driven by Gold‐catalyzed
Electrooxidation.” Angewandte Chemie International Edition, vol. 58, no.
45, Wiley, 2019, pp. 16008–12, doi:10.1002/anie.201906215.
short: Y. Zang, I. Stone, M.S. Inkpen, F. Ng, T.H. Lambert, C. Nuckolls, M.L. Steigerwald,
X. Roy, L. Venkataraman, Angewandte Chemie International Edition 58 (2019) 16008–16012.
date_created: 2024-09-09T07:41:47Z
date_published: 2019-11-04T00:00:00Z
date_updated: 2024-12-10T12:36:30Z
day: '04'
doi: 10.1002/anie.201906215
extern: '1'
external_id:
pmid:
- '31226235'
intvolume: ' 58'
issue: '45'
language:
- iso: eng
month: '11'
oa_version: None
page: 16008-16012
pmid: 1
publication: Angewandte Chemie International Edition
publication_identifier:
eissn:
- 1521-3773
issn:
- 1433-7851
publication_status: published
publisher: Wiley
quality_controlled: '1'
scopus_import: '1'
status: public
title: In situ coupling of single molecules driven by gold‐catalyzed electrooxidation
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 58
year: '2019'
...
---
OA_type: closed access
_id: '17918'
abstract:
- lang: eng
text: The single-molecule conductance of silanes is suppressed due to destructive
quantum interference in conformations with cisoid dihedral angles along the molecular
backbone. Yet, despite the structural similarity, σ-interference effects have
not been observed in alkanes. Here we report that the methyl substituents used
in silanes are a prerequisite for σ-interference in these systems. Through density
functional theory calculations, we find that the destructive interference is not
evident to the same extent in nonmethylated silanes. We find the same is true
in alkanes as the transmission is significantly suppressed in permethylated cyclic
and bicyclic alkanes. Using scanning tunneling microscope break-junction method
we determine the single-molecule conductance of functionalized cyclohexane and
bicyclo[2.2.2]octane that are found to be higher than that of equivalent permethylated
silanes. Rather than the difference between carbon and silicon atoms in the molecular
backbones, our calculations reveal that it is primarily the difference between
hydrogen and methyl substituents that result in the different electron transport
properties of nonmethylated alkanes and permethylated silanes. Chemical substituents
play an important role in determining the single-molecule conductance of saturated
molecules, and this must be considered when we improve and expand the chemical
design of insulating organic molecules.
article_processing_charge: No
article_type: original
author:
- first_name: Marc H.
full_name: Garner, Marc H.
last_name: Garner
- first_name: Haixing
full_name: Li, Haixing
last_name: Li
- first_name: Madhav
full_name: Neupane, Madhav
last_name: Neupane
- first_name: Qi
full_name: Zou, Qi
last_name: Zou
- first_name: Taifeng
full_name: Liu, Taifeng
last_name: Liu
- first_name: Timothy A.
full_name: Su, Timothy A.
last_name: Su
- first_name: Zhichun
full_name: Shangguan, Zhichun
last_name: Shangguan
- first_name: Daniel W.
full_name: Paley, Daniel W.
last_name: Paley
- first_name: Fay
full_name: Ng, Fay
last_name: Ng
- first_name: Shengxiong
full_name: Xiao, Shengxiong
last_name: Xiao
- first_name: Colin
full_name: Nuckolls, Colin
last_name: Nuckolls
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
- first_name: Gemma C.
full_name: Solomon, Gemma C.
last_name: Solomon
citation:
ama: Garner MH, Li H, Neupane M, et al. Permethylation introduces destructive quantum
interference in saturated silanes. Journal of the American Chemical Society.
2019;141(39):15471-15476. doi:10.1021/jacs.9b06965
apa: Garner, M. H., Li, H., Neupane, M., Zou, Q., Liu, T., Su, T. A., … Solomon,
G. C. (2019). Permethylation introduces destructive quantum interference in saturated
silanes. Journal of the American Chemical Society. American Chemical Society.
https://doi.org/10.1021/jacs.9b06965
chicago: Garner, Marc H., Haixing Li, Madhav Neupane, Qi Zou, Taifeng Liu, Timothy
A. Su, Zhichun Shangguan, et al. “Permethylation Introduces Destructive Quantum
Interference in Saturated Silanes.” Journal of the American Chemical Society.
American Chemical Society, 2019. https://doi.org/10.1021/jacs.9b06965.
ieee: M. H. Garner et al., “Permethylation introduces destructive quantum
interference in saturated silanes,” Journal of the American Chemical Society,
vol. 141, no. 39. American Chemical Society, pp. 15471–15476, 2019.
ista: Garner MH, Li H, Neupane M, Zou Q, Liu T, Su TA, Shangguan Z, Paley DW, Ng
F, Xiao S, Nuckolls C, Venkataraman L, Solomon GC. 2019. Permethylation introduces
destructive quantum interference in saturated silanes. Journal of the American
Chemical Society. 141(39), 15471–15476.
mla: Garner, Marc H., et al. “Permethylation Introduces Destructive Quantum Interference
in Saturated Silanes.” Journal of the American Chemical Society, vol. 141,
no. 39, American Chemical Society, 2019, pp. 15471–76, doi:10.1021/jacs.9b06965.
short: M.H. Garner, H. Li, M. Neupane, Q. Zou, T. Liu, T.A. Su, Z. Shangguan, D.W.
Paley, F. Ng, S. Xiao, C. Nuckolls, L. Venkataraman, G.C. Solomon, Journal of
the American Chemical Society 141 (2019) 15471–15476.
date_created: 2024-09-09T07:42:26Z
date_published: 2019-09-10T00:00:00Z
date_updated: 2024-12-10T12:39:27Z
day: '10'
doi: 10.1021/jacs.9b06965
extern: '1'
external_id:
pmid:
- '31500410'
intvolume: ' 141'
issue: '39'
language:
- iso: eng
month: '09'
oa_version: None
page: 15471-15476
pmid: 1
publication: Journal of the American Chemical Society
publication_identifier:
eissn:
- 1520-5126
issn:
- 0002-7863
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Permethylation introduces destructive quantum interference in saturated silanes
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 141
year: '2019'
...
---
OA_type: closed access
_id: '17919'
abstract:
- lang: eng
text: The adsorption geometry and the electronic structure of a Blatter radical
derivative on a gold surface were investigated by a combination of high‐resolution
noncontact atomic force microscopy and scanning tunneling microscopy. While the
hybridization with the substrate hinders direct access to the molecular states,
we show that the unpaired‐electron orbital can be probed with Ångström resolution
by mapping the spatial distribution of the Kondo resonance. The Blatter derivative
features a peculiar delocalization of the unpaired‐electron orbital over some
but not all moieties of the molecule, such that the Kondo signature can be related
to the spatial fingerprint of the orbital. We observe a direct correspondence
between these two quantities, including a pronounced nodal plane structure. Finally,
we demonstrate that the spatial signature of the Kondo resonance also persists
upon noncovalent dimerization of molecules.
article_processing_charge: No
article_type: original
author:
- first_name: Laerte L.
full_name: Patera, Laerte L.
last_name: Patera
- first_name: Sophia
full_name: Sokolov, Sophia
last_name: Sokolov
- first_name: Jonathan Z.
full_name: Low, Jonathan Z.
last_name: Low
- first_name: Luis M.
full_name: Campos, Luis M.
last_name: Campos
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
- first_name: Jascha
full_name: Repp, Jascha
last_name: Repp
citation:
ama: Patera LL, Sokolov S, Low JZ, Campos LM, Venkataraman L, Repp J. Resolving
the unpaired‐electron orbital distribution in a stable organic radical by Kondo
resonance mapping. Angewandte Chemie International Edition. 2019;58(32):11063-11067.
doi:10.1002/anie.201904851
apa: Patera, L. L., Sokolov, S., Low, J. Z., Campos, L. M., Venkataraman, L., &
Repp, J. (2019). Resolving the unpaired‐electron orbital distribution in a stable
organic radical by Kondo resonance mapping. Angewandte Chemie International
Edition. Wiley. https://doi.org/10.1002/anie.201904851
chicago: Patera, Laerte L., Sophia Sokolov, Jonathan Z. Low, Luis M. Campos, Latha
Venkataraman, and Jascha Repp. “Resolving the Unpaired‐electron Orbital Distribution
in a Stable Organic Radical by Kondo Resonance Mapping.” Angewandte Chemie
International Edition. Wiley, 2019. https://doi.org/10.1002/anie.201904851.
ieee: L. L. Patera, S. Sokolov, J. Z. Low, L. M. Campos, L. Venkataraman, and J.
Repp, “Resolving the unpaired‐electron orbital distribution in a stable organic
radical by Kondo resonance mapping,” Angewandte Chemie International Edition,
vol. 58, no. 32. Wiley, pp. 11063–11067, 2019.
ista: Patera LL, Sokolov S, Low JZ, Campos LM, Venkataraman L, Repp J. 2019. Resolving
the unpaired‐electron orbital distribution in a stable organic radical by Kondo
resonance mapping. Angewandte Chemie International Edition. 58(32), 11063–11067.
mla: Patera, Laerte L., et al. “Resolving the Unpaired‐electron Orbital Distribution
in a Stable Organic Radical by Kondo Resonance Mapping.” Angewandte Chemie
International Edition, vol. 58, no. 32, Wiley, 2019, pp. 11063–67, doi:10.1002/anie.201904851.
short: L.L. Patera, S. Sokolov, J.Z. Low, L.M. Campos, L. Venkataraman, J. Repp,
Angewandte Chemie International Edition 58 (2019) 11063–11067.
date_created: 2024-09-09T07:43:21Z
date_published: 2019-08-05T00:00:00Z
date_updated: 2024-12-10T12:41:49Z
day: '05'
doi: 10.1002/anie.201904851
extern: '1'
external_id:
pmid:
- '31115954'
intvolume: ' 58'
issue: '32'
language:
- iso: eng
month: '08'
oa_version: None
page: 11063-11067
pmid: 1
publication: Angewandte Chemie International Edition
publication_identifier:
eissn:
- 1521-3773
issn:
- 1433-7851
publication_status: published
publisher: Wiley
quality_controlled: '1'
scopus_import: '1'
status: public
title: Resolving the unpaired‐electron orbital distribution in a stable organic radical
by Kondo resonance mapping
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 58
year: '2019'
...
---
OA_type: closed access
_id: '17920'
abstract:
- lang: eng
text: Stable organic radicals have potential applications for building organic spintronic
devices. To fulfill this potential, the interface between organic radicals and
metal electrodes must be well characterized. Here, through a combined effort that
includes synthesis, scanning tunneling microscopy, X-ray spectroscopy, and single-molecule
conductance measurements, we comprehensively probe the electronic interaction
between gold metal electrodes and a benchtop stable radical—the Blatter radical.
We find that despite its open-shell character and having a half-filled orbital
close to the Fermi level, the radical is stable on a gold substrate under ultrahigh
vacuum. We observe a Kondo resonance arising from the radical and spectroscopic
signatures of its half-filled orbitals. By contrast, in solution-based single-molecule
conductance measurements, the radical character is lost through oxidation with
charge transfer occurring from the molecule to metal. Our experiments show that
the stability of radical states can be very sensitive to the environment around
the molecule.
article_processing_charge: No
article_type: original
author:
- first_name: Jonathan Z.
full_name: Low, Jonathan Z.
last_name: Low
- first_name: Gregor
full_name: Kladnik, Gregor
last_name: Kladnik
- first_name: Laerte L.
full_name: Patera, Laerte L.
last_name: Patera
- first_name: Sophia
full_name: Sokolov, Sophia
last_name: Sokolov
- first_name: Giacomo
full_name: Lovat, Giacomo
last_name: Lovat
- first_name: Elango
full_name: Kumarasamy, Elango
last_name: Kumarasamy
- first_name: Jascha
full_name: Repp, Jascha
last_name: Repp
- first_name: Luis M.
full_name: Campos, Luis M.
last_name: Campos
- first_name: Dean
full_name: Cvetko, Dean
last_name: Cvetko
- first_name: Alberto
full_name: Morgante, Alberto
last_name: Morgante
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
citation:
ama: Low JZ, Kladnik G, Patera LL, et al. The environment-dependent behavior of
the Blatter radical at the metal–molecule interface. Nano Letters. 2019;19(4):2543-2548.
doi:10.1021/acs.nanolett.9b00275
apa: Low, J. Z., Kladnik, G., Patera, L. L., Sokolov, S., Lovat, G., Kumarasamy,
E., … Venkataraman, L. (2019). The environment-dependent behavior of the Blatter
radical at the metal–molecule interface. Nano Letters. American Chemical
Society. https://doi.org/10.1021/acs.nanolett.9b00275
chicago: Low, Jonathan Z., Gregor Kladnik, Laerte L. Patera, Sophia Sokolov, Giacomo
Lovat, Elango Kumarasamy, Jascha Repp, et al. “The Environment-Dependent Behavior
of the Blatter Radical at the Metal–Molecule Interface.” Nano Letters.
American Chemical Society, 2019. https://doi.org/10.1021/acs.nanolett.9b00275.
ieee: J. Z. Low et al., “The environment-dependent behavior of the Blatter
radical at the metal–molecule interface,” Nano Letters, vol. 19, no. 4.
American Chemical Society, pp. 2543–2548, 2019.
ista: Low JZ, Kladnik G, Patera LL, Sokolov S, Lovat G, Kumarasamy E, Repp J, Campos
LM, Cvetko D, Morgante A, Venkataraman L. 2019. The environment-dependent behavior
of the Blatter radical at the metal–molecule interface. Nano Letters. 19(4), 2543–2548.
mla: Low, Jonathan Z., et al. “The Environment-Dependent Behavior of the Blatter
Radical at the Metal–Molecule Interface.” Nano Letters, vol. 19, no. 4,
American Chemical Society, 2019, pp. 2543–48, doi:10.1021/acs.nanolett.9b00275.
short: J.Z. Low, G. Kladnik, L.L. Patera, S. Sokolov, G. Lovat, E. Kumarasamy, J.
Repp, L.M. Campos, D. Cvetko, A. Morgante, L. Venkataraman, Nano Letters 19 (2019)
2543–2548.
date_created: 2024-09-09T07:44:44Z
date_published: 2019-03-18T00:00:00Z
date_updated: 2024-12-11T07:41:32Z
day: '18'
doi: 10.1021/acs.nanolett.9b00275
extern: '1'
external_id:
pmid:
- '30884240'
intvolume: ' 19'
issue: '4'
language:
- iso: eng
month: '03'
oa_version: None
page: 2543-2548
pmid: 1
publication: Nano Letters
publication_identifier:
eissn:
- 1530-6992
issn:
- 1530-6984
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: The environment-dependent behavior of the Blatter radical at the metal–molecule
interface
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 19
year: '2019'
...
---
OA_type: closed access
_id: '17921'
abstract:
- lang: eng
text: The promise of the field of single-molecule electronics is to reveal a new
class of quantum devices that leverages the strong electronic interactions inherent
to subnanometer scale systems. Here, we form Au–molecule–Au junctions using a
custom scanning tunneling microscope and explore charge transport through current–voltage
measurements. We focus on the resonant tunneling regime of two molecules, one
that is primarily an electron conductor and one that conducts primarily holes.
We find that in the high bias regime, junctions that do not rupture demonstrate
reproducible and pronounced negative differential resistance (NDR)-like features
followed by hysteresis with peak-to-valley ratios exceeding 100 in some cases.
Furthermore, we show that both junction rupture and NDR are induced by charging
of the molecular orbital dominating transport and find that the charging is reversible
at lower bias and with time with kinetic time scales on the order of hundreds
of milliseconds. We argue that these results cannot be explained by existing models
of charge transport and likely require theoretical advances describing the transition
from coherent to sequential tunneling. Our work also suggests new rules for operating
single-molecule devices at high bias to obtain highly nonlinear behavior.
article_processing_charge: No
article_type: original
author:
- first_name: E-Dean
full_name: Fung, E-Dean
last_name: Fung
- first_name: David
full_name: Gelbwaser, David
last_name: Gelbwaser
- first_name: Jeffrey
full_name: Taylor, Jeffrey
last_name: Taylor
- first_name: Jonathan
full_name: Low, Jonathan
last_name: Low
- first_name: Jianlong
full_name: Xia, Jianlong
last_name: Xia
- first_name: Iryna
full_name: Davydenko, Iryna
last_name: Davydenko
- first_name: Luis M.
full_name: Campos, Luis M.
last_name: Campos
- first_name: Seth
full_name: Marder, Seth
last_name: Marder
- first_name: Uri
full_name: Peskin, Uri
last_name: Peskin
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
citation:
ama: 'Fung E-D, Gelbwaser D, Taylor J, et al. Breaking down resonance: Nonlinear
transport and the breakdown of coherent tunneling models in single molecule junctions.
Nano Letters. 2019;19(4):2555-2561. doi:10.1021/acs.nanolett.9b00316'
apa: 'Fung, E.-D., Gelbwaser, D., Taylor, J., Low, J., Xia, J., Davydenko, I., …
Venkataraman, L. (2019). Breaking down resonance: Nonlinear transport and the
breakdown of coherent tunneling models in single molecule junctions. Nano Letters.
American Chemical Society. https://doi.org/10.1021/acs.nanolett.9b00316'
chicago: 'Fung, E-Dean, David Gelbwaser, Jeffrey Taylor, Jonathan Low, Jianlong
Xia, Iryna Davydenko, Luis M. Campos, Seth Marder, Uri Peskin, and Latha Venkataraman.
“Breaking down Resonance: Nonlinear Transport and the Breakdown of Coherent Tunneling
Models in Single Molecule Junctions.” Nano Letters. American Chemical Society,
2019. https://doi.org/10.1021/acs.nanolett.9b00316.'
ieee: 'E.-D. Fung et al., “Breaking down resonance: Nonlinear transport and
the breakdown of coherent tunneling models in single molecule junctions,” Nano
Letters, vol. 19, no. 4. American Chemical Society, pp. 2555–2561, 2019.'
ista: 'Fung E-D, Gelbwaser D, Taylor J, Low J, Xia J, Davydenko I, Campos LM, Marder
S, Peskin U, Venkataraman L. 2019. Breaking down resonance: Nonlinear transport
and the breakdown of coherent tunneling models in single molecule junctions. Nano
Letters. 19(4), 2555–2561.'
mla: 'Fung, E. Dean, et al. “Breaking down Resonance: Nonlinear Transport and the
Breakdown of Coherent Tunneling Models in Single Molecule Junctions.” Nano
Letters, vol. 19, no. 4, American Chemical Society, 2019, pp. 2555–61, doi:10.1021/acs.nanolett.9b00316.'
short: E.-D. Fung, D. Gelbwaser, J. Taylor, J. Low, J. Xia, I. Davydenko, L.M. Campos,
S. Marder, U. Peskin, L. Venkataraman, Nano Letters 19 (2019) 2555–2561.
date_created: 2024-09-09T07:46:01Z
date_published: 2019-03-01T00:00:00Z
date_updated: 2024-12-11T07:48:13Z
day: '01'
doi: 10.1021/acs.nanolett.9b00316
extern: '1'
external_id:
pmid:
- '30821465'
intvolume: ' 19'
issue: '4'
language:
- iso: eng
month: '03'
oa_version: None
page: 2555-2561
pmid: 1
publication: Nano Letters
publication_identifier:
eissn:
- 1530-6992
issn:
- 1530-6984
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'Breaking down resonance: Nonlinear transport and the breakdown of coherent
tunneling models in single molecule junctions'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 19
year: '2019'
...
---
OA_type: closed access
_id: '17922'
abstract:
- lang: eng
text: Gold–thiol contacts are ubiquitous across the physical and biological sciences
in connecting organic molecules to surfaces. When thiols bind to gold in self-assembled
monolayers (SAMs) the fate of the hydrogen remains a subject of profound debate—with
implications for our understanding of their physical properties, spectroscopic
features and formation mechanism(s). Exploiting measurements of the transmission
through a molecular junction, which is highly sensitive to the nature of the molecule–electrode
contact, we demonstrate here that the nature of the gold–sulfur bond in SAMs can
be probed via single-molecule conductance measurements. Critically, we find that
SAM measurements of dithiol-terminated molecular junctions yield a significantly
lower conductance than solution measurements of the same molecule. Through numerous
control experiments, conductance noise analysis and transport calculations based
on density functional theory, we show that the gold–sulfur bond in SAMs prepared
from the solution deposition of dithiols does not have chemisorbed character,
which strongly suggests that under these widely used preparation conditions the
hydrogen is retained.
article_processing_charge: No
article_type: original
author:
- first_name: Michael S.
full_name: Inkpen, Michael S.
last_name: Inkpen
- first_name: Zhen–Fei
full_name: Liu, Zhen–Fei
last_name: Liu
- first_name: Haixing
full_name: Li, Haixing
last_name: Li
- first_name: Luis M.
full_name: Campos, Luis M.
last_name: Campos
- first_name: Jeffrey B.
full_name: Neaton, Jeffrey B.
last_name: Neaton
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
citation:
ama: Inkpen MS, Liu Z, Li H, Campos LM, Neaton JB, Venkataraman L. Non-chemisorbed
gold–sulfur binding prevails in self-assembled monolayers. Nature Chemistry.
2019;11(4):351-358. doi:10.1038/s41557-019-0216-y
apa: Inkpen, M. S., Liu, Z., Li, H., Campos, L. M., Neaton, J. B., & Venkataraman,
L. (2019). Non-chemisorbed gold–sulfur binding prevails in self-assembled monolayers.
Nature Chemistry. Springer Nature. https://doi.org/10.1038/s41557-019-0216-y
chicago: Inkpen, Michael S., Zhen–Fei Liu, Haixing Li, Luis M. Campos, Jeffrey B.
Neaton, and Latha Venkataraman. “Non-Chemisorbed Gold–Sulfur Binding Prevails
in Self-Assembled Monolayers.” Nature Chemistry. Springer Nature, 2019.
https://doi.org/10.1038/s41557-019-0216-y.
ieee: M. S. Inkpen, Z. Liu, H. Li, L. M. Campos, J. B. Neaton, and L. Venkataraman,
“Non-chemisorbed gold–sulfur binding prevails in self-assembled monolayers,” Nature
Chemistry, vol. 11, no. 4. Springer Nature, pp. 351–358, 2019.
ista: Inkpen MS, Liu Z, Li H, Campos LM, Neaton JB, Venkataraman L. 2019. Non-chemisorbed
gold–sulfur binding prevails in self-assembled monolayers. Nature Chemistry. 11(4),
351–358.
mla: Inkpen, Michael S., et al. “Non-Chemisorbed Gold–Sulfur Binding Prevails in
Self-Assembled Monolayers.” Nature Chemistry, vol. 11, no. 4, Springer
Nature, 2019, pp. 351–58, doi:10.1038/s41557-019-0216-y.
short: M.S. Inkpen, Z. Liu, H. Li, L.M. Campos, J.B. Neaton, L. Venkataraman, Nature
Chemistry 11 (2019) 351–358.
date_created: 2024-09-09T07:48:03Z
date_published: 2019-04-01T00:00:00Z
date_updated: 2024-12-11T08:00:35Z
day: '01'
doi: 10.1038/s41557-019-0216-y
extern: '1'
external_id:
pmid:
- '30833721'
intvolume: ' 11'
issue: '4'
language:
- iso: eng
month: '04'
oa_version: None
page: 351-358
pmid: 1
publication: Nature Chemistry
publication_identifier:
eissn:
- 1755-4349
issn:
- 1755-4330
publication_status: published
publisher: Springer Nature
quality_controlled: '1'
scopus_import: '1'
status: public
title: Non-chemisorbed gold–sulfur binding prevails in self-assembled monolayers
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 11
year: '2019'
...
---
DOAJ_listed: '1'
OA_place: publisher
OA_type: gold
_id: '17924'
abstract:
- lang: eng
text: We demonstrate that imidazole based π–π stacked dimers form strong and efficient
conductance pathways in single-molecule junctions using the scanning-tunneling
microscope-break junction (STM-BJ) technique and density functional theory-based
calculations. We first characterize an imidazole-gold contact by measuring the
conductance of imidazolyl-terminated alkanes (im-N-im, N = 3–6). We show that
the conductance of these alkanes decays exponentially with increasing length,
indicating that the mechanism for electron transport is through tunneling or super-exchange.
We also reveal that π–π stacked dimers can be formed between imidazoles and have
better coupling than through-bond tunneling. These experimental results are rationalized
by calculations of molecular junction transmission using non-equilibrium Green's
function formalism. This study verifies the capability of imidazole as a Au-binding
ligand to form stable single- and π-stacked molecule junctions at room temperature.
article_processing_charge: Yes
article_type: original
author:
- first_name: Tianren
full_name: Fu, Tianren
last_name: Fu
- first_name: Shanelle
full_name: Smith, Shanelle
last_name: Smith
- first_name: María
full_name: Camarasa-Gómez, María
last_name: Camarasa-Gómez
- first_name: Xiaofang
full_name: Yu, Xiaofang
last_name: Yu
- first_name: Jiayi
full_name: Xue, Jiayi
last_name: Xue
- first_name: Colin
full_name: Nuckolls, Colin
last_name: Nuckolls
- first_name: Ferdinand
full_name: Evers, Ferdinand
last_name: Evers
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
- first_name: Sujun
full_name: Wei, Sujun
last_name: Wei
citation:
ama: Fu T, Smith S, Camarasa-Gómez M, et al. Enhanced coupling through π-stacking
in imidazole-based molecular junctions. Chemical Science. 2019;10(43):9998-10002.
doi:10.1039/c9sc03760h
apa: Fu, T., Smith, S., Camarasa-Gómez, M., Yu, X., Xue, J., Nuckolls, C., … Wei,
S. (2019). Enhanced coupling through π-stacking in imidazole-based molecular junctions.
Chemical Science. Royal Society of Chemistry. https://doi.org/10.1039/c9sc03760h
chicago: Fu, Tianren, Shanelle Smith, María Camarasa-Gómez, Xiaofang Yu, Jiayi Xue,
Colin Nuckolls, Ferdinand Evers, Latha Venkataraman, and Sujun Wei. “Enhanced
Coupling through π-Stacking in Imidazole-Based Molecular Junctions.” Chemical
Science. Royal Society of Chemistry, 2019. https://doi.org/10.1039/c9sc03760h.
ieee: T. Fu et al., “Enhanced coupling through π-stacking in imidazole-based
molecular junctions,” Chemical Science, vol. 10, no. 43. Royal Society
of Chemistry, pp. 9998–10002, 2019.
ista: Fu T, Smith S, Camarasa-Gómez M, Yu X, Xue J, Nuckolls C, Evers F, Venkataraman
L, Wei S. 2019. Enhanced coupling through π-stacking in imidazole-based molecular
junctions. Chemical Science. 10(43), 9998–10002.
mla: Fu, Tianren, et al. “Enhanced Coupling through π-Stacking in Imidazole-Based
Molecular Junctions.” Chemical Science, vol. 10, no. 43, Royal Society
of Chemistry, 2019, pp. 9998–10002, doi:10.1039/c9sc03760h.
short: T. Fu, S. Smith, M. Camarasa-Gómez, X. Yu, J. Xue, C. Nuckolls, F. Evers,
L. Venkataraman, S. Wei, Chemical Science 10 (2019) 9998–10002.
date_created: 2024-09-09T07:49:24Z
date_published: 2019-09-16T00:00:00Z
date_updated: 2024-12-11T08:08:34Z
day: '16'
doi: 10.1039/c9sc03760h
extern: '1'
external_id:
pmid:
- '32055356'
intvolume: ' 10'
issue: '43'
language:
- iso: eng
license: https://creativecommons.org/licenses/by-nc/3.0/
main_file_link:
- open_access: '1'
url: https://doi.org/10.1039/C9SC03760H
month: '09'
oa: 1
oa_version: Published Version
page: 9998-10002
pmid: 1
publication: Chemical Science
publication_identifier:
eissn:
- 2041-6539
issn:
- 2041-6520
publication_status: published
publisher: Royal Society of Chemistry
quality_controlled: '1'
scopus_import: '1'
status: public
title: Enhanced coupling through π-stacking in imidazole-based molecular junctions
tmp:
image: /images/cc_by_nc.png
legal_code_url: https://creativecommons.org/licenses/by-nc/3.0/legalcode
name: Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)
short: CC BY-NC (3.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 10
year: '2019'
...
---
DOAJ_listed: '1'
OA_place: publisher
OA_type: gold
_id: '17925'
abstract:
- lang: eng
text: Recent years have seen tremendous progress towards understanding the relation
between the molecular structure and function of organic field effect transistors.
The metrics for organic field effect transistors, which are characterized by mobility
and the on/off ratio, are known to be enhanced when the intermolecular interaction
is strong and the intramolecular reorganization energy is low. While these requirements
are adequate when describing organic field effect transistors with simple and
planar aromatic molecular components, they are insufficient for complex building
blocks, which have the potential to localize a carrier on the molecule. Here,
we show that intramolecular conductivity can play a role in controlling device
characteristics of organic field effect transistors made with macrocycle building
blocks. We use two isomeric macrocyclic semiconductors that consist of perylene
diimides linked with bithiophenes and find that the trans-linked macrocycle has
a higher mobility than the cis-based device. Through a combination of single molecule
junction conductance measurements of the components of the macrocycles, control
experiments with acyclic counterparts to the macrocycles, and analyses of each
of the materials using spectroscopy, electrochemistry, and density functional
theory, we attribute the difference in electron mobility of the OFETs created
with the two isomers to the difference in intramolecular conductivity of the two
macrocycles.
article_processing_charge: Yes
article_type: original
author:
- first_name: Melissa L.
full_name: Ball, Melissa L.
last_name: Ball
- first_name: Boyuan
full_name: Zhang, Boyuan
last_name: Zhang
- first_name: Tianren
full_name: Fu, Tianren
last_name: Fu
- first_name: Ayden M.
full_name: Schattman, Ayden M.
last_name: Schattman
- first_name: Daniel W.
full_name: Paley, Daniel W.
last_name: Paley
- first_name: Fay
full_name: Ng, Fay
last_name: Ng
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
- first_name: Colin
full_name: Nuckolls, Colin
last_name: Nuckolls
- first_name: Michael L.
full_name: Steigerwald, Michael L.
last_name: Steigerwald
citation:
ama: Ball ML, Zhang B, Fu T, et al. The importance of intramolecular conductivity
in three dimensional molecular solids. Chemical Science. 2019;10(40):9339-9344.
doi:10.1039/c9sc03144h
apa: Ball, M. L., Zhang, B., Fu, T., Schattman, A. M., Paley, D. W., Ng, F., … Steigerwald,
M. L. (2019). The importance of intramolecular conductivity in three dimensional
molecular solids. Chemical Science. Royal Society of Chemistry. https://doi.org/10.1039/c9sc03144h
chicago: Ball, Melissa L., Boyuan Zhang, Tianren Fu, Ayden M. Schattman, Daniel
W. Paley, Fay Ng, Latha Venkataraman, Colin Nuckolls, and Michael L. Steigerwald.
“The Importance of Intramolecular Conductivity in Three Dimensional Molecular
Solids.” Chemical Science. Royal Society of Chemistry, 2019. https://doi.org/10.1039/c9sc03144h.
ieee: M. L. Ball et al., “The importance of intramolecular conductivity in
three dimensional molecular solids,” Chemical Science, vol. 10, no. 40.
Royal Society of Chemistry, pp. 9339–9344, 2019.
ista: Ball ML, Zhang B, Fu T, Schattman AM, Paley DW, Ng F, Venkataraman L, Nuckolls
C, Steigerwald ML. 2019. The importance of intramolecular conductivity in three
dimensional molecular solids. Chemical Science. 10(40), 9339–9344.
mla: Ball, Melissa L., et al. “The Importance of Intramolecular Conductivity in
Three Dimensional Molecular Solids.” Chemical Science, vol. 10, no. 40,
Royal Society of Chemistry, 2019, pp. 9339–44, doi:10.1039/c9sc03144h.
short: M.L. Ball, B. Zhang, T. Fu, A.M. Schattman, D.W. Paley, F. Ng, L. Venkataraman,
C. Nuckolls, M.L. Steigerwald, Chemical Science 10 (2019) 9339–9344.
date_created: 2024-09-09T07:51:38Z
date_published: 2019-08-28T00:00:00Z
date_updated: 2024-12-11T08:12:09Z
day: '28'
doi: 10.1039/c9sc03144h
extern: '1'
external_id:
pmid:
- '32110297'
intvolume: ' 10'
issue: '40'
language:
- iso: eng
month: '08'
oa_version: Published Version
page: 9339-9344
pmid: 1
publication: Chemical Science
publication_identifier:
eissn:
- 2041-6539
issn:
- 2041-6520
publication_status: published
publisher: Royal Society of Chemistry
quality_controlled: '1'
scopus_import: '1'
status: public
title: The importance of intramolecular conductivity in three dimensional molecular
solids
tmp:
image: /images/cc_by_nc.png
legal_code_url: https://creativecommons.org/licenses/by-nc/3.0/legalcode
name: Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)
short: CC BY-NC (3.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 10
year: '2019'
...