---
_id: '7968'
abstract:
- lang: eng
text: Organic materials are known to feature long spin-diffusion times, originating
in a generally small spin–orbit coupling observed in these systems. From that
perspective, chiral molecules acting as efficient spin selectors pose a puzzle
that attracted a lot of attention in recent years. Here, we revisit the physical
origins of chiral-induced spin selectivity (CISS) and propose a simple analytic
minimal model to describe it. The model treats a chiral molecule as an anisotropic
wire with molecular dipole moments aligned arbitrarily with respect to the wire’s
axes and is therefore quite general. Importantly, it shows that the helical structure
of the molecule is not necessary to observe CISS and other chiral nonhelical molecules
can also be considered as potential candidates for the CISS effect. We also show
that the suggested simple model captures the main characteristics of CISS observed
in the experiment, without the need for additional constraints employed in the
previous studies. The results pave the way for understanding other related physical
phenomena where the CISS effect plays an essential role.
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Areg
full_name: Ghazaryan, Areg
id: 4AF46FD6-F248-11E8-B48F-1D18A9856A87
last_name: Ghazaryan
orcid: 0000-0001-9666-3543
- first_name: Yossi
full_name: Paltiel, Yossi
last_name: Paltiel
- first_name: Mikhail
full_name: Lemeshko, Mikhail
id: 37CB05FA-F248-11E8-B48F-1D18A9856A87
last_name: Lemeshko
orcid: 0000-0002-6990-7802
citation:
ama: Ghazaryan A, Paltiel Y, Lemeshko M. Analytic model of chiral-induced spin selectivity.
The Journal of Physical Chemistry C. 2020;124(21):11716-11721. doi:10.1021/acs.jpcc.0c02584
apa: Ghazaryan, A., Paltiel, Y., & Lemeshko, M. (2020). Analytic model of chiral-induced
spin selectivity. The Journal of Physical Chemistry C. American Chemical
Society. https://doi.org/10.1021/acs.jpcc.0c02584
chicago: Ghazaryan, Areg, Yossi Paltiel, and Mikhail Lemeshko. “Analytic Model of
Chiral-Induced Spin Selectivity.” The Journal of Physical Chemistry C.
American Chemical Society, 2020. https://doi.org/10.1021/acs.jpcc.0c02584.
ieee: A. Ghazaryan, Y. Paltiel, and M. Lemeshko, “Analytic model of chiral-induced
spin selectivity,” The Journal of Physical Chemistry C, vol. 124, no. 21.
American Chemical Society, pp. 11716–11721, 2020.
ista: Ghazaryan A, Paltiel Y, Lemeshko M. 2020. Analytic model of chiral-induced
spin selectivity. The Journal of Physical Chemistry C. 124(21), 11716–11721.
mla: Ghazaryan, Areg, et al. “Analytic Model of Chiral-Induced Spin Selectivity.”
The Journal of Physical Chemistry C, vol. 124, no. 21, American Chemical
Society, 2020, pp. 11716–21, doi:10.1021/acs.jpcc.0c02584.
short: A. Ghazaryan, Y. Paltiel, M. Lemeshko, The Journal of Physical Chemistry
C 124 (2020) 11716–11721.
corr_author: '1'
date_created: 2020-06-16T14:29:59Z
date_published: 2020-05-04T00:00:00Z
date_updated: 2025-06-12T07:19:01Z
day: '04'
ddc:
- '530'
department:
- _id: MiLe
doi: 10.1021/acs.jpcc.0c02584
ec_funded: 1
external_id:
isi:
- '000614616200006'
pmid:
- '32499842'
file:
- access_level: open_access
checksum: 25932bb1d0b0a955be0bea4d17facd49
content_type: application/pdf
creator: kschuh
date_created: 2020-10-20T14:39:47Z
date_updated: 2020-10-20T14:39:47Z
file_id: '8683'
file_name: 2020_PhysChemC_Ghazaryan.pdf
file_size: 1543429
relation: main_file
success: 1
file_date_updated: 2020-10-20T14:39:47Z
has_accepted_license: '1'
intvolume: ' 124'
isi: 1
issue: '21'
language:
- iso: eng
license: https://creativecommons.org/licenses/by/4.0/
month: '05'
oa: 1
oa_version: Published Version
page: 11716-11721
pmid: 1
project:
- _id: 260C2330-B435-11E9-9278-68D0E5697425
call_identifier: H2020
grant_number: '754411'
name: ISTplus - Postdoctoral Fellowships
- _id: 26031614-B435-11E9-9278-68D0E5697425
call_identifier: FWF
grant_number: P29902
name: Quantum rotations in the presence of a many-body environment
- _id: 2688CF98-B435-11E9-9278-68D0E5697425
call_identifier: H2020
grant_number: '801770'
name: 'Angulon: physics and applications of a new quasiparticle'
publication: The Journal of Physical Chemistry C
publication_identifier:
eissn:
- 1932-7455
issn:
- 1932-7447
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Analytic model of chiral-induced spin selectivity
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 124
year: '2020'
...
---
OA_type: closed access
_id: '17941'
abstract:
- lang: eng
text: How heteroatomic substitutions affect electron transport through π-conjugated
hydrocarbons has been the subject of some debate. In this paper we investigate
the effect of heteroatomic linkers in a molecular junction on the electron-transmission
spectrum, focusing on the occurrence of quantum interference (QI) close to the
Fermi level, where conductivity can be significantly suppressed. We find that
the substitution or addition of heteroatoms to a carbon skeleton at the contact
positions does not change the main feature of QI due to the underlying carbon
skeleton. QI in the overall system thus remains a robust feature. This empirical
observation leads us to derive, in two mathematical ways, that these findings
can be generalized. We note that addition or substitution of a carbon atom by
a heteroatom at the contact positions will increase or decrease the number of
electrons in the π-system, which will lead to a change in the alignment of the
molecular orbitals of the isolated system relative to the electrode Fermi level.
Both Hückel and density functional theory calculations on model systems probe
the effect of this Fermi level change and confirm qualitatively the implications
of the underlying mathematical proofs.
article_processing_charge: No
article_type: original
author:
- first_name: Yuta
full_name: Tsuji, Yuta
last_name: Tsuji
- first_name: Thijs
full_name: Stuyver, Thijs
last_name: Stuyver
- first_name: Suman
full_name: Gunasekaran, Suman
last_name: Gunasekaran
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
citation:
ama: 'Tsuji Y, Stuyver T, Gunasekaran S, Venkataraman L. The influence of linkers
on quantum interference: A linker theorem. The Journal of Physical Chemistry
C. 2017;121(27):14451-14462. doi:10.1021/acs.jpcc.7b03493'
apa: 'Tsuji, Y., Stuyver, T., Gunasekaran, S., & Venkataraman, L. (2017). The
influence of linkers on quantum interference: A linker theorem. The Journal
of Physical Chemistry C. American Chemical Society. https://doi.org/10.1021/acs.jpcc.7b03493'
chicago: 'Tsuji, Yuta, Thijs Stuyver, Suman Gunasekaran, and Latha Venkataraman.
“The Influence of Linkers on Quantum Interference: A Linker Theorem.” The Journal
of Physical Chemistry C. American Chemical Society, 2017. https://doi.org/10.1021/acs.jpcc.7b03493.'
ieee: 'Y. Tsuji, T. Stuyver, S. Gunasekaran, and L. Venkataraman, “The influence
of linkers on quantum interference: A linker theorem,” The Journal of Physical
Chemistry C, vol. 121, no. 27. American Chemical Society, pp. 14451–14462,
2017.'
ista: 'Tsuji Y, Stuyver T, Gunasekaran S, Venkataraman L. 2017. The influence of
linkers on quantum interference: A linker theorem. The Journal of Physical Chemistry
C. 121(27), 14451–14462.'
mla: 'Tsuji, Yuta, et al. “The Influence of Linkers on Quantum Interference: A Linker
Theorem.” The Journal of Physical Chemistry C, vol. 121, no. 27, American
Chemical Society, 2017, pp. 14451–62, doi:10.1021/acs.jpcc.7b03493.'
short: Y. Tsuji, T. Stuyver, S. Gunasekaran, L. Venkataraman, The Journal of Physical
Chemistry C 121 (2017) 14451–14462.
date_created: 2024-09-09T08:49:27Z
date_published: 2017-06-09T00:00:00Z
date_updated: 2024-12-18T07:29:42Z
day: '09'
doi: 10.1021/acs.jpcc.7b03493
extern: '1'
intvolume: ' 121'
issue: '27'
language:
- iso: eng
month: '06'
oa_version: None
page: 14451-14462
publication: The Journal of Physical Chemistry C
publication_identifier:
eissn:
- 1932-7455
issn:
- 1932-7447
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'The influence of linkers on quantum interference: A linker theorem'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 121
year: '2017'
...
---
OA_type: closed access
_id: '17977'
abstract:
- lang: eng
text: Primary amines can interact with neighbor molecules or with a metal substrate
via weak bonds involving the electron lone pair of their amino functional group.
Near edge X-ray absorption spectra (NEXAFS) on the N 1s edge show that the structure
of the empty molecular orbitals localized on the nitrogen atom is very sensitive
to these interactions. Here we investigate the origin of these changes by means
of theoretical calculations. NEXAFS spectra are simulated for the 1,4-benzenediamine
(BDA) molecule in its free, crystalline, and monolayer on Au(111) forms. We identify
the electronic states which are affected by these amino-based interactions. In
the case of the molecular layer grown on the gold substrate, we show how the results
of the calculations can be used to identify intermolecular interactions influencing
adsorption geometries in molecular monolayers.
article_processing_charge: No
article_type: original
author:
- first_name: Gabriele
full_name: Balducci, Gabriele
last_name: Balducci
- first_name: Michele
full_name: Romeo, Michele
last_name: Romeo
- first_name: Mauro
full_name: Stener, Mauro
last_name: Stener
- first_name: Giovanna
full_name: Fronzoni, Giovanna
last_name: Fronzoni
- first_name: Dean
full_name: Cvetko, Dean
last_name: Cvetko
- first_name: Albano
full_name: Cossaro, Albano
last_name: Cossaro
- first_name: Martina
full_name: Dell’Angela, Martina
last_name: Dell’Angela
- first_name: Gregor
full_name: Kladnik, Gregor
last_name: Kladnik
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
- first_name: Alberto
full_name: Morgante, Alberto
last_name: Morgante
citation:
ama: 'Balducci G, Romeo M, Stener M, et al. Computational study of amino mediated
molecular interaction evidenced in N 1s NEXAFS: 1,4-diaminobenzene on Au (111).
The Journal of Physical Chemistry C. 2014;119(4):1988-1995. doi:10.1021/jp512146t'
apa: 'Balducci, G., Romeo, M., Stener, M., Fronzoni, G., Cvetko, D., Cossaro, A.,
… Morgante, A. (2014). Computational study of amino mediated molecular interaction
evidenced in N 1s NEXAFS: 1,4-diaminobenzene on Au (111). The Journal of Physical
Chemistry C. American Chemical Society. https://doi.org/10.1021/jp512146t'
chicago: 'Balducci, Gabriele, Michele Romeo, Mauro Stener, Giovanna Fronzoni, Dean
Cvetko, Albano Cossaro, Martina Dell’Angela, Gregor Kladnik, Latha Venkataraman,
and Alberto Morgante. “Computational Study of Amino Mediated Molecular Interaction
Evidenced in N 1s NEXAFS: 1,4-Diaminobenzene on Au (111).” The Journal of Physical
Chemistry C. American Chemical Society, 2014. https://doi.org/10.1021/jp512146t.'
ieee: 'G. Balducci et al., “Computational study of amino mediated molecular
interaction evidenced in N 1s NEXAFS: 1,4-diaminobenzene on Au (111),” The
Journal of Physical Chemistry C, vol. 119, no. 4. American Chemical Society,
pp. 1988–1995, 2014.'
ista: 'Balducci G, Romeo M, Stener M, Fronzoni G, Cvetko D, Cossaro A, Dell’Angela
M, Kladnik G, Venkataraman L, Morgante A. 2014. Computational study of amino mediated
molecular interaction evidenced in N 1s NEXAFS: 1,4-diaminobenzene on Au (111).
The Journal of Physical Chemistry C. 119(4), 1988–1995.'
mla: 'Balducci, Gabriele, et al. “Computational Study of Amino Mediated Molecular
Interaction Evidenced in N 1s NEXAFS: 1,4-Diaminobenzene on Au (111).” The
Journal of Physical Chemistry C, vol. 119, no. 4, American Chemical Society,
2014, pp. 1988–95, doi:10.1021/jp512146t.'
short: G. Balducci, M. Romeo, M. Stener, G. Fronzoni, D. Cvetko, A. Cossaro, M.
Dell’Angela, G. Kladnik, L. Venkataraman, A. Morgante, The Journal of Physical
Chemistry C 119 (2014) 1988–1995.
date_created: 2024-09-09T10:56:21Z
date_published: 2014-12-29T00:00:00Z
date_updated: 2025-01-02T13:40:42Z
day: '29'
doi: 10.1021/jp512146t
extern: '1'
intvolume: ' 119'
issue: '4'
language:
- iso: eng
month: '12'
oa_version: None
page: 1988-1995
publication: The Journal of Physical Chemistry C
publication_identifier:
eissn:
- 1932-7455
issn:
- 1932-7447
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'Computational study of amino mediated molecular interaction evidenced in N
1s NEXAFS: 1,4-diaminobenzene on Au (111)'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 119
year: '2014'
...
---
_id: '7301'
abstract:
- lang: eng
text: Several problems arise at the O2 (positive) electrode in the Li-air battery,
including solvent/electrode decomposition and electrode passivation by insulating
Li2O2. Progress partially depends on exploring the basic electrochemistry of O2
reduction. Here we describe the effect of complexing-cations on the electrochemical
reduction of O2 in DMSO in the presence and absence of a Li salt. The solubility
of alkaline peroxides in DMSO is enhanced by the complexing-cations, consistent
with their strong interaction with reduced O2. The complexing-cations also increase
the rate of the 1-electron O2 reduction to O2•– by up to six-fold (k° = 2.4 ×10–3
to 1.5 × 10–2 cm s–1) whether or not Li+ ions are present. In the absence of Li+,
the complexing-cations also promote the reduction of O2•– to O22–. In the presence
of Li+ and complexing-cations, and despite the interaction of the reduced O2 with
the latter, SERS confirms that the product is still Li2O2.
article_processing_charge: No
article_type: original
author:
- first_name: Chunmei
full_name: Li, Chunmei
last_name: Li
- first_name: Olivier
full_name: Fontaine, Olivier
last_name: Fontaine
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Lee
full_name: Johnson, Lee
last_name: Johnson
- first_name: Sylvie
full_name: Grugeon, Sylvie
last_name: Grugeon
- first_name: Stéphane
full_name: Laruelle, Stéphane
last_name: Laruelle
- first_name: Peter G.
full_name: Bruce, Peter G.
last_name: Bruce
- first_name: Michel
full_name: Armand, Michel
last_name: Armand
citation:
ama: 'Li C, Fontaine O, Freunberger SA, et al. Aprotic Li–O2 battery: Influence
of complexing agents on oxygen reduction in an aprotic solvent. The Journal
of Physical Chemistry C. 2014;118(7):3393-3401. doi:10.1021/jp4093805'
apa: 'Li, C., Fontaine, O., Freunberger, S. A., Johnson, L., Grugeon, S., Laruelle,
S., … Armand, M. (2014). Aprotic Li–O2 battery: Influence of complexing agents
on oxygen reduction in an aprotic solvent. The Journal of Physical Chemistry
C. ACS. https://doi.org/10.1021/jp4093805'
chicago: 'Li, Chunmei, Olivier Fontaine, Stefan Alexander Freunberger, Lee Johnson,
Sylvie Grugeon, Stéphane Laruelle, Peter G. Bruce, and Michel Armand. “Aprotic
Li–O2 Battery: Influence of Complexing Agents on Oxygen Reduction in an Aprotic
Solvent.” The Journal of Physical Chemistry C. ACS, 2014. https://doi.org/10.1021/jp4093805.'
ieee: 'C. Li et al., “Aprotic Li–O2 battery: Influence of complexing agents
on oxygen reduction in an aprotic solvent,” The Journal of Physical Chemistry
C, vol. 118, no. 7. ACS, pp. 3393–3401, 2014.'
ista: 'Li C, Fontaine O, Freunberger SA, Johnson L, Grugeon S, Laruelle S, Bruce
PG, Armand M. 2014. Aprotic Li–O2 battery: Influence of complexing agents on oxygen
reduction in an aprotic solvent. The Journal of Physical Chemistry C. 118(7),
3393–3401.'
mla: 'Li, Chunmei, et al. “Aprotic Li–O2 Battery: Influence of Complexing Agents
on Oxygen Reduction in an Aprotic Solvent.” The Journal of Physical Chemistry
C, vol. 118, no. 7, ACS, 2014, pp. 3393–401, doi:10.1021/jp4093805.'
short: C. Li, O. Fontaine, S.A. Freunberger, L. Johnson, S. Grugeon, S. Laruelle,
P.G. Bruce, M. Armand, The Journal of Physical Chemistry C 118 (2014) 3393–3401.
date_created: 2020-01-15T12:17:28Z
date_published: 2014-01-29T00:00:00Z
date_updated: 2021-01-12T08:12:53Z
day: '29'
doi: 10.1021/jp4093805
extern: '1'
intvolume: ' 118'
issue: '7'
language:
- iso: eng
month: '01'
oa_version: None
page: 3393-3401
publication: The Journal of Physical Chemistry C
publication_identifier:
issn:
- 1932-7447
- 1932-7455
publication_status: published
publisher: ACS
quality_controlled: '1'
status: public
title: 'Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction
in an aprotic solvent'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 118
year: '2014'
...
---
OA_type: closed access
_id: '17994'
abstract:
- lang: eng
text: Charge transfer through noncovalent interactions is crucial to a variety of
chemical phenomena. These interactions are often weak and nonspecific and can
coexist, making it difficult to isolate the transfer efficiency of one type of
bond versus another. Here, we show how core-hole clock spectroscopy can be used
to measure charge transfer through noncovalent interactions. We study the model
system 1,4-benzenediamine molecules bound on an Au surface through an Au–N donor–acceptor
bond as these are known to provide a pathway for electronic conduction in molecular
devices. We study different phases of the molecule/Au system and map charge delocalization
times from carbon and nitrogen sites on the molecule. We show that charge delocalization
across Au–N donor–acceptor bond occurs in less than 500 as. Furthermore, the Au–N
bond also enhances delocalization times from neighboring carbon sites, demonstrating
that fast charge transfer across a metal–organic interface does not require a
covalently bonded system.
article_processing_charge: No
article_type: original
author:
- first_name: Gregor
full_name: Kladnik, Gregor
last_name: Kladnik
- first_name: Dean
full_name: Cvetko, Dean
last_name: Cvetko
- first_name: Arunabh
full_name: Batra, Arunabh
last_name: Batra
- first_name: Martina
full_name: Dell’Angela, Martina
last_name: Dell’Angela
- first_name: Albano
full_name: Cossaro, Albano
last_name: Cossaro
- first_name: Maria
full_name: Kamenetska, Maria
last_name: Kamenetska
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
- first_name: Alberto
full_name: Morgante, Alberto
last_name: Morgante
citation:
ama: Kladnik G, Cvetko D, Batra A, et al. Ultrafast charge transfer through noncovalent
Au–N interactions in molecular systems. The Journal of Physical Chemistry C.
2013;117(32):16477-16482. doi:10.1021/jp405229b
apa: Kladnik, G., Cvetko, D., Batra, A., Dell’Angela, M., Cossaro, A., Kamenetska,
M., … Morgante, A. (2013). Ultrafast charge transfer through noncovalent Au–N
interactions in molecular systems. The Journal of Physical Chemistry C.
American Chemical Society. https://doi.org/10.1021/jp405229b
chicago: Kladnik, Gregor, Dean Cvetko, Arunabh Batra, Martina Dell’Angela, Albano
Cossaro, Maria Kamenetska, Latha Venkataraman, and Alberto Morgante. “Ultrafast
Charge Transfer through Noncovalent Au–N Interactions in Molecular Systems.” The
Journal of Physical Chemistry C. American Chemical Society, 2013. https://doi.org/10.1021/jp405229b.
ieee: G. Kladnik et al., “Ultrafast charge transfer through noncovalent Au–N
interactions in molecular systems,” The Journal of Physical Chemistry C,
vol. 117, no. 32. American Chemical Society, pp. 16477–16482, 2013.
ista: Kladnik G, Cvetko D, Batra A, Dell’Angela M, Cossaro A, Kamenetska M, Venkataraman
L, Morgante A. 2013. Ultrafast charge transfer through noncovalent Au–N interactions
in molecular systems. The Journal of Physical Chemistry C. 117(32), 16477–16482.
mla: Kladnik, Gregor, et al. “Ultrafast Charge Transfer through Noncovalent Au–N
Interactions in Molecular Systems.” The Journal of Physical Chemistry C,
vol. 117, no. 32, American Chemical Society, 2013, pp. 16477–82, doi:10.1021/jp405229b.
short: G. Kladnik, D. Cvetko, A. Batra, M. Dell’Angela, A. Cossaro, M. Kamenetska,
L. Venkataraman, A. Morgante, The Journal of Physical Chemistry C 117 (2013) 16477–16482.
date_created: 2024-09-09T11:30:45Z
date_published: 2013-07-17T00:00:00Z
date_updated: 2025-01-03T07:59:05Z
day: '17'
doi: 10.1021/jp405229b
extern: '1'
intvolume: ' 117'
issue: '32'
language:
- iso: eng
month: '07'
oa_version: None
page: 16477-16482
publication: The Journal of Physical Chemistry C
publication_identifier:
eissn:
- 1932-7455
issn:
- 1932-7447
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Ultrafast charge transfer through noncovalent Au–N interactions in molecular
systems
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 117
year: '2013'
...
---
_id: '6370'
abstract:
- lang: eng
text: 'The molecular and supramolecular origins of the superior nonlinear optical
(NLO) properties observed in the organic phenolic triene material, OH1 (2-(3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile),
are presented. The molecular charge-transfer distribution is topographically mapped,
demonstrating that a uniformly delocalized passive electronic medium facilitates
the charge-transfer between the phenolic electron donor and the cyano electron
acceptors which lie at opposite ends of the molecule. Its ability to act as a
“push–pull” π-conjugated molecule is quantified, relative to similar materials,
by supporting empirical calculations; these include bond-length alternation and
harmonic-oscillator stabilization energy (HOSE) tests. Such tests, together with
frontier molecular orbital considerations, reveal that OH1 can exist readily in
its aromatic (neutral) or quinoidal (charge-separated) state, thereby overcoming
the “nonlinearity-thermal stability trade-off”. The HOSE calculation also reveals
a correlation between the quinoidal resonance contribution to the overall structure
of OH1 and the UV–vis absorption peak wavelength in the wider family of configurationally
locked polyene framework materials. Solid-state tensorial coefficients of the
molecular dipole, polarizability, and the first hyperpolarizability for OH1 are
derived from the first-, second-, and third-order electronic moments of the experimental
charge-density distribution. The overall solid-state molecular dipole moment is
compared with those from gas-phase calculations, revealing that crystal field
effects are very significant in OH1. The solid-state hyperpolarizability derived
from this charge-density study affords good agreement with gas-phase calculations
as well as optical measurements based on hyper-Rayleigh scattering (HRS) and electric-field-induced
second harmonic (EFISH) generation. This lends support to the further use of charge-density
studies to calculate solid-state hyperpolarizability coefficients in other organic
NLO materials. Finally, this charge-density study is also employed to provide
an advanced classification of hydrogen bonds in OH1, which requires more stringent
criteria than those from conventional structure analysis. As a result, only the
strongest OH···NC interaction is so classified as a true hydrogen bond. Indeed,
it is this electrostatic interaction that influences the molecular charge transfer:
the other four, weaker, nonbonded contacts nonetheless affect the crystal packing.
Overall, the establishment of these structure–property relationships lays a blueprint
for designing further, more NLO efficient, materials in this industrially leading
organic family of compounds.'
author:
- first_name: Tze-Chia
full_name: Lin, Tze-Chia
last_name: Lin
- first_name: Jacqueline M.
full_name: Cole, Jacqueline M.
last_name: Cole
- first_name: Andrew P
full_name: Higginbotham, Andrew P
id: 4AD6785A-F248-11E8-B48F-1D18A9856A87
last_name: Higginbotham
orcid: 0000-0003-2607-2363
- first_name: Alison J.
full_name: Edwards, Alison J.
last_name: Edwards
- first_name: Ross O.
full_name: Piltz, Ross O.
last_name: Piltz
- first_name: Javier
full_name: Pérez-Moreno, Javier
last_name: Pérez-Moreno
- first_name: Ji-Youn
full_name: Seo, Ji-Youn
last_name: Seo
- first_name: Seung-Chul
full_name: Lee, Seung-Chul
last_name: Lee
- first_name: Koen
full_name: Clays, Koen
last_name: Clays
- first_name: O-Pil
full_name: Kwon, O-Pil
last_name: Kwon
citation:
ama: 'Lin T-C, Cole JM, Higginbotham AP, et al. Molecular origins of the high-performance
nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density
distributions, hydrogen bonding, and ab initio calculations. The Journal of
Physical Chemistry C. 2013;117(18):9416-9430. doi:10.1021/jp400648q'
apa: 'Lin, T.-C., Cole, J. M., Higginbotham, A. P., Edwards, A. J., Piltz, R. O.,
Pérez-Moreno, J., … Kwon, O.-P. (2013). Molecular origins of the high-performance
nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density
distributions, hydrogen bonding, and ab initio calculations. The Journal of
Physical Chemistry C. American Chemical Society (ACS). https://doi.org/10.1021/jp400648q'
chicago: 'Lin, Tze-Chia, Jacqueline M. Cole, Andrew P Higginbotham, Alison J. Edwards,
Ross O. Piltz, Javier Pérez-Moreno, Ji-Youn Seo, Seung-Chul Lee, Koen Clays, and
O-Pil Kwon. “Molecular Origins of the High-Performance Nonlinear Optical Susceptibility
in a Phenolic Polyene Chromophore: Electron Density Distributions, Hydrogen Bonding,
and Ab Initio Calculations.” The Journal of Physical Chemistry C. American
Chemical Society (ACS), 2013. https://doi.org/10.1021/jp400648q.'
ieee: 'T.-C. Lin et al., “Molecular origins of the high-performance nonlinear
optical susceptibility in a phenolic polyene chromophore: Electron density distributions,
hydrogen bonding, and ab initio calculations,” The Journal of Physical Chemistry
C, vol. 117, no. 18. American Chemical Society (ACS), pp. 9416–9430, 2013.'
ista: 'Lin T-C, Cole JM, Higginbotham AP, Edwards AJ, Piltz RO, Pérez-Moreno J,
Seo J-Y, Lee S-C, Clays K, Kwon O-P. 2013. Molecular origins of the high-performance
nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density
distributions, hydrogen bonding, and ab initio calculations. The Journal of Physical
Chemistry C. 117(18), 9416–9430.'
mla: 'Lin, Tze-Chia, et al. “Molecular Origins of the High-Performance Nonlinear
Optical Susceptibility in a Phenolic Polyene Chromophore: Electron Density Distributions,
Hydrogen Bonding, and Ab Initio Calculations.” The Journal of Physical Chemistry
C, vol. 117, no. 18, American Chemical Society (ACS), 2013, pp. 9416–30, doi:10.1021/jp400648q.'
short: T.-C. Lin, J.M. Cole, A.P. Higginbotham, A.J. Edwards, R.O. Piltz, J. Pérez-Moreno,
J.-Y. Seo, S.-C. Lee, K. Clays, O.-P. Kwon, The Journal of Physical Chemistry
C 117 (2013) 9416–9430.
date_created: 2019-05-03T09:40:31Z
date_published: 2013-05-09T00:00:00Z
date_updated: 2021-01-12T08:07:17Z
day: '09'
doi: 10.1021/jp400648q
extern: '1'
intvolume: ' 117'
issue: '18'
language:
- iso: eng
month: '05'
oa_version: None
page: 9416-9430
publication: The Journal of Physical Chemistry C
publication_identifier:
issn:
- 1932-7447
- 1932-7455
publication_status: published
publisher: American Chemical Society (ACS)
quality_controlled: '1'
status: public
title: 'Molecular origins of the high-performance nonlinear optical susceptibility
in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding,
and ab initio calculations'
type: journal_article
user_id: 3E5EF7F0-F248-11E8-B48F-1D18A9856A87
volume: 117
year: '2013'
...
---
OA_type: closed access
_id: '18015'
abstract:
- lang: eng
text: We investigate the binding and energy level alignment of 2,3,5,6-tetramethyl-1,4-benzenediamine
(TMBDA) on Au(111) through a combination of helium atom scattering (HAS), X-ray
photoemission (XPS), and scanning tunneling microscopy (STM). We show that TMBDA
binds to step edges and to flat Au (111) terraces in a nearly flat-lying configuration.
Through combination of HAS and STM data, we determine that the molecules are bound
on step edges with an adsorption energy of about 1.2 eV, which is about 0.2 eV
stronger than the adsorption energy we measure on flat surface. Preferential bonding
to the under-coordinated Au atoms on step edges suggests that the molecules bind
to Au through the nitrogen lone pair. Finally, STM measurements on TMBDA in these
two different adsorption configurations show that the highest-occupied molecular
orbital is deeper relative to Fermi for the more strongly bound molecules on step
edges, confirming that the nitrogen bonds through charge donation to the Au.
article_processing_charge: No
article_type: original
author:
- first_name: M.
full_name: Kamenetska, M.
last_name: Kamenetska
- first_name: M.
full_name: Dell’Angela, M.
last_name: Dell’Angela
- first_name: J.R.
full_name: Widawsky, J.R.
last_name: Widawsky
- first_name: G.
full_name: Kladnik, G.
last_name: Kladnik
- first_name: A.
full_name: Verdini, A.
last_name: Verdini
- first_name: A.
full_name: Cossaro, A.
last_name: Cossaro
- first_name: D.
full_name: Cvetko, D.
last_name: Cvetko
- first_name: A.
full_name: Morgante, A.
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: Kamenetska M, Dell’Angela M, Widawsky JR, et al. Structure and energy level
alignment of tetramethyl benzenediamine on Au(111). The Journal of Physical
Chemistry C. 2011;115(25):12625-12630. doi:10.1021/jp202555d
apa: Kamenetska, M., Dell’Angela, M., Widawsky, J. R., Kladnik, G., Verdini, A.,
Cossaro, A., … Venkataraman, L. (2011). Structure and energy level alignment of
tetramethyl benzenediamine on Au(111). The Journal of Physical Chemistry C.
American Chemical Society. https://doi.org/10.1021/jp202555d
chicago: Kamenetska, M., M. Dell’Angela, J.R. Widawsky, G. Kladnik, A. Verdini,
A. Cossaro, D. Cvetko, A. Morgante, and Latha Venkataraman. “Structure and Energy
Level Alignment of Tetramethyl Benzenediamine on Au(111).” The Journal of Physical
Chemistry C. American Chemical Society, 2011. https://doi.org/10.1021/jp202555d.
ieee: M. Kamenetska et al., “Structure and energy level alignment of tetramethyl
benzenediamine on Au(111),” The Journal of Physical Chemistry C, vol. 115,
no. 25. American Chemical Society, pp. 12625–12630, 2011.
ista: Kamenetska M, Dell’Angela M, Widawsky JR, Kladnik G, Verdini A, Cossaro A,
Cvetko D, Morgante A, Venkataraman L. 2011. Structure and energy level alignment
of tetramethyl benzenediamine on Au(111). The Journal of Physical Chemistry C.
115(25), 12625–12630.
mla: Kamenetska, M., et al. “Structure and Energy Level Alignment of Tetramethyl
Benzenediamine on Au(111).” The Journal of Physical Chemistry C, vol. 115,
no. 25, American Chemical Society, 2011, pp. 12625–30, doi:10.1021/jp202555d.
short: M. Kamenetska, M. Dell’Angela, J.R. Widawsky, G. Kladnik, A. Verdini, A.
Cossaro, D. Cvetko, A. Morgante, L. Venkataraman, The Journal of Physical Chemistry
C 115 (2011) 12625–12630.
date_created: 2024-09-09T12:34:26Z
date_published: 2011-05-17T00:00:00Z
date_updated: 2025-01-03T09:36:40Z
day: '17'
doi: 10.1021/jp202555d
extern: '1'
intvolume: ' 115'
issue: '25'
language:
- iso: eng
month: '05'
oa_version: None
page: 12625-12630
publication: The Journal of Physical Chemistry C
publication_identifier:
eissn:
- 1932-7455
issn:
- 1932-7447
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Structure and energy level alignment of tetramethyl benzenediamine on Au(111)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 115
year: '2011'
...
---
OA_type: closed access
_id: '18036'
abstract:
- lang: eng
text: We measured conductance traces while breaking gold point contacts in a solution
of molecules containing the μ-p-phenylenediethynyl X−C⋮C−C6H4−C⋮C−X unit, with
eight different capping X groups: Au−P(OMe)3 (1), H (2), SiMe3 (3), Au−P(cy)3
(4), Au−PMe2Ph (5), Au−PMePh2 (6), Au−PMe3 (7), and Au−PPh3 (8). Our goal with
this work was to achieve a direct Au−C link with a conjugated organic group, potentially
forming a molecular junction without chemical link groups that typically decrease
junction conductances, such as thiols or amines. Conductance traces collected
in the presence of molecules 1, 2, 3, 5, and 7 reveal additional steps at conductances
as high as 0.1 G0 (G0 = 2e2/h) down to the measurable limits of the experimental
setup. Conductance histograms generated from these traces therefore show a broad
increase of counts when compared to a control histogram collected in the solvent
alone suggesting the binding of the molecules to the broken Au contacts. The histograms
for molecules 1, 5, 7, and 2 were not distinguishable, although that of molecule
3 had considerably fewer counts over the entire conductance range, suggesting
that the steric bulk of the SiMe3 prevented frequent junction formation. The histograms
collected in a solution of molecules 4, 6, or 8 did not differ from that of the
control histogram probably because of the steric bulk of the Au−PR3 capping groups
prevented the formation a molecular junction.
article_processing_charge: No
article_type: original
author:
- first_name: David
full_name: Millar, David
last_name: Millar
- first_name: Latha
full_name: Venkataraman, Latha
id: 9ebb78a5-cc0d-11ee-8322-fae086a32caf
last_name: Venkataraman
orcid: 0000-0002-6957-6089
- first_name: Linda H.
full_name: Doerrer, Linda H.
last_name: Doerrer
citation:
ama: Millar D, Venkataraman L, Doerrer LH. Efficacy of Au−Au contacts for scanning
tunneling microscopy molecular conductance measurements. The Journal of Physical
Chemistry C. 2007;111(47):17635-17639. doi:10.1021/jp0756101
apa: Millar, D., Venkataraman, L., & Doerrer, L. H. (2007). Efficacy of Au−Au
contacts for scanning tunneling microscopy molecular conductance measurements.
The Journal of Physical Chemistry C. American Chemical Society. https://doi.org/10.1021/jp0756101
chicago: Millar, David, Latha Venkataraman, and Linda H. Doerrer. “Efficacy of Au−Au
Contacts for Scanning Tunneling Microscopy Molecular Conductance Measurements.”
The Journal of Physical Chemistry C. American Chemical Society, 2007. https://doi.org/10.1021/jp0756101.
ieee: D. Millar, L. Venkataraman, and L. H. Doerrer, “Efficacy of Au−Au contacts
for scanning tunneling microscopy molecular conductance measurements,” The
Journal of Physical Chemistry C, vol. 111, no. 47. American Chemical Society,
pp. 17635–17639, 2007.
ista: Millar D, Venkataraman L, Doerrer LH. 2007. Efficacy of Au−Au contacts for
scanning tunneling microscopy molecular conductance measurements. The Journal
of Physical Chemistry C. 111(47), 17635–17639.
mla: Millar, David, et al. “Efficacy of Au−Au Contacts for Scanning Tunneling Microscopy
Molecular Conductance Measurements.” The Journal of Physical Chemistry C,
vol. 111, no. 47, American Chemical Society, 2007, pp. 17635–39, doi:10.1021/jp0756101.
short: D. Millar, L. Venkataraman, L.H. Doerrer, The Journal of Physical Chemistry
C 111 (2007) 17635–17639.
date_created: 2024-09-09T14:45:13Z
date_published: 2007-11-02T00:00:00Z
date_updated: 2025-01-03T11:02:03Z
day: '02'
doi: 10.1021/jp0756101
extern: '1'
intvolume: ' 111'
issue: '47'
language:
- iso: eng
month: '11'
oa_version: None
page: 17635-17639
publication: The Journal of Physical Chemistry C
publication_identifier:
eissn:
- 1932-7455
issn:
- 1932-7447
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Efficacy of Au−Au contacts for scanning tunneling microscopy molecular conductance
measurements
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 111
year: '2007'
...