---
_id: '5886'
abstract:
- lang: eng
  text: Problems involving quantum impurities, in which one or a few particles are
    interacting with a macroscopic environment, represent a pervasive paradigm, spanning
    across atomic, molecular, and condensed-matter physics. In this paper we introduce
    new variational approaches to quantum impurities and apply them to the Fröhlich
    polaron–a quasiparticle formed out of an electron (or other point-like impurity)
    in a polar medium, and to the angulon–a quasiparticle formed out of a rotating
    molecule in a bosonic bath. We benchmark these approaches against established
    theories, evaluating their accuracy as a function of the impurity-bath coupling.
article_processing_charge: No
author:
- first_name: Xiang
  full_name: Li, Xiang
  id: 4B7E523C-F248-11E8-B48F-1D18A9856A87
  last_name: Li
- first_name: Giacomo
  full_name: Bighin, Giacomo
  id: 4CA96FD4-F248-11E8-B48F-1D18A9856A87
  last_name: Bighin
  orcid: 0000-0001-8823-9777
- first_name: Enderalp
  full_name: Yakaboylu, Enderalp
  id: 38CB71F6-F248-11E8-B48F-1D18A9856A87
  last_name: Yakaboylu
  orcid: 0000-0001-5973-0874
- first_name: Mikhail
  full_name: Lemeshko, Mikhail
  id: 37CB05FA-F248-11E8-B48F-1D18A9856A87
  last_name: Lemeshko
  orcid: 0000-0002-6990-7802
citation:
  ama: 'Li X, Bighin G, Yakaboylu E, Lemeshko M. Variational approaches to quantum
    impurities: from the Fröhlich polaron to the angulon. <i>Molecular Physics</i>.
    2019. doi:<a href="https://doi.org/10.1080/00268976.2019.1567852">10.1080/00268976.2019.1567852</a>'
  apa: 'Li, X., Bighin, G., Yakaboylu, E., &#38; Lemeshko, M. (2019). Variational
    approaches to quantum impurities: from the Fröhlich polaron to the angulon. <i>Molecular
    Physics</i>. Taylor &#38; Francis. <a href="https://doi.org/10.1080/00268976.2019.1567852">https://doi.org/10.1080/00268976.2019.1567852</a>'
  chicago: 'Li, Xiang, Giacomo Bighin, Enderalp Yakaboylu, and Mikhail Lemeshko. “Variational
    Approaches to Quantum Impurities: From the Fröhlich Polaron to the Angulon.” <i>Molecular
    Physics</i>. Taylor &#38; Francis, 2019. <a href="https://doi.org/10.1080/00268976.2019.1567852">https://doi.org/10.1080/00268976.2019.1567852</a>.'
  ieee: 'X. Li, G. Bighin, E. Yakaboylu, and M. Lemeshko, “Variational approaches
    to quantum impurities: from the Fröhlich polaron to the angulon,” <i>Molecular
    Physics</i>. Taylor &#38; Francis, 2019.'
  ista: 'Li X, Bighin G, Yakaboylu E, Lemeshko M. 2019. Variational approaches to
    quantum impurities: from the Fröhlich polaron to the angulon. Molecular Physics.'
  mla: 'Li, Xiang, et al. “Variational Approaches to Quantum Impurities: From the
    Fröhlich Polaron to the Angulon.” <i>Molecular Physics</i>, Taylor &#38; Francis,
    2019, doi:<a href="https://doi.org/10.1080/00268976.2019.1567852">10.1080/00268976.2019.1567852</a>.'
  short: X. Li, G. Bighin, E. Yakaboylu, M. Lemeshko, Molecular Physics (2019).
das_tickbox: '1'
date_created: 2019-01-27T22:59:10Z
date_published: 2019-01-18T00:00:00Z
date_updated: 2026-07-07T05:31:10Z
day: '18'
ddc:
- '530'
department:
- _id: MiLe
doi: 10.1080/00268976.2019.1567852
ec_funded: 1
external_id:
  isi:
  - '000474641400008'
file:
- access_level: open_access
  checksum: 178964744b636a6f036372f4f090a657
  content_type: application/pdf
  creator: dernst
  date_created: 2019-01-29T08:32:57Z
  date_updated: 2020-07-14T12:47:13Z
  file_id: '5896'
  file_name: 2019_MolecularPhysics_Li.pdf
  file_size: 1309966
  relation: main_file
file_date_updated: 2020-07-14T12:47:13Z
fulldoi: https://doi.org/10.1080/00268976.2019.1567852
has_accepted_license: '1'
isi: 1
language:
- iso: eng
month: '01'
oa: 1
oa_version: Published Version
project:
- _id: 26031614-B435-11E9-9278-68D0E5697425
  call_identifier: FWF
  grant_number: P29902
  name: Quantum rotations in the presence of a many-body environment
- _id: 25681D80-B435-11E9-9278-68D0E5697425
  call_identifier: FP7
  grant_number: '291734'
  name: International IST Postdoc Fellowship Programme
publication: Molecular Physics
publication_identifier:
  issn:
  - 0026-8976
publication_status: published
publisher: Taylor & Francis
quality_controlled: '1'
related_material:
  record:
  - id: '8958'
    relation: dissertation_contains
    status: public
scopus_import: '1'
status: public
title: 'Variational approaches to quantum impurities: from the Fröhlich polaron to
  the angulon'
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
year: '2019'
...
---
_id: '10358'
abstract:
- lang: eng
  text: Probing reaction mechanisms of supramolecular processes in soft and biological
    matter, such as protein aggregation, is inherently challenging. This is because
    these processes involve multiple molecular mechanisms that are associated with
    the rearrangement of large numbers of weak bonds, resulting in complex free energy
    landscapes with many kinetic barriers. Reaction rate measurements at different
    temperatures can offer unprecedented insights into the underlying molecular mechanisms.
    However, to be able to interpret such measurements, a key challenge is to establish
    which properties of the complex free energy landscapes are probed by the reaction
    rate. Here, we present a reaction rate theory for supramolecular kinetics based
    on Kramers theory of diffusive reactions over multiple kinetic barriers. We find
    that reaction rates for protein aggregation are of the Arrhenius–Eyring type and
    that the associated activation energies probe only one relevant barrier along
    the respective free energy landscapes. We apply this advancement to interpret,
    in experiments and in coarse-grained computer simulations, reaction rates of amyloid
    aggregation in terms of molecular mechanisms and associated thermodynamic signatures.
    These results suggest a practical extension of the concept of rate-determining
    steps for complex supramolecular processes and establish a general platform for
    probing the underlying energy landscape using kinetic measurements.
acknowledgement: We thank Claudia Flandoli for the help with illustrations.
article_processing_charge: No
article_type: original
arxiv: 1
author:
- first_name: Thomas C. T.
  full_name: Michaels, Thomas C. T.
  last_name: Michaels
- first_name: Lucie X.
  full_name: Liu, Lucie X.
  last_name: Liu
- first_name: Samo
  full_name: Curk, Samo
  last_name: Curk
- first_name: Peter G.
  full_name: Bolhuis, Peter G.
  last_name: Bolhuis
- first_name: Anđela
  full_name: Šarić, Anđela
  id: bf63d406-f056-11eb-b41d-f263a6566d8b
  last_name: Šarić
  orcid: 0000-0002-7854-2139
- first_name: Tuomas P. J.
  full_name: Knowles, Tuomas P. J.
  last_name: Knowles
citation:
  ama: 'Michaels TCT, Liu LX, Curk S, Bolhuis PG, Šarić A, Knowles TPJ. Reaction rate
    theory for supramolecular kinetics: application to protein aggregation. <i>Molecular
    Physics</i>. 2018;116(21-22):3055-3065. doi:<a href="https://doi.org/10.1080/00268976.2018.1474280">10.1080/00268976.2018.1474280</a>'
  apa: 'Michaels, T. C. T., Liu, L. X., Curk, S., Bolhuis, P. G., Šarić, A., &#38;
    Knowles, T. P. J. (2018). Reaction rate theory for supramolecular kinetics: application
    to protein aggregation. <i>Molecular Physics</i>. Taylor &#38; Francis. <a href="https://doi.org/10.1080/00268976.2018.1474280">https://doi.org/10.1080/00268976.2018.1474280</a>'
  chicago: 'Michaels, Thomas C. T., Lucie X. Liu, Samo Curk, Peter G. Bolhuis, Anđela
    Šarić, and Tuomas P. J. Knowles. “Reaction Rate Theory for Supramolecular Kinetics:
    Application to Protein Aggregation.” <i>Molecular Physics</i>. Taylor &#38; Francis,
    2018. <a href="https://doi.org/10.1080/00268976.2018.1474280">https://doi.org/10.1080/00268976.2018.1474280</a>.'
  ieee: 'T. C. T. Michaels, L. X. Liu, S. Curk, P. G. Bolhuis, A. Šarić, and T. P.
    J. Knowles, “Reaction rate theory for supramolecular kinetics: application to
    protein aggregation,” <i>Molecular Physics</i>, vol. 116, no. 21–22. Taylor &#38;
    Francis, pp. 3055–3065, 2018.'
  ista: 'Michaels TCT, Liu LX, Curk S, Bolhuis PG, Šarić A, Knowles TPJ. 2018. Reaction
    rate theory for supramolecular kinetics: application to protein aggregation. Molecular
    Physics. 116(21–22), 3055–3065.'
  mla: 'Michaels, Thomas C. T., et al. “Reaction Rate Theory for Supramolecular Kinetics:
    Application to Protein Aggregation.” <i>Molecular Physics</i>, vol. 116, no. 21–22,
    Taylor &#38; Francis, 2018, pp. 3055–65, doi:<a href="https://doi.org/10.1080/00268976.2018.1474280">10.1080/00268976.2018.1474280</a>.'
  short: T.C.T. Michaels, L.X. Liu, S. Curk, P.G. Bolhuis, A. Šarić, T.P.J. Knowles,
    Molecular Physics 116 (2018) 3055–3065.
date_created: 2021-11-26T12:08:02Z
date_published: 2018-05-24T00:00:00Z
date_updated: 2021-11-26T12:39:58Z
day: '24'
doi: 10.1080/00268976.2018.1474280
extern: '1'
external_id:
  arxiv:
  - '1803.04851'
fulldoi: https://doi.org/10.1080/00268976.2018.1474280
intvolume: '       116'
issue: 21-22
keyword:
- physical chemistry
language:
- iso: eng
main_file_link:
- open_access: '1'
  url: https://arxiv.org/abs/1803.04851
month: '05'
oa: 1
oa_version: Preprint
page: 3055-3065
publication: Molecular Physics
publication_identifier:
  eissn:
  - 1362-3028
  issn:
  - 0026-8976
publication_status: published
publisher: Taylor & Francis
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'Reaction rate theory for supramolecular kinetics: application to protein aggregation'
type: journal_article
user_id: 8b945eb4-e2f2-11eb-945a-df72226e66a9
volume: 116
year: '2018'
...