Limits of the Nuclear Ensemble Method for Electronic Spectra Simulations: Temperature Dependence of the (E)-Azobenzene Spectrum
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F20%3A43920930" target="_blank" >RIV/60461373:22340/20:43920930 - isvavai.cz</a>
Alternative codes found
RIV/00216224:14310/20:00114554
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.jctc.0c00579" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jctc.0c00579</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jctc.0c00579" target="_blank" >10.1021/acs.jctc.0c00579</a>
Alternative languages
Result language
angličtina
Original language name
Limits of the Nuclear Ensemble Method for Electronic Spectra Simulations: Temperature Dependence of the (E)-Azobenzene Spectrum
Original language description
We explore the range of applicability of the nuclear ensemble method (NEM) for quantitative simulations of absorption spectra and their temperature variations. We formulate a "good practice"for the NEM based on statistical theory. Special attention is paid to proper treatment of uncertainty estimation including the convergence with the number of samples, which is often neglected in the field. As a testbed, we have selected a well-known chromophore, (E)-azobenzene. We measured its temperature difference UV-vis absorption spectra in methanol, which displayed two dominant features: a moderate increase in the intensity of the nπ∗ band and a pronounced decrease in intensity of the low-energy part of the ππ∗ band. We attributed both features to increasing non-Condon effects with temperature. We show that the NEM based on the path integral molecular dynamics combined with range-separated hybrid functionals provides quantitatively accurate spectra and their differences. Experimentally, the depletion of the absorption in the ππ∗ band showed a characteristic vibrational progression that cannot be reproduced with the NEM. We show that hundreds of thousands of samples are necessary to achieve an accuracy sufficient for the unambiguous explanation of the observed temperature effects. We provide a detailed analysis of the temperature effects on the spectrum based on the harmonic model of the system combined with the NEM. We also rationalize the vibrational structure of the spectrum using the Franck-Condon principle. Copyright © 2020 American Chemical Society.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Chemical Theory and Computation
ISSN
1549-9618
e-ISSN
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Volume of the periodical
16
Issue of the periodical within the volume
10
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
6428-6438
UT code for WoS article
000580954000039
EID of the result in the Scopus database
2-s2.0-85092945198