| SRŠEŇ, Štěpán, Jaroslav SITA, Petr SLAVÍČEK, Vít LADÁNYI a Dominik HEGER. Limits of the Nuclear Ensemble Method for Electronic Spectra Simulations: Temperature Dependence of the (E)-Azobenzene Spectrum. Journal of Chemical Theory and Computation. Washington DC: American Chemical Society, 2020, roč. 16, č. 10, s. 6428-6438. ISSN 1549-9618. Dostupné z: https://dx.doi.org/10.1021/acs.jctc.0c00579. |
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@article{1705996,
author = {Sršeň, Štěpán and Sita, Jaroslav and Slavíček, Petr and Ladányi, Vít and Heger, Dominik},
article_location = {Washington DC},
article_number = {10},
doi = {http://dx.doi.org/10.1021/acs.jctc.0c00579},
keywords = {Absorption; Chemical structure; Nanoelectromechanical systems; Mathematical methods; Absorption spectroscopy},
language = {eng},
issn = {1549-9618},
journal = {Journal of Chemical Theory and Computation},
title = {Limits of the Nuclear Ensemble Method for Electronic Spectra Simulations: Temperature Dependence of the (E)-Azobenzene Spectrum},
url = {https://doi.org/10.1021/acs.jctc.0c00579},
volume = {16},
year = {2020}
}
TY - JOUR
ID - 1705996
AU - Sršeň, Štěpán - Sita, Jaroslav - Slavíček, Petr - Ladányi, Vít - Heger, Dominik
PY - 2020
TI - Limits of the Nuclear Ensemble Method for Electronic Spectra Simulations: Temperature Dependence of the (E)-Azobenzene Spectrum
JF - Journal of Chemical Theory and Computation
VL - 16
IS - 10
SP - 6428-6438
EP - 6428-6438
PB - American Chemical Society
SN - 15499618
KW - Absorption
KW - Chemical structure
KW - Nanoelectromechanical systems
KW - Mathematical methods
KW - Absorption spectroscopy
UR - https://doi.org/10.1021/acs.jctc.0c00579
L2 - https://doi.org/10.1021/acs.jctc.0c00579
N2 - 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 n pi* band and a pronounced decrease in intensity of the low-energy part of the pi pi* 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 pi pi* 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.
ER -
SRŠEŇ, Štěpán, Jaroslav SITA, Petr SLAVÍČEK, Vít LADÁNYI a Dominik HEGER. Limits of the Nuclear Ensemble Method for Electronic Spectra Simulations: Temperature Dependence of the (E)-Azobenzene Spectrum. \textit{Journal of Chemical Theory and Computation}. Washington DC: American Chemical Society, 2020, roč.~16, č.~10, s.~6428-6438. ISSN~1549-9618. Dostupné z: https://dx.doi.org/10.1021/acs.jctc.0c00579.
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