Limits of the Nuclear Ensemble Method for Electronic Spectra
Simulations: Temperature Dependence of the (E)-Azobenzene
Spectrum

J 2020

Limits of the Nuclear Ensemble Method for Electronic Spectra Simulations: Temperature Dependence of the (E)-Azobenzene Spectrum

SRŠEŇ, Štěpán, Jaroslav SITA, Petr SLAVÍČEK, Vít LADÁNYI, Dominik HEGER et. al.

Základní údaje

Originální název

Limits of the Nuclear Ensemble Method for Electronic Spectra Simulations: Temperature Dependence of the (E)-Azobenzene Spectrum

Autoři

SRŠEŇ, Štěpán, Jaroslav SITA, Petr SLAVÍČEK, Vít LADÁNYI (203 Česká republika, domácí) a Dominik HEGER (203 Česká republika, domácí)

Vydání

Journal of Chemical Theory and Computation, Washington DC, American Chemical Society, 2020, 1549-9618

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 6.006

Kód RIV

RIV/00216224:14310/20:00114554

Organizační jednotka

Přírodovědecká fakulta

DOI

http://dx.doi.org/10.1021/acs.jctc.0c00579

UT WoS

000580954000039

Klíčová slova anglicky

Absorption; Chemical structure; Nanoelectromechanical systems; Mathematical methods; Absorption spectroscopy

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 8. 12. 2020 15:19, Mgr. Marie Šípková, DiS.

Anotace

V originále

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.

Návaznosti

GA19-08239S, projekt VaV

Název: Spektroskopie a mikroskopie chemických látek v ledu pro environmentální a farmaceutické účely

Investor: Grantová agentura ČR, Spektroskopie a mikroskopie chemických látek v ledu pro environmentální a farmaceutické účely

Citovat

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.

@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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