Sensitivity Analysis in Photodynamics: How Does the Electronic Structure Control cis-Stilbene Photodynamics?

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F24%3A43930931" target="_blank" >RIV/60461373:22340/24:43930931 - isvavai.cz</a>

Result on the web

<a href="https://pubs.acs.org/doi/10.1021/acs.jctc.4c01008" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jctc.4c01008</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.4c01008" target="_blank" >10.1021/acs.jctc.4c01008</a>

Result language

angličtina

Original language name

Sensitivity Analysis in Photodynamics: How Does the Electronic Structure Control cis-Stilbene Photodynamics?

Original language description

The techniques of computational photodynamics are increasingly employed to unravel reaction mechanisms and interpret experiments. However, misinterpretations in nonadiabatic dynamics caused by inaccurate underlying potentials are often difficult to foresee. This work focuses on revealing the systematic errors in the nonadiabatic simulations due to the underlying potentials and suggests a thrifty approach to evaluate the sensitivity of the simulations to the potential. This issue is exemplified in the photochemistry of cis-stilbene, where similar experimental outcomes have been differently interpreted based on the electronic structure methods supporting nonadiabatic dynamics. We examine the predictions of cis-stilbene photochemistry using trajectory surface hopping methods coupled with various electronic structure methods (OM3-MRCISD, SA2-CASSCF, XMS-SA2-CASPT2, and XMS-SA3-CASPT2) and assess their ability to interpret experimental observations. While the excited-state lifetimes and calculated photoelectron spectra show consistency with experiments, the reaction quantum yields vary significantly: either completely suppressing cyclization or isomerization. Intriguingly, analyzing stationary points on the potential energy surface does not hint at any major discrepancy, making the electronic structure methods seemingly reliable when treated separately. We show that performing an ensemble of simulations with different potentials provides an estimate of the electronic structure sensitivity. However, this ensemble approach is costly. Thus, we propose running nonadiabatic simulations with an external bias at a resource-efficient underlying potential (semiempirical or machine-learned) for the sensitivity analysis. We demonstrate this approach using a semiempirical OM3-MRCISD method with a harmonic bias toward cyclization. © 2024 The Authors. Published by American Chemical Society.

Czech name

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Czech description

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Type

J_SC - Article in a specialist periodical, which is included in the SCOPUS database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA23-07066S" target="_blank" >GA23-07066S: Time-dependent simulations for time-resolved electronic spectroscopies</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2024

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

1549-9626

Volume of the periodical

20

Issue of the periodical within the volume

24

Country of publishing house

US - UNITED STATES

Number of pages

14

Pages from-to

10972-10985

UT code for WoS article

—

EID of the result in the Scopus database

2-s2.0-85212048043