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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_SC - Článek v periodiku v databázi SCOPUS

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA23-07066S" target="_blank" >GA23-07066S: Časově závislé simulace pro časově rozlišené elektronové spektroskopie</a><br>

Návaznosti

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

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

1549-9626

Svazek periodika

20

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

10972-10985

Kód UT WoS článku

—

EID výsledku v databázi Scopus

2-s2.0-85212048043