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ZENODO
Dataset . 2024
License: CC BY
Data sources: ZENODO
ZENODO
Dataset . 2024
License: CC BY
Data sources: Datacite
ZENODO
Dataset . 2024
License: CC BY
Data sources: Datacite
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Dataset of "Sensitivity analysis in photodynamics: How the electronic structure controls cis-stilbene photodynamics?"

Authors: Slavíček, Petr; Bouzek, Karel; Carda, Michal;

Dataset of "Sensitivity analysis in photodynamics: How the electronic structure controls cis-stilbene photodynamics?"

Abstract

The techniques of computational photodynamics are increasingly employed to unravel reaction mechanisms and interpret experiments. However, inaccuracies in nonadiabatic dynamics can lead to misinterpretations, particularly when calculated observables exhibit low sensitivity to the underlying dynamics. This issue is exemplified in the photochemistry of cis-stilbene, where similar experimental outcomes have been differently interpreted based on the electronic structures supporting nonadiabatic dynamics. This study examines the predictions of cis-stilbene photochemistry using trajectory surface hopping methods coupled with various electronic structures (OM3-MRCISD, SA2-CASSCF, XMS-SA2-CASPT2, and XMS-SA3-CASPT2) and assesses their ability to interpret experimental observations. Although the excited-state lifetimes show consistency, ranging from 360 fs to 295 fs, the reaction quantum yields vary significantly. The quantum yield for cyclization ranges from nearly zero to 35% while the photoisomerization channel can either exceed 50% or be entirely suppressed completely in the second case. Intriguingly, the calculated photoelectron signal is not strikingly different for different reaction scenarios, making the methods seemingly reliable when treated separately Furthermore, analyzing stationary points on the potential energy surface does not reliably predict simulation outcomes, nor does it aid in selecting a specific method before simulations. Therefore, we advocate for incorporating sensitivity analyses in the simulation protocol. While employing an ensemble of methods is impractical, nonadiabatic simulations with external bias present a resource-efficient approach to achieve this goal.

Related Organizations
Keywords

VZ4, sensitivity analysis, stilbene photoisomerization, 214 021, VSCHT, stilbene dynamics, 214 024

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
0
Average
Average
Average