On the importance of initial conditions for excited-state dynamics
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F18%3A43916695" target="_blank" >RIV/60461373:22340/18:43916695 - isvavai.cz</a>
Result on the web
<a href="https://pubs.rsc.org/en/content/articlepdf/2018/fd/c8fd00088c" target="_blank" >https://pubs.rsc.org/en/content/articlepdf/2018/fd/c8fd00088c</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/c8fd00088c" target="_blank" >10.1039/c8fd00088c</a>
Alternative languages
Result language
angličtina
Original language name
On the importance of initial conditions for excited-state dynamics
Original language description
Photodynamical simulations are increasingly used to explore photochemical mechanisms and interpret laser experiments. The vast majority of ab initio excited-state simulations are performed within semiclassical, trajectory-based approaches. Apart from underlying electronic-structure theory, the reliability of simulations is controlled by a selection of initial conditions for the classical trajectories. We discuss appropriate choices of initial conditions for simulations of different experimental arrangements: dynamics initiated by continuum-wave (CW) laser fields or triggered by ultrashort laser pulses. We introduce a new technique, CW-sampling, to treat the former case, based on the ideas of importance sampling, combined with the quantum thermostat approach based on the Generalized Langevin Equation (GLE) that allows for efficient sampling of both position and momentum space. The CW-sampling is particularly important for photodynamical processes initiated by absorption at the tail of the UV absorption spectrum. We also emphasize the importance of non-Condon effects for the dynamics. We demonstrate the performance of our approach on the photodissociation of the CF2Cl2 molecule (Freon CFC-12). A quantitative agreement with the experimental data is achieved with the use of empirical correlation energy correction (CEC) factor on top of FOMO-CASCI potential energy surfaces. © The Royal Society of Chemistry.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA18-23756S" target="_blank" >GA18-23756S: Transforming molecules with X-rays: Ab initio simulations in liquids</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Faraday Discussions
ISSN
1359-6640
e-ISSN
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Volume of the periodical
212
Issue of the periodical within the volume
May
Country of publishing house
GB - UNITED KINGDOM
Number of pages
24
Pages from-to
307-330
UT code for WoS article
000455021000015
EID of the result in the Scopus database
2-s2.0-85058875690