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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

  • Czech description

Classification

  • Type

    J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database

  • CEP classification

  • 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

  • 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