The vertical excitation energies and a lifetime of the two lowest singlet excited states of the conjugated polyenes from C2 to C22: Ab initio, DFT, and semiclassical MNDO-MD simulations
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F23%3A10475139" target="_blank" >RIV/00216208:11320/23:10475139 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=U0g8QajoEf" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=U0g8QajoEf</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/jcc.27040" target="_blank" >10.1002/jcc.27040</a>
Alternative languages
Result language
angličtina
Original language name
The vertical excitation energies and a lifetime of the two lowest singlet excited states of the conjugated polyenes from C2 to C22: Ab initio, DFT, and semiclassical MNDO-MD simulations
Original language description
Electronic excited states in the series of polyene molecules were explored. Optimal ground-state geometry was used for the evaluation of vertical excitation energies. Results of a chosen set of functionals were compared to post-HF methods (EOM-CCSD, NEVPT2, CASPT2, and MRCI). In addition, the semiempirical OM2/MNDO method using MRCISD computational level was confronted with the above-mentioned techniques. Despite the fact that the first excited state has a significant double-excitation character some functionals were able to qualitatively determine the correct state order (where the lowest excited state has a A(g)(-) character). The most successful functionals in transition energies predictions were PBE, TPSS and BLYP in Tamm-Dancoff approach (TDA), which had the smallest root-mean-square deviation (RMSD) scoring towards the experimental values. Regarding RMSD scoring, the OM2/MNDO method performed fairly well, too. Besides absorption spectra, lifetimes of the first two excited states were estimated based on a stochastic approach exploring a swarm of OM2/MNDO hopping dynamics using the Tully fewest switch algorithm for each molecule. The longest lifetime of the first excited state (S-1) was found for decapentaene (about 5 ps). Further elongation of the conjugated chain caused a mild decrease of this value to ca 1.5 ps for docosaundecaene.
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
10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)
Result continuities
Project
<a href="/en/project/GA19-06860S" target="_blank" >GA19-06860S: Time evolution of conjugated systems in excited states by surface hopping nonadiabatic molecular dynamics</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Computational Chemistry
ISSN
0192-8651
e-ISSN
1096-987X
Volume of the periodical
44
Issue of the periodical within the volume
6
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
777-787
UT code for WoS article
000892265200001
EID of the result in the Scopus database
2-s2.0-85142915409