Quantum Chemical and Trajectory Surface Hopping Molecular Dynamics Study of Iodine-Based BODIPY Photosensitizer
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00618180" target="_blank" >RIV/61388963:_____/25:00618180 - isvavai.cz</a>
Alternative codes found
RIV/61388955:_____/25:00618180 RIV/00216208:11310/25:10497912
Result on the web
<a href="https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70026" target="_blank" >https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70026</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/jcc.70026" target="_blank" >10.1002/jcc.70026</a>
Alternative languages
Result language
angličtina
Original language name
Quantum Chemical and Trajectory Surface Hopping Molecular Dynamics Study of Iodine-Based BODIPY Photosensitizer
Original language description
A computational study of I-BODIPY (2- ethyl- 4,4- difluoro- 6,7- diiodo-1,3- dimethyl- 4-bora-3a,4a- diaza-s-indacene) has been carried out to investigate its key photophysical properties as a potential triplet photosensitizer capable of generating singlet oxygen. Multireference CASPT2 and CASSCF methods have been used to calculate vertical excitation energies and spin–norbit couplings (SOCs), respectively, in a model (mono-iodinated BODIPY) molecule to assess the applicability of the single- reference second- order algebraic diagrammatic construction, ADC(2), method to this and similar molecules. Subsequently, time- dependent density functional theory (TD-DFT), possibly within the Tamm–Dancoff approximation (TDA), using several exchange- correlation functionals has been tested on I-BODIPY against ADC(2), both employing a basis set with a two-component pseudopotential on the iodine atoms. Finally, the magnitudes of SOC between excited electronic states of all types found have thoroughly been discussed using the Slater–Condon rules applied to an arbitrary one- electron one- center effective spin– orbit Hamiltonian. The geometry dependence of SOCs between the lowest-lying states has also been addressed. Based on these investigations, the TD-DFT/B3LYP and TD-DFT(TDA)/BHLYP approaches have been selected as the methods of choice for the subsequent nuclear ensemble approach absorption spectra simulations and mixed quantum- classical trajectory surface hopping (TSH) molecular dynamics (MD) simulations, respectively. Two bright states in the visible spectrum of I-BODIPY have been found, exhibiting a redshift of the main peak with respect to unsubstituted BODIPY caused by theniodine substituents. Excited-state MD simulations including both non-adiabatic effects and SOCs have been performed to investigate the relaxation processes in I-BODIPY after its photoexcitation to the S1 state. The TSH MD simulations revealed that intersystem crossings occur on a time scale comparable to internal conversions and that after an initial phase of triplet population growth a “saturation” is reached where the ratio of the net triplet to singlet populations is about 4:1. The calculated triplet quantum yield of 0.85 is in qualitative agreement with the previously reported experimental singlet oxygen generation yield of 0.99 ± 0.06.
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/GA23-06364S" target="_blank" >GA23-06364S: Excited state molecular dynamics with non-adiabatic and spin-orbit effects assisted by machine learning</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
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
46
Issue of the periodical within the volume
7
Country of publishing house
US - UNITED STATES
Number of pages
20
Pages from-to
e70026
UT code for WoS article
001441395200001
EID of the result in the Scopus database
2-s2.0-105000209458