Ab Initio Calculation of UV-vis Absorption of Parent Mg, Fe, Co, Ni, Cu, and Zn Metalloporphyrins
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00586513" target="_blank" >RIV/61388963:_____/24:00586513 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1021/acs.inorgchem.3c04460" target="_blank" >https://doi.org/10.1021/acs.inorgchem.3c04460</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.3c04460" target="_blank" >10.1021/acs.inorgchem.3c04460</a>
Alternative languages
Result language
angličtina
Original language name
Ab Initio Calculation of UV-vis Absorption of Parent Mg, Fe, Co, Ni, Cu, and Zn Metalloporphyrins
Original language description
Relativistic restricted active space (RAS) second-order multireference perturbation theory (MRPT2) methods, incorporating spin-orbit (SO) coupling perturbatively via state interaction (SO-MRPT2/RASSCF), were used to reproduce the absorption spectra of parent metalloporphyrins containing the Mg2+, Zn2+, Co2+, Ni2+, Cu2+, or FeCl2+ ions in the 12,500-40,000 cm(-1) region. Particular attention was paid to the interaction between the porphyrin ring and the metal 3d electrons in states of different multiplicities (we used metal 3d and double d-shell or 3d' orbitals). For this class of compounds, the N-electron valence state perturbation theory (NEVPT2) method is superior to the complete active space perturbation theory (CASPT2) and successfully reproduces the energies of all four characteristic transitions (Q, B, N, and L) of closed-shell metalloporphyrins. Inclusion of SO coupling was found to have very little effect on excitation energies and oscillator strengths. For FeCl2+ porphyrin, we treated ligand-to-metal charge-transfer (LMCT, pi,d), metal ligand field (d,d), and metal-to-ligand charge-transfer (MLCT, d,pi*) transitions within the same framework. The broad and intense spectral features associated with its B (Soret) band are attributed to multiconfigurational LMCT (d,pi*) bands involving strong metal-ligand orbital mixing.
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
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
63
Issue of the periodical within the volume
22
Country of publishing house
US - UNITED STATES
Number of pages
16
Pages from-to
10127-10142
UT code for WoS article
001228921600001
EID of the result in the Scopus database
2-s2.0-85193932381