Ab Initio Calculation of UV-vis Absorption of Parent Mg, Fe, Co, Ni, Cu, and Zn Metalloporphyrins
Identifikátory výsledku
Kód výsledku v 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>
Výsledek na webu
<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>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Ab Initio Calculation of UV-vis Absorption of Parent Mg, Fe, Co, Ni, Cu, and Zn Metalloporphyrins
Popis výsledku v původním jazyce
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.
Název v anglickém jazyce
Ab Initio Calculation of UV-vis Absorption of Parent Mg, Fe, Co, Ni, Cu, and Zn Metalloporphyrins
Popis výsledku anglicky
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.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10403 - Physical chemistry
Návaznosti výsledku
Projekt
Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.
Návaznosti
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Ostatní
Rok uplatnění
2024
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
1520-510X
Svazek periodika
63
Číslo periodika v rámci svazku
22
Stát vydavatele periodika
US - Spojené státy americké
Počet stran výsledku
16
Strana od-do
10127-10142
Kód UT WoS článku
001228921600001
EID výsledku v databázi Scopus
2-s2.0-85193932381