| Autor: |
Ganguly G; Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague 6 16610, Czech Republic., Havlas Z; Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague 6 16610, Czech Republic., Michl J; Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague 6 16610, Czech Republic.; Department of Chemistry, University of Colorado, Boulder, Colorado 80309, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2024 Jun 03; Vol. 63 (22), pp. 10127-10142. Date of Electronic Publication: 2024 May 21. |
| DOI: |
10.1021/acs.inorgchem.3c04460 |
| Abstrakt: |
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 Mg 2+ , Zn 2+ , Co 2+ , Ni 2+ , Cu 2+ , or FeCl 2+ ions in the 12,500-40,000 cm -1 region. Particular attention was paid to the interaction between the porphyrin ring and the metal 3 d electrons in states of different multiplicities (we used metal 3 d and double d -shell or 3 d ' 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 FeCl 2+ porphyrin, we treated ligand-to-metal charge-transfer (LMCT; π ,d ), metal ligand field ( d,d ), and metal-to-ligand charge-transfer (MLCT; d ,π*) transitions within the same framework. The broad and intense spectral features associated with its B (Soret) band are attributed to multiconfigurational LMCT ( d ,π*) bands involving strong metal-ligand orbital mixing. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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