title: Electronic structure of the S1 state in methylcobalamin: insight from CASSCF/MC-XQDPT2, EOM-CCSD, and TD-DFT calculations.
abstract: The methylcobalamin cofactor (MeCbl), which is one of the biologically active forms of vitamin B12, has been the subject of many spectroscopic and theoretical investigations. Traditionally, the lowest-energy part of the photoabsorption spectrum of MeCbl (the so-called α/β band) has been interpreted as an S0→S1 electronic transition dominated by π→π* excitations associated with the C=C stretching of the corrin ring. However, a more quantitative band-shape analysis of the α/β spectral region, along with circular dichroism (CD), magnetic CD, and resonance Raman data, has revealed the presence of a second electronic transition that involves the Co-C(Me) bond weakening. Conversely, the lowest-energy excitations based on transient absorption spectroscopy measurements have been interpreted as metal-to-ligand charge transfer (MLCT) transitions. To resolve the existing controversy about the interpretation of the S1 state of MeCbl, calculations have been performed using two independent ab initio wavefunction-based methods. These include the modified variant of the second-order multiconfigurational quasi-degenerate perturbation theory (MC-XQDPT2), using complete active space self-consistent field orbitals, and the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) approach using restricted Hartree-Fock orbitals. It is shown that both ab initio methods provide a consistent description of the S1 state as having an MLCT character. In addition, the performance of different types of functionals, including hybrid (B3LYP, MPW1PW91, TPSSh), generalized-gradient-approximation-type (GGA-type) (BP86, BLYP, MPWPW91), meta-GGA (TPSS), and range-separated (CAM-B3LYP, LC-BLYP) approaches, has been examined and the results of the corresponding time-dependent density functional theory calculations have been benchmarked against the MC-XQDPT2 and EOM-CCSD data. The hybrid functionals support the interpretation in which the S1 state represents a π→π* transition localized on corrin, while pure GGA, meta-GGA, and LC-BLYP functionals produce results consistent with the MLCT assignment.
authors: Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
authors: Karina
authors: K
authors: Kornobis
authors: Neeraj
authors: N
authors: Kumar
authors: Piotr
authors: P
authors: Lodowski
authors: Maria
authors: M
authors: Jaworska
authors: Piotr
authors: P
authors: Piecuch
authors: Jesse J
authors: JJ
authors: Lutz
authors: Bryan M
authors: BM
authors: Wong
authors: Pawel M
authors: PM
authors: Kozlowski
mesh_terms: D004583:Electrons; D015394:Molecular Structure; D011789:Quantum Theory; D014805:Vitamin B 12 / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: C019476:mecobalamin; D014805:Vitamin B 12