Electronic structure of the S1 state in methylcobalamin: Insight from CASSCF/MC‐XQDPT2, EOM‐CCSD, and TD‐DFT calculations. Issue 12 (19th January 2013)

• Record Type: Journal Article
• Authors: Kornobis, Karina; Kumar, Neeraj; Lodowski, Piotr; Jaworska, Maria; Piecuch, Piotr; Lutz, Jesse J.; Wong, Bryan M.; Kozlowski, Pawel M.
• Is Part Of: Journal of computational chemistry. Volume 34:Issue 12(2013)
• Page Start: 987
• Page End: 1004
• Publication Date: 2013-01-19
• Subjects: Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.23204
• Languages: English
• ISSNs: 0192-8651

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The methylcobalamin cofactor (MeCbl), which is one of the biologically active forms of vitamin B<sub>12</sub>, 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 S<sub>0</sub>→S<sub>1</sub> 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<sub>M</sub><sub>e</sub> 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 S<sub>1</sub> state of MeCbl, calculations have been performed using two independent <italic>ab initio</italic> 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 <italic>ab initio</italic> methods provide a consistent description of the S<sub>1</sub> 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 S<sub>1</sub> 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. © 2013 Wiley Periodicals, Inc.</p> </abstract>