title: Electronically excited states of vitamin B12: benchmark calculations including time-dependent density functional theory and correlated ab initio methods.
abstract: Time-dependent density functional theory (TD-DFT) and correlated ab initio methods have been applied to explore the electronically excited states of vitamin B(12) (cyanocobalamin or CNCbl). Different experimental techniques have been used to probe the excited states of CNCbl, revealing many issues that remain poorly understood from an electronic structure point of view. Due to its efficient scaling with size, TD-DFT emerges as one of the most practical tools that can be used to study the electronic properties of these fairly complex molecules. However, the description of excited states is strongly dependent on the type of functional used in the calculations. In the present contribution, the choice of a proper functional for vitamin B(12) was evaluated in terms of its agreement with both experimental results and correlated ab initio calculations. Three different functionals, i.e., B3LYP, BP86, and LC-BLYP, were tested. In addition, the effect of the relative contributions of DFT and HF to the exchange-correlation functional was investigated as a function of the range-separation parameter, μ. The issues related to the underestimation of charge-transfer excitation energies by TD-DFT were validated by the Λ diagnostic, which measures the spatial overlap between occupied and virtual orbitals involved in the particular excitation. The nature of the low-lying excited states was also analyzed based on a comparison of TD-DFT and ab initio results. Based on an extensive comparison with experimental results and ab initio benchmark calculations, the BP86 functional was found to be the most appropriate in describing the electronic properties of CNCbl. Finally, an analysis of electronic transitions and reassignment of some excitations were discussed.
authors.affiliation: Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
authors.forename: Karina
authors.initials: K
authors.lastname: Kornobis
authors.forename: Neeraj
authors.initials: N
authors.lastname: Kumar
authors.forename: Bryan M
authors.initials: BM
authors.lastname: Wong
authors.forename: Piotr
authors.initials: P
authors.lastname: Lodowski
authors.forename: Maria
authors.initials: M
authors.lastname: Jaworska
authors.forename: Tadeusz
authors.initials: T
authors.lastname: Andruniów
authors.forename: Kenneth
authors.initials: K
authors.lastname: Ruud
authors.forename: Pawel M
authors.initials: PM
authors.lastname: Kozlowski
mesh_terms: D004563:Electrochemistry; D004579:Electron Transport; D004581:Electronics / Q000379:methods; D004735:Energy Transfer; D008956:Models, Chemical; D015394:Molecular Structure; D011789:Quantum Theory; D014805:Vitamin B 12 / Q000737:chemistry*; D014803:Vitamin B Complex / Q000737:chemistry
chemical_list: D014803:Vitamin B Complex; D014805:Vitamin B 12