Citation: Theodore E. Wiley, Brenden C. Arruda, Nicholas A. Miller, Michael Lenard, Roseanne J. Sension. Excited electronic states and internal conversion in cyanocobalamin[J]. Chinese Chemical Letters, ;2015, 26(4): 439-443. doi: 10.1016/j.cclet.2015.03.003 shu

Excited electronic states and internal conversion in cyanocobalamin

1.
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055, USA

Corresponding author: Roseanne J. Sension,
Received Date: 22 December 2014
Available Online: 15 January 2015
Fund Project:

Cyanocobalamin (CNCbl) is a paradigm system for the study of excited electronic states and biological cofactors including the B₁₂ vitamers. The photophysics of CNCbl has been thoroughly investigated using both ultrafast spectroscopy and time dependent density functional theory (TD-DFT). Herewe review the spectroscopic and theoretical investigations of CNCbl with emphasis on the nature of S₁, the lowest excited electronic state, and extend the spectroscopic measurements to include the ultraviolet region of the spectrum. Ultrafast transient absorption measurements in the visible αβ band region and in the midinfrared led to assignment of the S₁ state to a ligand-to-metal charge transfer (LMCT) with lengthened axial bonds and a ~3 kcal/mol barrier for internal conversion to the ground state. The present measurements encompassing the γ band region of the spectrum provide further support for the assignment of the S₁ state. The experiments are in good agreement with the results of TD-DFT calculations which confirm the expected lengthening of the axial bonds in S₁ and account for the observed barrier for internal conversion back to the ground state.
- Cyanocobalamin,
- Excited electronic states,
- Ultrafast spectroscopy,
- Time dependent density functional theory,
- Ligand-to-metal charge transfer
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