Characterization of the Relevant Excited States in the Photodissociation of CO-Ligated Hemoglobin and Myoglobin

Abstract
The relevant excited states in the rapid photodissociation process of hemoglobin and myoglobin are examined by means of time-dependent density functional theory. Our calculations clearly show that the photodissociation is mediated by two repulsive states (5 A‘ ‘ and 3 A‘) which cross the lowest excited states (1 A‘ and 1 A‘ ‘) at an internuclear Fe−C distance of about 2 Å. Electron detachment/attachment density plots nicely explain the repulsive nature of the 5 A‘ ‘ and 3 A‘ states.

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