The lowest 2A' excited state of the water-hydroxyl complex.
Vertical and adiabatic excitation energies of the lowest (2)A(') excited state in the water-hydroxyl complex have been determined using coupled cluster, multireference configuration interaction, multireference perturbation theory, and density-functional methods. A significant redshift of about 0.4 eV in the vertical excitation energy of the complex compared to that of the hydroxyl radical monomer is found with the coupled cluster calculations validating previous results. Electronic excitation leads to a structure with near-equal sharing of the hydroxyl hydrogen by both oxygen atoms and a concomitantly large redshift of the adiabatic excitation energy of approximately 1 eV relative to the vertical excitation energy. The combination of redshifts ensures that the electronic transition in the complex lies well outside the equivalent excitation in the hydroxyl radical monomer. The complex is approximately five times more strongly bound in the excited state than in the ground state.
Crawford
T Daniel
TD
Department of Chemistry, Virginia Tech, Blacksburg, VA 24061, USA. crawdad@vt.edu
Abrams
Micah L
ML
King
Rollin A
RA
Lane
Joseph R
JR
Schofield
Daniel P
DP
Kjaergaard
Henrik G
HG