Electronically excited states of water clusters of 7-azaindole: Structures, relative energies, and electronic nature of the excited states

The geometries of 1H-7-azaindole and the 1H-7-azaindole(H2O)(1-2) complexes and the respective 7H tautomers in their ground and two lowest electronically excited pi-pi(*) singlet states have been optimized by using the second-order approximated coupled cluster model within the resolution-of-the-identity approximation. Based on these optimized structures, adiabatic excitation spectra were computed by using the combined density functional theory/multireference configuration interaction method. Special attention was paid to comparison of the orientation of transition dipole moments and excited state permanent dipole moments, which can be determined accurately with rotationally resolved electronic Stark spectroscopy. The electronic nature of the lowest excited state is shown to change from L-b to L-a upon water complexation. (c) 2008 American Institute of Physics.