Resonance Raman Spectroscopic and Theoretical Study of Geometry Distortion of Thiourea in 21A State

The A-band resonance Raman spectra of thiourea were obtained in water and acetonitrile solution. B3LYP/6-311++G(3df,3pd) and RCIS/6-311++G(3df,3pd) calculations were done to elucidate the ultraviolet electronic transitions, the distorted geometry structure and the saddle point of thiourea in 21A excited state, respectively. The resonance Raman spectra were assigned. The absorption spectrum and resonance Raman intensities were modeled using Heller's time-dependent wavepacket approach to resonance Raman scattering. The results indicate that largest change in the displacement takes place with the C=S stretch mode ν6 (|Δ|=0.95) and noticeable changes appear in the H5N3H6+H8N4H7 wag ν5 (|Δ|=0.19), NCN symmetric stretch+C=S stretch+N3H6+H8N4 wag ν4 (|Δ|=0.18), while the moderate intensities of 2ν15 and 4ν15 are mostly due to the large excited state frequency changes of ν15, but not due to its significant change in the normal mode displacement. The mechanism of the appearance of even overtones of the S=CN2 out of plane deformation is explored. The results indicate that a Franck-Condon region saddle point is the driving force for the quadric phonon mechanism within the standard A-term of resonance Raman scattering, which leads to the pyramidalization of the carbon center and the geometry distortion of thiourea molecule in 21A excited state.