화학공학소재연구정보센터
Journal of Chemical Physics, Vol.106, No.23, 9483-9496, 1997
A Quantum Dynamical Study of CH Overtones in Fluoroform .2. Eigenstate Analysis of the V(CH)=1 and V(CH)=2 Regions
In this series, the multiple time scales and mechanisms of intramolecular vibrational-energy redistribution (IVR) present in the CH overtones of fluoroform is investigated. In part II, we analyze the ab initio vibrational spectrum and dynamics of the upsilon(CH)=1 and upsilon(CH)=2 regions, explicitly treating all vibrational degrees of freedom. A wave operator sorting algorithm is used to develop an efficient vibrational basis. Spectral transformation, by a filtered-lanczos method, is used to accelerate eigenstate analysis. The theoretical spectrum of the fundamental is nontrivial, predicting a close triplet of lines (width <6 cm(-1)) centered at 3048.3 cm(-1) and a weak line 20 cm(-1) upfield, due to coupling with a small subsystem of background modes : nu(4)(+/-) + nu(5)(+/-) + nu(6)(+/-), nu(2)(+/-) + nu(4)(+/-) + nu(6)(+/-), nu(3) + (2) nu(5). Furthermore, these background states mix with one another and other nearby background states via resonances omega(5) approximate to (omega(3) + omega(6)), omega(2) approximate to omega(5), and (omega(4) + omega(6)) approximate to (omega(3) + omega(5)). An effective Hamiltonian is used to assess chromophore-background and background-background coupling. In contrast, the first overtone exhibits no strong background resonances, rather the background modes function as a weakly coupled reservoir. IVR time scales and eigenstate convergence, with respect to the active space, are presented.