화학공학소재연구정보센터
Journal of Chemical Physics, Vol.121, No.19, 9389-9395, 2004
On the ultraviolet photodissociation of H2Te
The photodissociation of H2Te through excitation in the first absorption band is investigated by means of multireference spin-orbit configuration interaction (CI) calculations. Bending potentials for low-lying electronic states of H2Te are obtained in C-2v symmetry for Te-H distances fixed at the ground state equilibrium value of 3.14a(0), as well as for the minimum energy path constrained to R-1=R-2. Asymmetric cuts of potential energy surfaces for excited states (at R-1=3.14a(0) and theta=90.3degrees) are obtained for the first time. It is shown that vibrational structure in the 380-400 nm region of the long wavelength absorption tail is due to transitions to 3A('), which has a shallow minimum at large HTe-H separations. Transitions to this state are polarized in the molecular plane, and this state converges to the excited TeH((2)Pi(1/2))+H(S-2) limit. These theoretical data are in accord with the selectivity toward TeH((2)Pi(1/2)) relative to TeH((2)Pi(3/2)) that has been found experimentally for 355 nm H2Te photodissociation. The calculated 3A'<--(X) over tildeA' transition dipole moment increases rapidly with HTe-H distance; this explains the observation of 3A(') vibrational structure for low vibrational levels, despite unfavorable Franck-Condon factors. According to the calculated vertical energies and transition moment data, the maximum in the first absorption band at approximate to245 nm is caused by excitation to 4A", which has predominantly 2(1)A(") (B-1(1) in C-2v symmetry) character. (C) 2004 American Institute of Physics.