Nonadiabatic effects in the photodissociation of H2S in the first absorption band : an ab initio study

• Published in: The Journal of chemical physics 1993-04, Vol.98 (7), p.5508-5525
• Main Authors: HEUMANN, B, WEIDE, K, DÜREN, R, SCHINKE, R
• Format: Article
• Language: English
• Subjects: Atomic and molecular physics; Exact sciences and technology; Molecular properties and interactions with photons; Molecular spectra; Physics
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.465063

The photodissociation of H2S through excitation in the first absorption band (λ≊195 nm) is investigated by means of extensive ab initio calculations. Employing the MRD-CI method we calculate the potential energy surfaces for the lowest two electronic states of 1A″ symmetry varying both HS bond distances as well as the HSH bending angle. (In the C2v point group these states have electronic symmetry 1B1 and 1A2, respectively.) The lower adiabatic potential energy surface is dissociative when one H atom is pulled away whereas the upper one is binding. For the equilibrium angle of 92° in the electronic ground state they have two conical intersections, one occurring near the Franck–Condon point. Because of the very small energy separation between these two states nonadiabatic coupling induced by the kinetic energy operator in the nuclear degrees of freedom are substantial and must be incorporated in order to describe the absorption and subsequent dissociation process in a realistic way. In the present work we treat the coupling between the two electronic states in a diabatic representation extracting the coordinate-dependent mixing angle from the CI coefficients of the electronic wave functions. The nuclear motion is treated in three dimensions in an exact quantum mechanical approach by propagation of a two-component time-dependent wave packet. The calculated absorption spectra for H2S and D2S satisfactorily agree with the measured spectra. In particular, the calculations reproduce the diffuse structures with energy spacing of about 1200 and 850 cm−1 for H2S and D2S, respectively. Furthermore, the calculated rotational- and vibrational-state distributions of the HS and DS fragments reproduce recent measurements in a convincing way. The photodissociation of H2S is a prototype for very fast electronic predissociation. The photon preferentially excites the binding (diabatic) state. This state, however, is quickly depleted by strong coupling to the dissociative (diabatic) state with the complex finally breaking up into products H and HS. The electronic quenching takes place on the time scale of one internal vibrational period only. Our calculations unambiguously confirm that the diffuse structures superimposed to the broad background are caused by symmetric stretch motion—in the binding state—and not by activity in the bending mode as originally assumed.