No abstract

No abstract

A new hierarchical expansion of the kinetic energy operator in curvilinear coordinates is presented and modified vibrational self-consistent field (VSCF) equations are derived including all kinematic effects within the mean field approximation. The new concept for the kinetic energy operator is based on many-body expansions for all G matrix elements and its determinant. As a test application VSCF computations were performed on the H(2)O(2) molecule using an analytic potential (PCPSDE) and different hierarchical approximations for the kinetic energy operator. The results indicate that coordinate-dependent reduced masses account for the largest part of the kinetic energy. Neither kinematic couplings nor derivatives of the G matrix nor its determinant had significant effects on the VSCF energies. Only the zero-point value of the pseudopotential yields an offset to absolute energies which, however, is irrelevant for spectroscopic problems.

The hierarchical expansion of the kinetic energy operator in curvilinear coordinates presented earlier for the vibrational self-consistent field technique is extended to the vibrational configuration interaction (VCI) method. The high accuracy of the modified VCI method is demonstrated by computing first excitation energies of the H(2)O(2) molecule using an analytic potential (PCPSDE) and showing convergence to accurate results from full dimensional discrete variable representation calculations.

A two-dimensional model for hydrogen pair exchange in transition metal trihydrides is used to interpret NMR data observed for [cp(PPh3)IrH3]+. Inspired by quantum chemical results for [cp(PH3)IrH3]+, the model describes a combined process of rotational tunneling and IrH2 bending that merges into an H2 “lift-off’’ motion at a small proton–proton distance. The condensed environment with which the tunneling system interacts is represented by a heat bath. A second-order perturbation treatment yields a master equation for the populations of the vibrational states within each of the rotational symmetry species A and B and for the respective AB coherences. A theoretical basis is provided for the evolution of the tunneling (AB) coherence as a damped oscillation in agreement with an independent treatment very recently published by Szymanski [J. Chem. Phys. 104, 8216 (1996)]. A simplified model assumption, containing one adjustable parameter, is made for the system–bath interaction. The temperature-dependent frequency of the tunneling process is found to be close to the Boltzmann average of the tunnel frequencies in the individual vibrational states. Both the calculated temperature-dependent coherence damping-rate constant and the tunnel frequency fit the experimental data after adjustment of three parameters describing the potential energy surface and of the parameter representing the system–bath interaction strength.