Stereodynamical Control of Nonadiabatic Quenching Dynamics of OH(A2S+) by H2: Full-Dimensional Quantum Dynamics

The breakdown of the Born-Oppenheimer approximation is omnipresent in chemistry, but our detailed understanding of the nonadiabatic dynamics is still incomplete. In the present work, nonadiabatic quenching of electronically excited OH(A2S+) molecules by H2 molecules is investigated by a full-dimensional quantum dynamical method using a high quality diabatic potential energy matrix. Good agreement with experiment is found for the OH(X2P) ro-vibrational and L-doublet distributions. Furthermore, the nonadiabatic dynamics is shown to be controlled by stereodynamics, namely the orientation of the two reactants. The uncovering of a major (in)elastic channel, neglected in all previous analyses, resolves a long-standing experiment-theory disagreement concerning the branching ratio of the two electronic quenching channels.

Influence of the Pauli principle on two-cluster potential energy

We study effects of the Pauli principle on the potential energy of two-cluster systems. The object of the investigation is the lightest nuclei of p-shell with a dominant \boldsymbol{\alpha}𝛂-cluster channel. For this aim we construct matrix elements of two-cluster potential energy between cluster oscillator functions with and without full antisymmetrization. Eigenvalues and eigenfunctions of the potential energy matrix are studied in detail. Eigenfunctions of the potential energy operator are presented in oscillator, coordinate and momentum spaces. We demonstrate that the Pauli principle affects more strongly the eigenfunctions than the eigenvalues of the matrix and leads to the formation of resonance and trapped states.

Natural Frequencies of a Body of Revolution Vibrating Transversely in a Fluid

IN A PREVIOUS PAPER [1]3 a procedure for determining the natural frequencies of a body vibrating in a fluid was described and applied to a flexible circular cylinder. A more practical and more difficult application of the method, to the case of a body of revolution, is presented in the present work. As was shown in [1], the natural frequencies are given by the eigenvalues of the potential energy matrix of the elastic body with respect to an inertia matrix, the latter being derived from the mass distribution of the body and the kinetic energy of the fluid. Thus two matrices must be obtained, and since the determination of the former is a problem in elasticity, and the determination of the latter one in hydrodynamics, these will be treated in separate sections. Then, in the final section, a particular body of revolution with prescribed elastic and inertial characteristics will be assumed, and its natural frequencies of vibration in air and in water will be calculated. For vibration in water, results obtained by means of strip theory and by the present matrix technique will be compared.