Quantum Dynamics with ab Initio Potentials

A rapidly advancing area in chemical dynamics is the construction of chemically, and sometimes even spectroscopically, accurate global potential energy surfaces from high level ab initio calculations. This new development essentially eliminates the uncertainty in the Born-Oppenheimer potentials, allowing meaningful comparisons of dynamical calculations with experiment. Indeed, several recent studies have demonstrated that fully quantum mechanical characterizations of chemical dynamics on high quality potential energy surfaces not only reproduce observations, but also predict, and sometimes correct, experiments.

The emergence of accurate potential energy surfaces has also stimulated new quantum theory, exact and approximate. Such quantum mechanical treatments of spectroscopy and dynamics are necessary to understand quantum effects such as zero-point energy, resonances, non-adiabatic transitions, tunneling, and interference effects, in inelastic collisions, unimolecular and bimolecular reactions, photochemistry, and molecular spectroscopy.

This special topic calls for contributions from the theoretical chemical physics community on new methods and applications of quantum dynamics using ab initio electronic potential energies. These contributions may include the construction of accurate ab initio potential energy surfaces and the characterization of the quantum dynamics on these surfaces, “on the fly” simulations of quantum dynamics using ab initio potentials, or the development of novel computationally efficient quantum dynamics methods. Classical treatments of the nuclear motion in photochemistry also are within the scope of the special topic if the focus is on quantitatively accurate descriptions of electronic coherence and population dynamics, preferably verified by comparison with exact quantum calculations of the nuclear motion. We are particularly interested in theoretical studies that can be compared with experimental measurements and that reveal new physical insights in chemical dynamics.