Electronic energy levels with the help of trajectory-guided random grid of coupled wave packets. I. Six-dimensional simulation of H2.
As a preliminary to future work on the behavior of atoms and molecules in strong time-dependent fields, we apply the coupled coherent-states (CCS) technique of multidimensional phase-space quantum dynamics to obtain Born-Oppenheimer energy levels of electrons in molecules. Unlike traditional approaches based on atomic and molecular-orbital basis sets and time-independent Schrodinger equation the CCS method exploits the solution of the time-dependent Schrodinger equation in the basis of Monte Carlo-selected trajectory-guided coherent states, which treat classical electron correlations exactly. In addition the CCS trajectories move over averaged potentials, which remove the Coulombic singularities.
Physical and Theoretical Chemistry Laboratory Oxford University, South Parks Road, Oxford OX1 3QZ, United Kingdom. dmitry.shalashilin@chem.ox.ac.uk
Dmitrii V
DV
Shalashilin
Mark S
MS
Child