Construction of basis sets for time-dependent studies

摘要

The common basis sets constructed for use in electronic structure calculations have been foundinadequate for the representation of electrons participating in nonadiabatic time-dependentdynamics calculations. In this paper we outline an approach to construct electronic bases bettersuited for dynamical processes such as energy deposition and charge transfer in binary collisions ofions, atoms, and molecules. Since electrons of many-atom systems commonly are represented byorbitals formed as linear combinations of atomic orbitals, the focus is on atomic basis sets. The mainidea is to construct basis sets that adequately reproduce the first few excitation energies of neutralatoms. In this paper we outline a method for such basis set construction of various levels of accuracyfor first-row atoms and give a few illustrative examples