We extend our ab initio molecular dynamics methods to more exact wave functions, including complete active space multiconfiguration self-consistent-field (CASSCF) and full configuration interaction (full CI) wave functions. These extensions are critical for describing properly the dynamics of bond formation/ dissociation and isomerization, as we illustrate here by examining the bond dissociation/formation of Na2 and the isomerization ("pseudorotation") of Na3 with full CI dynamics. Equivalencing of all three atoms of Na3 is found to proceed first via facile inversions through linear structures, which occur more often than conventional pseudorotation (via obtuse to acute to obtuse isosceles triangles).
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry