| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 5390578 | Chemical Physics Letters | 2006 | 4 Pages |
Abstract
The concept of a Born-Oppenheimer (BO) potential energy surface (PES) has been extended to non-adiabatic wavefunctions by Hunter and by Wilson. A Hunter non-adiabatic PES corresponding to an excited vibrational state has a set of spikes superimposed on a BO-like PES. It was believed that Wilson PESs were spike-free. We show that it is not the case and that the Wilson PES value at a given nuclear configuration is not the expectation value of a quantum observable but a quotient of such expectation values. Consequently, BO PESs have the quantum interpretation of quotients of approximate expectation values of observables.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Patrick Cassam-Chenaï,