NATURAL ORBITAL ANALYSIS OF NON-ADIABATIC H2+ WAVE-FUNCTIONS

Previously determined nonadiabatic wave functions for H2+ (containing several hundred terms) are analyzed by using natural orbitals. This is the first time that the natural orbital concept has been applied to other than purely electronic wave functions. We find that the natural orbital expansion converges rapidly and that five or six terms are sufficient to reproduce the exact expectation values. Several plots are given of the orbitals so found and these allow a visualization of the somewhat abstract nonadiabatic wave function in a format more reminiscent of everyday quantum‐mechanical pictures. Copyright © 1979 John Wiley & Sons, Inc.