Correlation entropy of the H2 molecule

Correlation of a quantum many-body state makes the one-particle density matrix nonidempotent. Therefore, the Shannon entropy of the natural occupation numbers measures the correlation strength on the one-particle level. Here, it is shown how this general idea of a correlation entropy must be adapted for two-electron systems in view of conservation laws which mix Slater determinants even in the noninteracting limit. Results are presented for the correlation entropy s of H2 as a function of the nucleus-nucleus separation R. In the ground state, the entropy of the spatial factor of the wave function maximizes 1.7 bohr beyond the Coulson-Fischer separation. The role of the correlation entropy in density functional theory is also discussed. © 1997 John Wiley & Sons, Inc.