Generalized Integral Hellmann-Feynam Theorem and Configuration Interaction in Crystal Field Theory

[摘要] The integral Hellmann-Feynman Theorem of Parr is generalized to give a full significance to the off-diagonal form, and certain aspects of it are discussed. By use of the generalized form of the theorem, effects of configuration interaction to the crystal field theory are examined, taking perturbation energies of all order collectively into account. Thus, it is shown that there do not exist, especially when the field is strong, the radial integral which is common to all states characterized by, ¥Ó, S and m, and could be parametrized. If, however, one restricts the perturbing excited states only to those angularly undistorted and radially equally distorted, there results simple scaling of the crystal field parameter 10 Dq and Condon-Slater parameter Fn defined within the framework of the classical crystal field theory.

[学科分类] 化学（综合）