ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The generalized Hellmann-Feynman and curvature theorems are derived for the generalized Sturm-Liouville-type eigenvalue equation which is widely encountered in many branches of physics. In classical mechanics, the Sturm-Liouville eigenvalue equation primarily arises from applying the theory of small oscillations to vibration problems while, in quantum mechanics, the most important example is the time-independent Schrödinger equation. The generalized theorems, respectively, provide simple useful expressions for the first and second λ derivatives of the eigenvalue where λ is an arbitrary real parameter appearing in the eigenvalue equation. These results, which apply to both classical and quantal systems, include as special cases the well-known quantum mechanical Hellmann-Feynman and curvature theorems for the time-independent Schrödinger equation, thus unifying the formalism. This connection between classical and quantum mechanics is of interest per se, and also because classical eigenvalue equations find application in the treatment of some quantum chemical problems. Two derivations of both generalizations are presented, the first proof applying to exact and Rayleigh-Ritz (linear variational) solutions of the eigenvalue problem, and the second, more general one, to arbitrary optimal variational as well as exact solutions. Necessary and sufficient conditions for the validity of the results are discussed. To demonstrate the insight they afford, several applications of the theorems in conjunction with perturbation theory are described.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560250512
