NASA Logo

NTRS

NTRS - NASA Technical Reports Server

Back to Results
Analytic computation of energy derivatives - Relationships among partial derivatives of a variationally determined functionFormulas are presented relating Taylor series expansion coefficients of three functions of several variables, the energy of the trial wave function (W), the energy computed using the optimized variational wave function (E), and the response function (lambda), under certain conditions. Partial derivatives of lambda are obtained through solution of a recursive system of linear equations, and solution through order n yields derivatives of E through order 2n + 1, extending Puley's application of Wigner's 2n + 1 rule to partial derivatives in couple perturbation theory. An examination of numerical accuracy shows that the usual two-term second derivative formula is less stable than an alternative four-term formula, and that previous claims that energy derivatives are stationary properties of the wave function are fallacious. The results have application to quantum theoretical methods for the computation of derivative properties such as infrared frequencies and intensities.
Document ID
19860054553
Acquisition Source
Legacy CDMS
Document Type
Reprint (Version printed in journal)
External Source(s)
Authors
King, H. F.
(New York, State University Buffalo, United States)
Komornicki, A.
(Polyatomics Research Institute Mountain View, CA, United States)
Date Acquired
August 12, 2013
Publication Date
May 15, 1986
Publication Information
Publication: Journal of Chemical Physics
Volume: 84
ISSN: 0021-9606
Subject Category
Inorganic And Physical Chemistry
Accession Number
86A39291
Funding Number(s)
CONTRACT_GRANT: NCC2-154
CONTRACT_GRANT: NCC2-339
Distribution Limits
Public
Copyright
Other

Available Downloads

There are no available downloads for this record.
No Preview Available