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:
A generalization of the Gibbs-Bogoliubov inequality F ≤ F0 + 〈H - H0〉0 for the free energy F is studied which leads to a variation principle for this quantity that may be of importance in certain computational applications to quantum systems. This approach is coupled with a study of the perturbation expansion of the free energy for a canonical ensemble with H = H0 + λV in the general case when H0 and V do not commute. The second- and high-order derivatives of the free energy with respect to the perturbation parameter λ are calculated. From the second-order term is finally obtained a second-order correction to the previous variational minimum for the free energy.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560350619
