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Time‐dependent variational principle for nonlinear Hamiltonians and its application to molecules in the liquid phase
Author(s) -
Cammi R.,
Tomasi J.
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)60:1<297::aid-qua30>3.0.co;2-9
Subject(s) - variational principle , nonlinear system , variety (cybernetics) , wave function , phase (matter) , energy (signal processing) , point (geometry) , statistical physics , energy functional , physics , computer science , classical mechanics , mathematics , quantum mechanics , geometry , artificial intelligence
The formulation of the time‐dependent Frenkel variational principle for Hamiltonians containing a term depending on the wave function is here considered. Starting from the basic principles, it is shown that it requires the introduction of a related functional, G, which, for the systems we are considering, has the status of a free energy. An explicit use of functional G as starting point to obtain variational wave functions makes it easier to implement computational methods for a variety of physical and chemical problems in solution, the first one among them being the calculation of frequency‐dependent nonlinear optical properties of components of the liquid phase. A concise overview of applications of this approach which are presently being worked out in our laboratory is also given. © 1996 John Wiley & Sons, Inc.