Time-dependent variational principle for nonlinear Hamiltonians and its application to molecules in the liquid phase

✍ Scribed by R. Cammi; J. Tomasi

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 784 KB
• Volume: 60
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1996)60:1<297::aid-qua30>3.0.co;2-9

✦ Synopsis

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, 3', which, for the systems we are considering, has the status of a free energy. An explicit use of functional I ? ' 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.