Path integral formulation for many-electron system

✍ Scribed by H. Kawabe; H. Nagao; K. Nishikawa

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 740 KB
• Volume: 59
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1996)59:6<457::aid-qua3>3.0.co;2-x

✦ Synopsis

The Feynman path integral method is applied to the many-electron problem of quantum chemistry. We begin with constructing new closure relations in terms of the linear combination of atomic orbital (LCAO) coefficients and investigate the transition amplitude and the partition function of the system in question; then a "classical path of electrons," which is described by the time-dependent Hartree-Fock-Roothaan equation, is obtained by minimizing the action integral of the system with respect to the "electron coordinate." The next order approximation is obtained by evaluating the deviation from this classical path, which is approximately written by a Gaussian integral. The result is expected to be the random-phase approximation.