Relativistic electronic structure theory

✍ Scribed by Takahito Nakajima; Takeshi Yanai; Kimihiko Hirao

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: English
• Weight: 148 KB
• Volume: 23
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.10059

✦ Synopsis

The theoretical and technical foundations are presented for the efficient relativistic electronic structure theories to treat heavy-atomic molecular systems. This review contains two surveys of four-component and two-component quasi-relativistic approaches. First, we review our highly efficient computational scheme for four-component relativistic ab initio molecular orbital (MO) methods over generally contracted spherical harmonic Gaussian-type spinors (GTSs). Illustrative calculations, which are performed with a new four-component relativistic ab initio molecular orbital program package REL4D, clearly show the efficiency of our computational scheme by the Dirac-Hartree-Fock (DHF) and Dirac-Hartree-Fock (DKS) methods. Next, in the two-component quasi-relativistic framework, two relativistic Hamiltonians, RESC and higher order Douglas-Kroll (DK) Hamiltonians, are introduced, and several illustrative calculations are shown. Numerical results for several systems show that good accuracy can be obtained with our third-order DK (DK3) Hamiltonian.