화학공학소재연구정보센터
Journal of Chemical Physics, Vol.113, No.22, 9957-9965, 2000
An improved ab initio relativistic zeroth-order regular approximation correct to order 1/c(2)
The equations of the original ab initio scalar-relativistic zeroth-order regular approximation (ZORA) and the infinite-order regular approximation (IORA) are expanded in orders of 1/c(2). It is shown that previous ZORA/IORA implementations in ab initio quantum chemistry programs were not correct to order 1/c(2), but contained imperfections leading to fictitious self-interactions. These errors can be avoided by adding exchange-type terms (coupling the large and small components) to the relativistic ZORA correction to the Hamiltonian, yielding improved ab initio relativistic zeroth- and infinite-order regular approximations that are correct to order 1/c(2). The new methods have been tested numerically by computing the total energies, orbital energies, and static electric dipole polarizabilities of the rare gas atoms He through Xe.