An algorithm for quantum-mechanical nonrelativistic variational calculations of L = 0 and M = 0 states of atoms with an arbitrary number of s electrons and with three p electrons have been implemented and tested in the calculations of the ground 4S state of the nitrogen atom. The spatial part of the wave function is expanded in terms of all-electrons explicitly correlated Gaussian functions with the appropriate pre-exponential Cartesian angular factors for states with the L = 0 andM= 0 symmetry. The algorithm includes formulas for calculating the Hamiltonian and overlap matrix elements, as well as formulas for calculating the analytic energy gradient determined with respect to the Gaussian exponential parameters. The gradient is used in the variational optimization of these parameters. The Hamiltonian used in the approach is obtained by rigorously separating the center-of-mass motion from the laboratory-frame all-particle Hamiltonian, and thus it explicitly depends on the finite mass of the nucleus. With that, the mass effect on the total ground-state energy is determined.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry