Numerical variational solution of hydrogen molecule and ions using one-dimensional hydrogen as basis functions
Yanoar Pribadi Sarwono, Faiz Rahman, Ruiqin Zhang
Abstract
Abstract The ground state solution of hydrogen molecule and ions are numerically obtained as an application of our scheme to solve many-electron multi-center potential Schrödinger equation by using one-dimensional hydrogen wavefunctions as basis functions. The all-electron sparse Hamiltonian matrix for the given system is generated with the standard order finite-difference method, then the electronic trial wavefunction to describe the ground state is constructed based on the molecular orbital treatment, and finally an effective and accurate iteration process is implemented to systematically improve the result. Many problems associated with the evaluation of the matrix elements of the Hamiltonian in more general basis and potential are circumvented. Compared with the standard results, the variationally obtained energy of H 2 + is within 0.1 mhartree accuracy, while that of H 2 and H 3 + include the electron correlation effect. The equilibrium bond length is highly consistent with the accurate results and the virial theorem is satisfied to an accuracy of − V / T = 2.0.