A new computational framework for spinor-based relativistic exact two-component calculations using contracted basis functions

Abstract

A new computational framework for spinor-based relativistic exact two-component (X2C) calculations is developed using contracted basis sets with a spin–orbit contraction scheme. Generally contracted, j-adapted basis sets of p-block elements using primitive functions in the correlation-consistent basis sets are constructed for the X2C Hamiltonian with atomic mean-field spin–orbit integrals (the X2CAMF scheme). The contraction coefficients are taken from atomic X2CAMF Hartree–Fock spinors, thereby following the simple concept of a linear combination of atomic orbitals. Benchmark calculations of spin–orbit splittings, equilibrium bond lengths, and harmonic vibrational frequencies demonstrate the accuracy and efficacy of the j-adapted spin–orbit contraction scheme.