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

TL;DR

This paper introduces a novel computational framework for relativistic two-component calculations using contracted basis functions, improving accuracy and efficiency in spin-orbit coupling computations.

Contribution

It develops a new spinor-based X2C method with contracted basis sets and a spin-orbit contraction scheme, enhancing computational performance.

Findings

Accurate spin-orbit splittings achieved

Precise equilibrium bond lengths obtained

Reliable vibrational frequency calculations

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 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, hereby following the simple concept of linear combination of atomic orbitals (LCAOs). 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.