One-step treatment of spin-orbit coupling and electron correlation in large active spaces

TL;DR

This paper demonstrates that heat bath configuration interaction (HCI) can effectively treat relativistic effects and electron correlation simultaneously in large active spaces, enabling accurate calculations of complex systems with manageable computational resources.

Contribution

The work introduces the application of HCI to relativistic systems with spin-orbit coupling in large active spaces, showing its ability to handle significant Hilbert space sizes and compare different relativistic Hamiltonians.

Findings

HCI can handle large active spaces with spin-orbit coupling effectively.

Converged energies achieved with over 10^7 determinants in large systems.

Different relativistic Hamiltonians vary in accuracy across atomic numbers.

Abstract

In this work we demonstrate that the heat bath configuration interaction (HCI) and its semistochastic extension can be used to treat relativistic effects and electron correlation on an equal footing in large active spaces to calculate the low energy spectrum of several systems including halogens group atoms (F, Cl, Br, I), coinage atoms (Cu, Au) and the Neptunyl(VI) dioxide radical. This work demonstrates that despite a significant increase in the size of the Hilbert space due to spin symmetry breaking by the spin-orbit coupling terms, HCI retains the ability to discard large parts of the low importance Hilbert space to deliver converged absolute and relative energies. For instance, by using just over $10^7$ determinants we get converged excitation energies for Au atom in an active space containing (150o,25e) which has over $10^{30}$ determinants. We also investigate the accuracy of five different two-component relativistic Hamiltonians in which different levels of approximations are made in deriving the one-electron and two-electrons Hamiltonians, ranging from Breit-Pauli (BP) to various flavors of exact two-component (X2C) theory. The relative accuracy of the different Hamiltonians are compared on systems that range in atomic number from first row atoms to actinides.