Monte Carlo configuration interaction applied to multipole moments, ionisation energies and electron affinities

TL;DR

This paper demonstrates that Monte Carlo configuration interaction (MCCI) can accurately compute multipole moments, ionisation energies, and electron affinities with significantly reduced configuration space, showing promising results compared to full CI and other methods.

Contribution

The study applies MCCI to calculate multipole moments and ionisation energies, showing it as an efficient alternative to full CI with good accuracy for these properties.

Findings

MCCI yields good agreement with experimental multipole moments.

MCCI performs comparably to FCI for ionisation energies.

Electron affinities are more challenging but still comparable in absolute error.

Abstract

The method of Monte Carlo configuration interaction (MCCI) [1,2] is applied to the calculation of multipole moments. We look at the ground and excited state dipole moments in carbon monoxide. We then consider the dipole of NO, the quadrupole of the nitrogen molecule and of BH. An octupole of methane is also calculated. We consider experimental geometries and also stretched bonds. We show that these non-variational quantities may be found to relatively good accuracy when compared with FCI results, yet using only a small fraction of the full configuration interaction space. MCCI results in the aug-cc-pVDZ basis are seen to generally have reasonably good agreement with experiment. We also investigate the performance of MCCI when applied to ionisation energies and electron affinities of atoms in an aug-cc-pVQZ basis. We compare the MCCI results with full configuration-interaction quantum Monte Carlo [3,4] and `exact' non-relativistic results [3,4]. We show that MCCI could be a useful alternative for the calculation of atomic ionisation energies however electron affinities appear much more challenging for MCCI. Due to the small magnitude of the electron affinities their percentage errors can be high, but with regards to absolute errors MCCI performs similarly for ionisation energies and electron affinities.