Advanced perturbation scheme for efficient polarizability computations

TL;DR

This paper introduces a momentum-based perturbation scheme that significantly reduces computational costs for calculating molecular polarizability tensors, especially in grid-based quantum chemistry methods, with high accuracy and broad applicability.

Contribution

The authors develop a novel momentum-based perturbation method that is more efficient and easier to integrate into existing quantum chemistry codes than traditional energy-based schemes.

Findings

Reduces explicit computations by a factor of 30.

Achieves high accuracy with an extrapolation scheme to minimize numerical errors.

Applicable to various small molecules and symmetry groups.

Abstract

We present an efficient momentum based perturbation scheme to evaluate polarizability tensors of small molecules and at the fraction of the computational cost compared to conventional energy based perturbation schemes. Furthermore, the simplicity of the scheme allows for the seamless integration into modern quantum chemistry codes. We apply the method to systems where the wavefunctions are described on a real-space grid and are therefore not subject to finite size basis set errors. In the grid-based scheme errors can be attributed to the resolution and the size of the grid-space. The applicability and generality of the method is exhibited by calculating polarizability tensors including the dipole-dipole and up to the quadrupole-quadrupole for a series of small molecules, representing the most common symmetry groups. By a direct comparison with standard techniques based on energy perturbation we show that the method reduces the number of explicit computations by a factor of 30. Numerical errors introduced due to the arrangement of the explicit point charges are eliminated with an extrapolation scheme to the effective zero-perturbation limit.