Partition of Optical Properties Into Orbital Contributions

TL;DR

This paper introduces PNOC, a novel orbital partitioning method for analyzing nonlinear optical properties, enabling local visualization, method performance assessment, and basis set optimization for large molecular systems.

Contribution

The paper presents a new orbital-based partitioning technique (PNOC) for analyzing nonlinear optical properties, enhancing visualization and computational efficiency.

Findings

PNOC provides local visualization of optical properties.

PNOC assesses electronic structure method performance.

PNOC aids in designing efficient basis sets for large systems.

Abstract

Nonlinear optical properties (NLOPs) play a major role in photonics, electro-optics and optoelectronics, and other fields of modern optics. The design of new NLO molecules and materials has benefited from the development of computational tools to analyze the relationship between the electronic structure of molecules and its optical response. In this paper, we present a new means to analyze the response property through the partition of NLOPs in terms of orbital contributions (PNOC). This tool can be used to obtain a local representation of the NLOPs, providing a powerful visualization aid to connect the magnitude of the optical property with some parts of the molecule. Unlike other methods to analyze NLOPs, the PNOC decomposes the optical property into orbitals of the unperturbed system, furnishing this method with the ability to assess the performance of single- and multi-determinant electronic structure methods. PNOC can be also used to design small basis sets for an accurate description of large systems, saving a substantial amount of computer time for the calculation of optical properties.