RPA, an Accurate and Fast Method for the Computation of Static Nonlinear Optical Properties

The accurate computation of static nonlinear optical properties (SNLOPs) in large polymers requires accounting for electronic correlation effects with a reasonable computational cost. The Random Phase Approximation (RPA) used in the adiabatic connection fluctuation theorem is known to be a reliable...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2023-09, Vol.19 (18), p.6062-6069
Main Authors: Besalú-Sala, Pau, Bruneval, Fabien, Pérez-Jiménez, Ángel José, Sancho-García, Juan Carlos, Rodríguez-Mayorga, Mauricio
Format: Article
Language:English
Subjects:
Computing costs
Electric fields
Finite difference method
Letter
Nonlinear optics
Optical properties
Self consistent fields
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Summary:The accurate computation of static nonlinear optical properties (SNLOPs) in large polymers requires accounting for electronic correlation effects with a reasonable computational cost. The Random Phase Approximation (RPA) used in the adiabatic connection fluctuation theorem is known to be a reliable and cost-effective method to render electronic correlation effects when combined with density-fitting techniques and integration over imaginary frequencies. We explore the ability of the RPA energy expression to predict SNLOPs by evaluating RPA electronic energies in the presence of finite electric fields to obtain (using the finite difference method) static polarizabilities and hyperpolarizabilities. We show that the RPA based on hybrid functional self-consistent field calculations yields accurate SNLOPs as the best-tuned double-hybrid functionals developed today, with the additional advantage that the RPA avoids any system-specific adjustment.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.3c00674