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

Pau Besalú-Sala; Fabien Bruneval; Ángel José Pérez-Jiménez; Juan Carlos Sancho-García; Mauricio Rodríguez-Mayorga

doi:10.1021/acs.jctc.3c00674

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

Pau Besalú-Sala
, Fabien Bruneval
, Ángel José Pérez-Jiménez
, Juan Carlos Sancho-García
, Mauricio Rodríguez-Mayorga^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

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.

Original language	English
Pages (from-to)	6062-6069
Number of pages	8
Journal	JCTC - Journal of chemical theory and computation
Volume	19
Issue number	18
Early online date	11 Sept 2023
DOIs	https://doi.org/10.1021/acs.jctc.3c00674
Publication status	Published - 26 Sept 2023

Bibliographical note

Funding Information:
A.J.P.-J., J.C.S.-G., and M.R.-M. acknowledge the Ministerio de Ciencia e Innovación de España for Grant No. PID2019-106114GB-I00. P.B.-S. acknowledges the financial support received from the Vrije Universiteit Amsterdam. F.B. and M.R.-M. acknowledge the financial support provided by the Cross-Disciplinary Program on Numerical Simulation of the French Alternative Energies and Atomic Energy Commission (CEA) (ABIDM project). We also acknowledge the computational resources of the Institut de Química Computacional i Catàlisi of the Universitat de Girona. Finally, the authors thank É. Brémond for the discussions related to the implementation of double-hybrid KS DFT functionals.

Publisher Copyright:
© 2023 American Chemical Society.

Funding

A.J.P.-J., J.C.S.-G., and M.R.-M. acknowledge the Ministerio de Ciencia e Innovación de España for Grant No. PID2019-106114GB-I00. P.B.-S. acknowledges the financial support received from the Vrije Universiteit Amsterdam. F.B. and M.R.-M. acknowledge the financial support provided by the Cross-Disciplinary Program on Numerical Simulation of the French Alternative Energies and Atomic Energy Commission (CEA) (ABIDM project). We also acknowledge the computational resources of the Institut de Química Computacional i Catàlisi of the Universitat de Girona. Finally, the authors thank É. Brémond for the discussions related to the implementation of double-hybrid KS DFT functionals.

Funders	Funder number
Universitat de Girona
Ministerio de Ciencia e Innovación	PID2019-106114GB-I00
Commissariat à l'Énergie Atomique et aux Énergies Alternatives

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Cite this

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

abstract = "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.",

author = "Pau Besal{\'u}-Sala and Fabien Bruneval and P{\'e}rez-Jim{\'e}nez, \{{\'A}ngel Jos{\'e}\} and Sancho-Garc{\'i}a, \{Juan Carlos\} and Mauricio Rodr{\'i}guez-Mayorga",

note = "Funding Information: A.J.P.-J., J.C.S.-G., and M.R.-M. acknowledge the Ministerio de Ciencia e Innovaci{\'o}n de Espa{\~n}a for Grant No. PID2019-106114GB-I00. P.B.-S. acknowledges the financial support received from the Vrije Universiteit Amsterdam. F.B. and M.R.-M. acknowledge the financial support provided by the Cross-Disciplinary Program on Numerical Simulation of the French Alternative Energies and Atomic Energy Commission (CEA) (ABIDM project). We also acknowledge the computational resources of the Institut de Qu{\'i}mica Computacional i Cat{\`a}lisi of the Universitat de Girona. Finally, the authors thank {\'E}. Br{\'e}mond for the discussions related to the implementation of double-hybrid KS DFT functionals. Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

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

Abstract

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