Double Excitation Energies from Quantum Monte Carlo Using State-Specific Energy Optimization

Stuart Shepard; Ramón L. Panadés-Barrueta; Saverio Moroni; Anthony Scemama; Claudia Filippi

doi:10.1021/acs.jctc.2c00769

Double Excitation Energies from Quantum Monte Carlo Using State-Specific Energy Optimization

Stuart Shepard^*, Ramón L. Panadés-Barrueta, Saverio Moroni, Anthony Scemama, Claudia Filippi

^*Corresponding author for this work

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

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Abstract

We show that recently developed quantum Monte Carlo methods, which provide accurate vertical transition energies for single excitations, also successfully treat double excitations. We study the double excitations in medium-sized molecules, some of which are challenging for high-level coupled-cluster calculations to model accurately. Our fixed-node diffusion Monte Carlo excitation energies are in very good agreement with reliable benchmarks, when available, and provide accurate predictions for excitation energies of difficult systems where reference values are lacking.

Original language	English
Pages (from-to)	6722-6731
Number of pages	10
Journal	Journal of chemical theory and computation
Volume	18
Issue number	11
DOIs	https://doi.org/10.1021/acs.jctc.2c00769
Publication status	Published - 31 Oct 2022

Keywords

UT-Hybrid-D

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Shepard-2022-Double-excitation-energies-from-quaFinal published version, 2.16 MBLicence: CC BY

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title = "Double Excitation Energies from Quantum Monte Carlo Using State-Specific Energy Optimization",

abstract = "We show that recently developed quantum Monte Carlo methods, which provide accurate vertical transition energies for single excitations, also successfully treat double excitations. We study the double excitations in medium-sized molecules, some of which are challenging for high-level coupled-cluster calculations to model accurately. Our fixed-node diffusion Monte Carlo excitation energies are in very good agreement with reliable benchmarks, when available, and provide accurate predictions for excitation energies of difficult systems where reference values are lacking.",

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author = "Stuart Shepard and Panad{\'e}s-Barrueta, {Ram{\'o}n L.} and Saverio Moroni and Anthony Scemama and Claudia Filippi",

note = "Funding Information: We thank Pierre-Fran{\c c}ois Loos for useful discussions. This work was supported by the European Centre of Excellence in Exascale Computing TREX─Targeting Real Chemical Accuracy at the Exascale. This project has received funding from the European Union{\textquoteright}s Horizon 2020─Research and Innovation program─under grant agreement no. 952165. The calculations were carried out on the Dutch national supercomputer Cartesius with the support of SURF Cooperative. Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

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month = oct,

day = "31",

doi = "10.1021/acs.jctc.2c00769",

language = "English",

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AU - Shepard, Stuart

AU - Panadés-Barrueta, Ramón L.

AU - Moroni, Saverio

AU - Scemama, Anthony

AU - Filippi, Claudia

N1 - Funding Information: We thank Pierre-François Loos for useful discussions. This work was supported by the European Centre of Excellence in Exascale Computing TREX─Targeting Real Chemical Accuracy at the Exascale. This project has received funding from the European Union’s Horizon 2020─Research and Innovation program─under grant agreement no. 952165. The calculations were carried out on the Dutch national supercomputer Cartesius with the support of SURF Cooperative. Publisher Copyright: © 2022 American Chemical Society.

PY - 2022/10/31

Y1 - 2022/10/31

N2 - We show that recently developed quantum Monte Carlo methods, which provide accurate vertical transition energies for single excitations, also successfully treat double excitations. We study the double excitations in medium-sized molecules, some of which are challenging for high-level coupled-cluster calculations to model accurately. Our fixed-node diffusion Monte Carlo excitation energies are in very good agreement with reliable benchmarks, when available, and provide accurate predictions for excitation energies of difficult systems where reference values are lacking.

AB - We show that recently developed quantum Monte Carlo methods, which provide accurate vertical transition energies for single excitations, also successfully treat double excitations. We study the double excitations in medium-sized molecules, some of which are challenging for high-level coupled-cluster calculations to model accurately. Our fixed-node diffusion Monte Carlo excitation energies are in very good agreement with reliable benchmarks, when available, and provide accurate predictions for excitation energies of difficult systems where reference values are lacking.

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Double Excitation Energies from Quantum Monte Carlo Using State-Specific Energy Optimization

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