Computing excited states of molecules using normalizing flows

Fuente: arXiv
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Main Authors: Saleh, Yahya, Corral, Álvaro Fernández, Vogt, Emil, Iske, Armin, Küpper, Jochen, Yachmenev, Andrey
Format: Preprint
Published: 2023
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author Saleh, Yahya
Corral, Álvaro Fernández
Vogt, Emil
Iske, Armin
Küpper, Jochen
Yachmenev, Andrey
author_facet Saleh, Yahya
Corral, Álvaro Fernández
Vogt, Emil
Iske, Armin
Küpper, Jochen
Yachmenev, Andrey
contents Calculations of highly excited and delocalized molecular vibrational states are computationally challenging tasks, which strongly depends on the choice of coordinates for describing vibrational motions. We introduce a new method that leverages normalizing flows -- parametrized invertible functions -- to learn optimal vibrational coordinates that satisfy the variational principle. This approach produces coordinates tailored to the vibrational problem at hand, significantly increasing the accuracy and enhancing basis-set convergence of the calculated energy spectrum. The efficiency of the method is demonstrated in calculations of the 100 lowest excited vibrational states of H$_2$S, H$_2$CO, and HCN/HNC. The method effectively captures the essential vibrational behavior of molecules by enhancing the separability of the Hamiltonian and hence allows for an effective assignment of approximate quantum numbers. We demonstrate that the optimized coordinates are transferable across different levels of basis-set truncation, enabling a cost-efficient protocol for computing vibrational spectra of high-dimensional systems.
format Preprint
id arxiv_https___arxiv_org_abs_2308_16468
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Computing excited states of molecules using normalizing flows
Saleh, Yahya
Corral, Álvaro Fernández
Vogt, Emil
Iske, Armin
Küpper, Jochen
Yachmenev, Andrey
Chemical Physics
Machine Learning
Calculations of highly excited and delocalized molecular vibrational states are computationally challenging tasks, which strongly depends on the choice of coordinates for describing vibrational motions. We introduce a new method that leverages normalizing flows -- parametrized invertible functions -- to learn optimal vibrational coordinates that satisfy the variational principle. This approach produces coordinates tailored to the vibrational problem at hand, significantly increasing the accuracy and enhancing basis-set convergence of the calculated energy spectrum. The efficiency of the method is demonstrated in calculations of the 100 lowest excited vibrational states of H$_2$S, H$_2$CO, and HCN/HNC. The method effectively captures the essential vibrational behavior of molecules by enhancing the separability of the Hamiltonian and hence allows for an effective assignment of approximate quantum numbers. We demonstrate that the optimized coordinates are transferable across different levels of basis-set truncation, enabling a cost-efficient protocol for computing vibrational spectra of high-dimensional systems.
title Computing excited states of molecules using normalizing flows
topic Chemical Physics
Machine Learning
url https://arxiv.org/abs/2308.16468