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research article

Machine learning models of the energy curvature vs particle number for optimal tuning of long-range corrected functionals

Fabrizio, Alberto  
•
Meyer, Benjamin  
•
Corminboeuf, Clemence  
April 21, 2020
Journal Of Chemical Physics

The average energy curvature as a function of the particle number is a molecule-specific quantity, which measures the deviation of a given functional from the exact conditions of density functional theory. Related to the lack of derivative discontinuity in approximate exchange-correlation potentials, the information about the curvature has been successfully used to restore the physical meaning of Kohn-Sham orbital eigenvalues and to develop non-empirical tuning and correction schemes for density functional approximations. In this work, we propose the construction of a machine-learning framework targeting the average energy curvature between the neutral and the radical cation state of thousands of small organic molecules (QM7 database). The applicability of the model is demonstrated in the context of system-specific gamma-tuning of the LC-omega PBE functional and validated against the molecular first ionization potentials at equation-of-motion coupled-cluster references. In addition, we propose a local version of the non-linear regression model and demonstrate its transferability and predictive power by determining the optimal range-separation parameter for two large molecules relevant to the field of hole-transporting materials. Finally, we explore the underlying structure of the QM7 database with the t-SNE dimensionality-reduction algorithm and identify structural and compositional patterns that promote the deviation from the piecewise linearity condition.

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Type
research article
DOI
10.1063/5.0005039
Web of Science ID

WOS:000529233100001

Author(s)
Fabrizio, Alberto  
Meyer, Benjamin  
Corminboeuf, Clemence  
Date Issued

2020-04-21

Publisher

AMER INST PHYSICS

Published in
Journal Of Chemical Physics
Volume

152

Issue

15

Article Number

154103

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

nonlinear dimensionality reduction

•

frontier orbital energies

•

density functionals

•

delocalization error

•

small molecules

•

parameters

•

landscapes

•

discontinuities

•

transferability

•

performance

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCMD  
Available on Infoscience
May 14, 2020
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/168724
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