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research article

Accurate molecular polarizabilities with coupled cluster theory and machine learning

Wilkins, David M.  
•
Grisafi, Andrea  
•
Yang, Yang
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2019
Proceedings Of The National Academy Of Sciences Of The United States Of America (PNAS)

The molecular dipole polarizability describes the tendency of a molecule to change its dipole moment in response to an applied electric field. This quantity governs key intra- and intermolecular interactions, such as induction and dispersion; plays a vital role in determining the spectroscopic signatures of molecules; and is an essential ingredient in polarizable force fields. Compared with other ground-state properties, an accurate prediction of the molecular polarizability is considerably more difficult, as this response quantity is quite sensitive to the underlying electronic structure description. In this work, we present highly accurate quantum mechanical calculations of the static dipole polarizability tensors of 7,211 small organic molecules computed using linear response coupled cluster singles and doubles theory (LR-CCSD). Using a symmetry-adapted machine-learning approach, we demonstrate that it is possible to predict the LR-CCSD molecular polarizabilities of these small molecules with an error that is an order of magnitude smaller than that of hybrid density functional theory (DFT) at a negligible computational cost. The resultant model is robust and transferable, yielding molecular polarizabilities for a diverse set of 52 larger molecules (including challenging conjugated systems, carbohydrates, small drugs, amino acids, nucleobases, and hydrocarbon isomers) at an accuracy that exceeds that of hybrid DFT. The atom-centered decomposition implicit in our machine-learning approach offers some insight into the shortcomings of DFT in the prediction of this fundamental quantity of interest.

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Type
research article
DOI
10.1073/pnas.1816132116
Web of Science ID

WOS:000459694400016

Scopus ID

2-s2.0-85062028573

Author(s)
Wilkins, David M.  
Grisafi, Andrea  
Yang, Yang
Lao, Ka Un
DiStasio, Robert A.
Ceriotti, Michele  
Date Issued

2019

Published in
Proceedings Of The National Academy Of Sciences Of The United States Of America (PNAS)
Volume

116

Issue

9

Start page

3401

End page

3406

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
COSMO  
Available on Infoscience
September 7, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/160919
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