A compact and accurate semi-global potential energy surface for malonaldehyde from constrained least squares regression

Wataru Mizukami, Scott Habershon, David P. Tew

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

We present a new approach to semi-global potential energy surface fitting that uses the least absolute shrinkage and selection operator (LASSO) constrained least squares procedure to exploit an extremely flexible form for the potential function, while at the same time controlling the risk of overfitting and avoiding the introduction of unphysical features such as divergences or high-frequency oscillations. Drawing from a massively redundant set of overlapping distributed multi-dimensional Gaussian functions of inter-atomic separations we build a compact full-dimensional surface for malonaldehyde, fit to explicitly correlated coupled cluster CCSD(T)(F12∗) energies with a root mean square deviations accuracy of 0.3%-0.5% up to 25 000 cm-1 above equilibrium. Importance-sampled diffusion Monte Carlo calculations predict zero point energies for malonaldehyde and its deuterated isotopologue of 14 715.4(2) and 13 997.9(2) cm-1 and hydrogen transfer tunnelling splittings of 21.0(4) and 3.2(4) cm-1, respectively, which are in excellent agreement with the experimental values of 21.583 and 2.915(4) cm-1.

Original languageEnglish
Article number144310
JournalJournal of Chemical Physics
Volume141
Issue number14
DOIs
Publication statusPublished - Jan 1 2014
Externally publishedYes

Fingerprint

Potential energy surfaces
Malondialdehyde
regression analysis
potential energy
zero point energy
shrinkage
Hydrogen
divergence
deviation
operators
oscillations
hydrogen
energy

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

A compact and accurate semi-global potential energy surface for malonaldehyde from constrained least squares regression. / Mizukami, Wataru; Habershon, Scott; Tew, David P.

In: Journal of Chemical Physics, Vol. 141, No. 14, 144310, 01.01.2014.

Research output: Contribution to journalArticle

@article{37711a54846e472a9138b95a89d9afca,
title = "A compact and accurate semi-global potential energy surface for malonaldehyde from constrained least squares regression",
abstract = "We present a new approach to semi-global potential energy surface fitting that uses the least absolute shrinkage and selection operator (LASSO) constrained least squares procedure to exploit an extremely flexible form for the potential function, while at the same time controlling the risk of overfitting and avoiding the introduction of unphysical features such as divergences or high-frequency oscillations. Drawing from a massively redundant set of overlapping distributed multi-dimensional Gaussian functions of inter-atomic separations we build a compact full-dimensional surface for malonaldehyde, fit to explicitly correlated coupled cluster CCSD(T)(F12∗) energies with a root mean square deviations accuracy of 0.3{\%}-0.5{\%} up to 25 000 cm-1 above equilibrium. Importance-sampled diffusion Monte Carlo calculations predict zero point energies for malonaldehyde and its deuterated isotopologue of 14 715.4(2) and 13 997.9(2) cm-1 and hydrogen transfer tunnelling splittings of 21.0(4) and 3.2(4) cm-1, respectively, which are in excellent agreement with the experimental values of 21.583 and 2.915(4) cm-1.",
author = "Wataru Mizukami and Scott Habershon and Tew, {David P.}",
year = "2014",
month = "1",
day = "1",
doi = "10.1063/1.4897486",
language = "English",
volume = "141",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "14",

}

TY - JOUR

T1 - A compact and accurate semi-global potential energy surface for malonaldehyde from constrained least squares regression

AU - Mizukami, Wataru

AU - Habershon, Scott

AU - Tew, David P.

PY - 2014/1/1

Y1 - 2014/1/1

N2 - We present a new approach to semi-global potential energy surface fitting that uses the least absolute shrinkage and selection operator (LASSO) constrained least squares procedure to exploit an extremely flexible form for the potential function, while at the same time controlling the risk of overfitting and avoiding the introduction of unphysical features such as divergences or high-frequency oscillations. Drawing from a massively redundant set of overlapping distributed multi-dimensional Gaussian functions of inter-atomic separations we build a compact full-dimensional surface for malonaldehyde, fit to explicitly correlated coupled cluster CCSD(T)(F12∗) energies with a root mean square deviations accuracy of 0.3%-0.5% up to 25 000 cm-1 above equilibrium. Importance-sampled diffusion Monte Carlo calculations predict zero point energies for malonaldehyde and its deuterated isotopologue of 14 715.4(2) and 13 997.9(2) cm-1 and hydrogen transfer tunnelling splittings of 21.0(4) and 3.2(4) cm-1, respectively, which are in excellent agreement with the experimental values of 21.583 and 2.915(4) cm-1.

AB - We present a new approach to semi-global potential energy surface fitting that uses the least absolute shrinkage and selection operator (LASSO) constrained least squares procedure to exploit an extremely flexible form for the potential function, while at the same time controlling the risk of overfitting and avoiding the introduction of unphysical features such as divergences or high-frequency oscillations. Drawing from a massively redundant set of overlapping distributed multi-dimensional Gaussian functions of inter-atomic separations we build a compact full-dimensional surface for malonaldehyde, fit to explicitly correlated coupled cluster CCSD(T)(F12∗) energies with a root mean square deviations accuracy of 0.3%-0.5% up to 25 000 cm-1 above equilibrium. Importance-sampled diffusion Monte Carlo calculations predict zero point energies for malonaldehyde and its deuterated isotopologue of 14 715.4(2) and 13 997.9(2) cm-1 and hydrogen transfer tunnelling splittings of 21.0(4) and 3.2(4) cm-1, respectively, which are in excellent agreement with the experimental values of 21.583 and 2.915(4) cm-1.

UR - http://www.scopus.com/inward/record.url?scp=84907983241&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84907983241&partnerID=8YFLogxK

U2 - 10.1063/1.4897486

DO - 10.1063/1.4897486

M3 - Article

VL - 141

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 14

M1 - 144310

ER -