Zero-Cost Estimation of Zero-Point Energies

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

An additive, linear, atom-type-based (ATB) scheme is developed allowing no-cost estimation of zero-point vibrational energies (ZPVE) of neutral, closed-shell molecules in their ground electronic states. The atom types employed correspond to those defined within the MM2 molecular mechanics force field approach. The reference training set of 156 molecules cover chained and branched alkanes, alkenes, cycloalkanes and cycloalkenes, alkynes, alcohols, aldehydes, carboxylic acids, amines, amides, ethers, esters, ketones, benzene derivatives, heterocycles, nucleobases, all the natural amino acids, some dipeptides and sugars, as well as further simple molecules and ones containing several structural units, including several vitamins. A weighted linear least-squares fit of atom-type-based ZPVE increments results in recommended values for the following atoms, with the number of atom types defined in parentheses: H(8), D(1), B(1), C(6), N(7), O(3), F(1), Si(1), P(2), S(3), and Cl(1). The average accuracy of the ATB ZPVEs is considerably better than 1 kcal mol-1, that is, better than chemical accuracy. The proposed ATB scheme could be extended to many more atoms and atom types, following a careful validation procedure; deviation from the MM2 atom types seems to be necessary, especially for third-row elements.

Original languageEnglish
Pages (from-to)10229-10240
Number of pages12
JournalJournal of Physical Chemistry A
Volume119
Issue number40
DOIs
Publication statusPublished - Oct 8 2015

Fingerprint

zero point energy
costs
Atoms
atoms
Costs
Cycloparaffins
Molecules
Benzene Derivatives
molecules
vitamins
Molecular mechanics
Alkanes
Alkynes
Ethers
Dipeptides
Alkenes
Electronic states
alkynes
sugars
Carboxylic Acids

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Zero-Cost Estimation of Zero-Point Energies. / Császár, A.; Furtenbacher, T.

In: Journal of Physical Chemistry A, Vol. 119, No. 40, 08.10.2015, p. 10229-10240.

Research output: Contribution to journalArticle

@article{642f23d670264320859cda1c766299f1,
title = "Zero-Cost Estimation of Zero-Point Energies",
abstract = "An additive, linear, atom-type-based (ATB) scheme is developed allowing no-cost estimation of zero-point vibrational energies (ZPVE) of neutral, closed-shell molecules in their ground electronic states. The atom types employed correspond to those defined within the MM2 molecular mechanics force field approach. The reference training set of 156 molecules cover chained and branched alkanes, alkenes, cycloalkanes and cycloalkenes, alkynes, alcohols, aldehydes, carboxylic acids, amines, amides, ethers, esters, ketones, benzene derivatives, heterocycles, nucleobases, all the natural amino acids, some dipeptides and sugars, as well as further simple molecules and ones containing several structural units, including several vitamins. A weighted linear least-squares fit of atom-type-based ZPVE increments results in recommended values for the following atoms, with the number of atom types defined in parentheses: H(8), D(1), B(1), C(6), N(7), O(3), F(1), Si(1), P(2), S(3), and Cl(1). The average accuracy of the ATB ZPVEs is considerably better than 1 kcal mol-1, that is, better than chemical accuracy. The proposed ATB scheme could be extended to many more atoms and atom types, following a careful validation procedure; deviation from the MM2 atom types seems to be necessary, especially for third-row elements.",
author = "A. Cs{\'a}sz{\'a}r and T. Furtenbacher",
year = "2015",
month = "10",
day = "8",
doi = "10.1021/acs.jpca.5b07156",
language = "English",
volume = "119",
pages = "10229--10240",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "40",

}

TY - JOUR

T1 - Zero-Cost Estimation of Zero-Point Energies

AU - Császár, A.

AU - Furtenbacher, T.

PY - 2015/10/8

Y1 - 2015/10/8

N2 - An additive, linear, atom-type-based (ATB) scheme is developed allowing no-cost estimation of zero-point vibrational energies (ZPVE) of neutral, closed-shell molecules in their ground electronic states. The atom types employed correspond to those defined within the MM2 molecular mechanics force field approach. The reference training set of 156 molecules cover chained and branched alkanes, alkenes, cycloalkanes and cycloalkenes, alkynes, alcohols, aldehydes, carboxylic acids, amines, amides, ethers, esters, ketones, benzene derivatives, heterocycles, nucleobases, all the natural amino acids, some dipeptides and sugars, as well as further simple molecules and ones containing several structural units, including several vitamins. A weighted linear least-squares fit of atom-type-based ZPVE increments results in recommended values for the following atoms, with the number of atom types defined in parentheses: H(8), D(1), B(1), C(6), N(7), O(3), F(1), Si(1), P(2), S(3), and Cl(1). The average accuracy of the ATB ZPVEs is considerably better than 1 kcal mol-1, that is, better than chemical accuracy. The proposed ATB scheme could be extended to many more atoms and atom types, following a careful validation procedure; deviation from the MM2 atom types seems to be necessary, especially for third-row elements.

AB - An additive, linear, atom-type-based (ATB) scheme is developed allowing no-cost estimation of zero-point vibrational energies (ZPVE) of neutral, closed-shell molecules in their ground electronic states. The atom types employed correspond to those defined within the MM2 molecular mechanics force field approach. The reference training set of 156 molecules cover chained and branched alkanes, alkenes, cycloalkanes and cycloalkenes, alkynes, alcohols, aldehydes, carboxylic acids, amines, amides, ethers, esters, ketones, benzene derivatives, heterocycles, nucleobases, all the natural amino acids, some dipeptides and sugars, as well as further simple molecules and ones containing several structural units, including several vitamins. A weighted linear least-squares fit of atom-type-based ZPVE increments results in recommended values for the following atoms, with the number of atom types defined in parentheses: H(8), D(1), B(1), C(6), N(7), O(3), F(1), Si(1), P(2), S(3), and Cl(1). The average accuracy of the ATB ZPVEs is considerably better than 1 kcal mol-1, that is, better than chemical accuracy. The proposed ATB scheme could be extended to many more atoms and atom types, following a careful validation procedure; deviation from the MM2 atom types seems to be necessary, especially for third-row elements.

UR - http://www.scopus.com/inward/record.url?scp=84943611264&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84943611264&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.5b07156

DO - 10.1021/acs.jpca.5b07156

M3 - Article

AN - SCOPUS:84943611264

VL - 119

SP - 10229

EP - 10240

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 40

ER -