Weak interactions in alkaline earth metal dimers by pair-density functional theory

Research output: Contribution to journalArticle

Abstract

Alkaline earth dimers have small bond energies (less than 5 kcal/mol) that provide a difficult challenge for electronic structure calculations. They are especially challenging for Kohn-Sham density functional theory (KS-DFT) using generalized gradient approximations (GGAs) as the exchange-correlation density functional because GGAs often do not provide accurate results for weak interactions. Here we treat alkaline earth dimers from six different rows of the periodic table. We show that the dominant correlating configurations are the same in all six dimers. We also show that multiconfiguration pair-density functional theory (MC-PDFT) using a fully translated GGA as the on-top density functional not only performs much better than KS-DFT with GGAs in predicting equilibrium distances and dissociation energies but also performs better than the more computationally demanding complete active space second-order perturbation theory (CASPT2) with large basis sets and performs even better than CASPT2 with smaller basis sets.

Original languageEnglish (US)
Pages (from-to)799-805
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume10
Issue number4
DOIs
StatePublished - Feb 21 2019

Fingerprint

Alkaline Earth Metals
Alkaline earth metals
alkaline earth metals
Dimers
Density functional theory
dimers
density functional theory
gradients
Earth (planet)
approximation
Electronic structure
perturbation theory
dissociation
electronic structure
energy
configurations

PubMed: MeSH publication types

  • Journal Article

Cite this

Weak interactions in alkaline earth metal dimers by pair-density functional theory. / Bao, Jie J.; Gagliardi, Laura; Truhlar, Donald G.

In: Journal of Physical Chemistry Letters, Vol. 10, No. 4, 21.02.2019, p. 799-805.

Research output: Contribution to journalArticle

@article{1f969aaadd8248e6a819bbf1d865dc14,
title = "Weak interactions in alkaline earth metal dimers by pair-density functional theory",
abstract = "Alkaline earth dimers have small bond energies (less than 5 kcal/mol) that provide a difficult challenge for electronic structure calculations. They are especially challenging for Kohn-Sham density functional theory (KS-DFT) using generalized gradient approximations (GGAs) as the exchange-correlation density functional because GGAs often do not provide accurate results for weak interactions. Here we treat alkaline earth dimers from six different rows of the periodic table. We show that the dominant correlating configurations are the same in all six dimers. We also show that multiconfiguration pair-density functional theory (MC-PDFT) using a fully translated GGA as the on-top density functional not only performs much better than KS-DFT with GGAs in predicting equilibrium distances and dissociation energies but also performs better than the more computationally demanding complete active space second-order perturbation theory (CASPT2) with large basis sets and performs even better than CASPT2 with smaller basis sets.",
author = "Bao, {Jie J.} and Laura Gagliardi and Truhlar, {Donald G}",
year = "2019",
month = "2",
day = "21",
doi = "10.1021/acs.jpclett.8b03846",
language = "English (US)",
volume = "10",
pages = "799--805",
journal = "Journal of Physical Chemistry Letters",
issn = "1948-7185",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Weak interactions in alkaline earth metal dimers by pair-density functional theory

AU - Bao, Jie J.

AU - Gagliardi, Laura

AU - Truhlar, Donald G

PY - 2019/2/21

Y1 - 2019/2/21

N2 - Alkaline earth dimers have small bond energies (less than 5 kcal/mol) that provide a difficult challenge for electronic structure calculations. They are especially challenging for Kohn-Sham density functional theory (KS-DFT) using generalized gradient approximations (GGAs) as the exchange-correlation density functional because GGAs often do not provide accurate results for weak interactions. Here we treat alkaline earth dimers from six different rows of the periodic table. We show that the dominant correlating configurations are the same in all six dimers. We also show that multiconfiguration pair-density functional theory (MC-PDFT) using a fully translated GGA as the on-top density functional not only performs much better than KS-DFT with GGAs in predicting equilibrium distances and dissociation energies but also performs better than the more computationally demanding complete active space second-order perturbation theory (CASPT2) with large basis sets and performs even better than CASPT2 with smaller basis sets.

AB - Alkaline earth dimers have small bond energies (less than 5 kcal/mol) that provide a difficult challenge for electronic structure calculations. They are especially challenging for Kohn-Sham density functional theory (KS-DFT) using generalized gradient approximations (GGAs) as the exchange-correlation density functional because GGAs often do not provide accurate results for weak interactions. Here we treat alkaline earth dimers from six different rows of the periodic table. We show that the dominant correlating configurations are the same in all six dimers. We also show that multiconfiguration pair-density functional theory (MC-PDFT) using a fully translated GGA as the on-top density functional not only performs much better than KS-DFT with GGAs in predicting equilibrium distances and dissociation energies but also performs better than the more computationally demanding complete active space second-order perturbation theory (CASPT2) with large basis sets and performs even better than CASPT2 with smaller basis sets.

UR - http://www.scopus.com/inward/record.url?scp=85061958188&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85061958188&partnerID=8YFLogxK

U2 - 10.1021/acs.jpclett.8b03846

DO - 10.1021/acs.jpclett.8b03846

M3 - Article

VL - 10

SP - 799

EP - 805

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 4

ER -