Binding energy curves from nonempirical density functionals. I. Covalent bonds in closed-shell and radical molecules

Adrienn Ruzsinszky, John P. Perdew, G. Csonka

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Binding or potential energy curves have been calculated for the ground-state diatomics H2+, He2+, LiH+, H2, N2, and C2, for the transition state H3, and for the triplet first excited state of H2 using the nonempirical density functionals from the first three rungs of a ladder of approximations: the local spin density (LSD) approximation, the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and the Tao-Perdew-Staroverov-Scuseria (TPSS) meta GGA. Good binding energy curves in agreement with coupled cluster or configuration interaction calculations are found from the PBE GGA and especially from the TPSS meta GGA. Expected exceptions are the symmetric radicals H2+ and He 2+, where the functionals suffer from self-interaction error, and the exotically bonded C2. Although the energy barrier for the reaction H2 + H → H + H2 is better in PBE than in TPSS, the transition state H3 is a more properly positioned and curved saddle point of the energy surface in TPSS. The triplet first excited state of H2 obeys the Aufbau principle and thus is one of the exceptional excited states that are computable in principle from the ground-state functional. The PBE GGA and TPSS meta GGA are useful not only for chemical applications but also for the construction of higher-rung nonempirical functionals that can further improve the binding energy curves.

Original languageEnglish
Pages (from-to)11006-11014
Number of pages9
JournalJournal of Physical Chemistry A
Volume109
Issue number48
DOIs
Publication statusPublished - Dec 8 2005

Fingerprint

Covalent bonds
covalent bonds
Binding energy
Excited states
functionals
binding energy
Ground state
Molecules
curves
approximation
gradients
molecules
Energy barriers
Ladders
Potential energy
Interfacial energy
excitation
ground state
saddle points
ladders

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Binding energy curves from nonempirical density functionals. I. Covalent bonds in closed-shell and radical molecules. / Ruzsinszky, Adrienn; Perdew, John P.; Csonka, G.

In: Journal of Physical Chemistry A, Vol. 109, No. 48, 08.12.2005, p. 11006-11014.

Research output: Contribution to journalArticle

@article{f97ae3e9465b44bba55634264d359726,
title = "Binding energy curves from nonempirical density functionals. I. Covalent bonds in closed-shell and radical molecules",
abstract = "Binding or potential energy curves have been calculated for the ground-state diatomics H2+, He2+, LiH+, H2, N2, and C2, for the transition state H3, and for the triplet first excited state of H2 using the nonempirical density functionals from the first three rungs of a ladder of approximations: the local spin density (LSD) approximation, the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and the Tao-Perdew-Staroverov-Scuseria (TPSS) meta GGA. Good binding energy curves in agreement with coupled cluster or configuration interaction calculations are found from the PBE GGA and especially from the TPSS meta GGA. Expected exceptions are the symmetric radicals H2+ and He 2+, where the functionals suffer from self-interaction error, and the exotically bonded C2. Although the energy barrier for the reaction H2 + H → H + H2 is better in PBE than in TPSS, the transition state H3 is a more properly positioned and curved saddle point of the energy surface in TPSS. The triplet first excited state of H2 obeys the Aufbau principle and thus is one of the exceptional excited states that are computable in principle from the ground-state functional. The PBE GGA and TPSS meta GGA are useful not only for chemical applications but also for the construction of higher-rung nonempirical functionals that can further improve the binding energy curves.",
author = "Adrienn Ruzsinszky and Perdew, {John P.} and G. Csonka",
year = "2005",
month = "12",
day = "8",
doi = "10.1021/jp0534479",
language = "English",
volume = "109",
pages = "11006--11014",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "48",

}

TY - JOUR

T1 - Binding energy curves from nonempirical density functionals. I. Covalent bonds in closed-shell and radical molecules

AU - Ruzsinszky, Adrienn

AU - Perdew, John P.

AU - Csonka, G.

PY - 2005/12/8

Y1 - 2005/12/8

N2 - Binding or potential energy curves have been calculated for the ground-state diatomics H2+, He2+, LiH+, H2, N2, and C2, for the transition state H3, and for the triplet first excited state of H2 using the nonempirical density functionals from the first three rungs of a ladder of approximations: the local spin density (LSD) approximation, the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and the Tao-Perdew-Staroverov-Scuseria (TPSS) meta GGA. Good binding energy curves in agreement with coupled cluster or configuration interaction calculations are found from the PBE GGA and especially from the TPSS meta GGA. Expected exceptions are the symmetric radicals H2+ and He 2+, where the functionals suffer from self-interaction error, and the exotically bonded C2. Although the energy barrier for the reaction H2 + H → H + H2 is better in PBE than in TPSS, the transition state H3 is a more properly positioned and curved saddle point of the energy surface in TPSS. The triplet first excited state of H2 obeys the Aufbau principle and thus is one of the exceptional excited states that are computable in principle from the ground-state functional. The PBE GGA and TPSS meta GGA are useful not only for chemical applications but also for the construction of higher-rung nonempirical functionals that can further improve the binding energy curves.

AB - Binding or potential energy curves have been calculated for the ground-state diatomics H2+, He2+, LiH+, H2, N2, and C2, for the transition state H3, and for the triplet first excited state of H2 using the nonempirical density functionals from the first three rungs of a ladder of approximations: the local spin density (LSD) approximation, the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and the Tao-Perdew-Staroverov-Scuseria (TPSS) meta GGA. Good binding energy curves in agreement with coupled cluster or configuration interaction calculations are found from the PBE GGA and especially from the TPSS meta GGA. Expected exceptions are the symmetric radicals H2+ and He 2+, where the functionals suffer from self-interaction error, and the exotically bonded C2. Although the energy barrier for the reaction H2 + H → H + H2 is better in PBE than in TPSS, the transition state H3 is a more properly positioned and curved saddle point of the energy surface in TPSS. The triplet first excited state of H2 obeys the Aufbau principle and thus is one of the exceptional excited states that are computable in principle from the ground-state functional. The PBE GGA and TPSS meta GGA are useful not only for chemical applications but also for the construction of higher-rung nonempirical functionals that can further improve the binding energy curves.

UR - http://www.scopus.com/inward/record.url?scp=29444437386&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=29444437386&partnerID=8YFLogxK

U2 - 10.1021/jp0534479

DO - 10.1021/jp0534479

M3 - Article

C2 - 16331944

AN - SCOPUS:29444437386

VL - 109

SP - 11006

EP - 11014

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 48

ER -