Theoretical three-dimensional potential-energy surface for the reaction of Be with HF

Sally Chapman, Michel Dupuis, Sheldon Green

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

The three-dimensional potential-energy surface for reaction of Be and HF has been computed and fit with an analytic form. Several hundred points on the surface were obtained from a two-configuration MC SCF function using a DZ GTO basis set. Comparisons with much larger calculations at a smalle rnumber of points suggest that this level of approximation gives a good qualitative and probably a reasonable quantitative description. The present surface is in good accord with a previous collinear surface (although the barrier is significantly higher in the present work) and also with a recently published valence-bond calculation. The surface is found to be quite insensitive to orientation for angles of approach between collinear and perpendicular: the minimum-energy path is not collinear. An analytic fit to the surface has been obtained. The general features are reproduced by a three-structure effective hamiltonian which is motivated by valence-bond-like ideas and which accurately reproduces the asymptotic diatomic limits. In the region of strong interaction this model is augmented by a damped fourth-order polynomial in the internuclear separations. Despite the complexity of this fitting function, it provides only a fair quantitative representation.

Original languageEnglish
Pages (from-to)93-105
Number of pages13
JournalChemical Physics
Volume78
Issue number1
DOIs
Publication statusPublished - Jul 1 1983

Fingerprint

Potential energy surfaces
potential energy
Hamiltonians
valence
self consistent fields
Polynomials
polynomials
configurations
approximation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Theoretical three-dimensional potential-energy surface for the reaction of Be with HF. / Chapman, Sally; Dupuis, Michel; Green, Sheldon.

In: Chemical Physics, Vol. 78, No. 1, 01.07.1983, p. 93-105.

Research output: Contribution to journalArticle

@article{b67531de1d0e46b0ab6fe8064b709483,
title = "Theoretical three-dimensional potential-energy surface for the reaction of Be with HF",
abstract = "The three-dimensional potential-energy surface for reaction of Be and HF has been computed and fit with an analytic form. Several hundred points on the surface were obtained from a two-configuration MC SCF function using a DZ GTO basis set. Comparisons with much larger calculations at a smalle rnumber of points suggest that this level of approximation gives a good qualitative and probably a reasonable quantitative description. The present surface is in good accord with a previous collinear surface (although the barrier is significantly higher in the present work) and also with a recently published valence-bond calculation. The surface is found to be quite insensitive to orientation for angles of approach between collinear and perpendicular: the minimum-energy path is not collinear. An analytic fit to the surface has been obtained. The general features are reproduced by a three-structure effective hamiltonian which is motivated by valence-bond-like ideas and which accurately reproduces the asymptotic diatomic limits. In the region of strong interaction this model is augmented by a damped fourth-order polynomial in the internuclear separations. Despite the complexity of this fitting function, it provides only a fair quantitative representation.",
author = "Sally Chapman and Michel Dupuis and Sheldon Green",
year = "1983",
month = "7",
day = "1",
doi = "10.1016/0301-0104(83)87010-4",
language = "English",
volume = "78",
pages = "93--105",
journal = "Chemical Physics",
issn = "0301-0104",
publisher = "Elsevier",
number = "1",

}

TY - JOUR

T1 - Theoretical three-dimensional potential-energy surface for the reaction of Be with HF

AU - Chapman, Sally

AU - Dupuis, Michel

AU - Green, Sheldon

PY - 1983/7/1

Y1 - 1983/7/1

N2 - The three-dimensional potential-energy surface for reaction of Be and HF has been computed and fit with an analytic form. Several hundred points on the surface were obtained from a two-configuration MC SCF function using a DZ GTO basis set. Comparisons with much larger calculations at a smalle rnumber of points suggest that this level of approximation gives a good qualitative and probably a reasonable quantitative description. The present surface is in good accord with a previous collinear surface (although the barrier is significantly higher in the present work) and also with a recently published valence-bond calculation. The surface is found to be quite insensitive to orientation for angles of approach between collinear and perpendicular: the minimum-energy path is not collinear. An analytic fit to the surface has been obtained. The general features are reproduced by a three-structure effective hamiltonian which is motivated by valence-bond-like ideas and which accurately reproduces the asymptotic diatomic limits. In the region of strong interaction this model is augmented by a damped fourth-order polynomial in the internuclear separations. Despite the complexity of this fitting function, it provides only a fair quantitative representation.

AB - The three-dimensional potential-energy surface for reaction of Be and HF has been computed and fit with an analytic form. Several hundred points on the surface were obtained from a two-configuration MC SCF function using a DZ GTO basis set. Comparisons with much larger calculations at a smalle rnumber of points suggest that this level of approximation gives a good qualitative and probably a reasonable quantitative description. The present surface is in good accord with a previous collinear surface (although the barrier is significantly higher in the present work) and also with a recently published valence-bond calculation. The surface is found to be quite insensitive to orientation for angles of approach between collinear and perpendicular: the minimum-energy path is not collinear. An analytic fit to the surface has been obtained. The general features are reproduced by a three-structure effective hamiltonian which is motivated by valence-bond-like ideas and which accurately reproduces the asymptotic diatomic limits. In the region of strong interaction this model is augmented by a damped fourth-order polynomial in the internuclear separations. Despite the complexity of this fitting function, it provides only a fair quantitative representation.

UR - http://www.scopus.com/inward/record.url?scp=0002032071&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0002032071&partnerID=8YFLogxK

U2 - 10.1016/0301-0104(83)87010-4

DO - 10.1016/0301-0104(83)87010-4

M3 - Article

VL - 78

SP - 93

EP - 105

JO - Chemical Physics

JF - Chemical Physics

SN - 0301-0104

IS - 1

ER -