The semiclassical self-consistent-field method for polyatomic vibrations: Use of hyperspherical coordinates for H2O and CO2

Lester L. Gibson, R. M. Roth, Mark A Ratner, R. B. Gerber

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The use of hyperspherical coordinates within the semiclassical self-consistent-field model (SCSCF) is investigated for two-mode models, corresponding to nonbending CO2 and H2O. The hyperspherical coordinate set is highly collective; since the screening which is characteristic of collective coordinates should result in increased accuracy of SCF methods, it might be expected that these coordinates would lead to very good SCF results. Numerical tests show that indeed the hyperspherical SCF results are accurate and superior to SCF either in local- or in normal-mode coordinates, the improvement being larger for CO2 than for H 2O. These calculations show as does recent work on HCN that proper choice of the coordinate system can lead to much improved SCF results.

Original languageEnglish
Pages (from-to)3425-3431
Number of pages7
JournalJournal of Chemical Physics
Volume85
Issue number6
Publication statusPublished - 1986

Fingerprint

self consistent fields
vibration
Screening
screening

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

The semiclassical self-consistent-field method for polyatomic vibrations : Use of hyperspherical coordinates for H2O and CO2. / Gibson, Lester L.; Roth, R. M.; Ratner, Mark A; Gerber, R. B.

In: Journal of Chemical Physics, Vol. 85, No. 6, 1986, p. 3425-3431.

Research output: Contribution to journalArticle

@article{5aa15bf3de614fa6b967c2f77adb43b4,
title = "The semiclassical self-consistent-field method for polyatomic vibrations: Use of hyperspherical coordinates for H2O and CO2",
abstract = "The use of hyperspherical coordinates within the semiclassical self-consistent-field model (SCSCF) is investigated for two-mode models, corresponding to nonbending CO2 and H2O. The hyperspherical coordinate set is highly collective; since the screening which is characteristic of collective coordinates should result in increased accuracy of SCF methods, it might be expected that these coordinates would lead to very good SCF results. Numerical tests show that indeed the hyperspherical SCF results are accurate and superior to SCF either in local- or in normal-mode coordinates, the improvement being larger for CO2 than for H 2O. These calculations show as does recent work on HCN that proper choice of the coordinate system can lead to much improved SCF results.",
author = "Gibson, {Lester L.} and Roth, {R. M.} and Ratner, {Mark A} and Gerber, {R. B.}",
year = "1986",
language = "English",
volume = "85",
pages = "3425--3431",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "6",

}

TY - JOUR

T1 - The semiclassical self-consistent-field method for polyatomic vibrations

T2 - Use of hyperspherical coordinates for H2O and CO2

AU - Gibson, Lester L.

AU - Roth, R. M.

AU - Ratner, Mark A

AU - Gerber, R. B.

PY - 1986

Y1 - 1986

N2 - The use of hyperspherical coordinates within the semiclassical self-consistent-field model (SCSCF) is investigated for two-mode models, corresponding to nonbending CO2 and H2O. The hyperspherical coordinate set is highly collective; since the screening which is characteristic of collective coordinates should result in increased accuracy of SCF methods, it might be expected that these coordinates would lead to very good SCF results. Numerical tests show that indeed the hyperspherical SCF results are accurate and superior to SCF either in local- or in normal-mode coordinates, the improvement being larger for CO2 than for H 2O. These calculations show as does recent work on HCN that proper choice of the coordinate system can lead to much improved SCF results.

AB - The use of hyperspherical coordinates within the semiclassical self-consistent-field model (SCSCF) is investigated for two-mode models, corresponding to nonbending CO2 and H2O. The hyperspherical coordinate set is highly collective; since the screening which is characteristic of collective coordinates should result in increased accuracy of SCF methods, it might be expected that these coordinates would lead to very good SCF results. Numerical tests show that indeed the hyperspherical SCF results are accurate and superior to SCF either in local- or in normal-mode coordinates, the improvement being larger for CO2 than for H 2O. These calculations show as does recent work on HCN that proper choice of the coordinate system can lead to much improved SCF results.

UR - http://www.scopus.com/inward/record.url?scp=0039906214&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0039906214&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0039906214

VL - 85

SP - 3425

EP - 3431

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 6

ER -