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Geometry and force constant determination from correlated wave functions for polyatomic molecules: Ground states of H2O and CH2

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Abstract

Ab initio calculations including electron correlation are reported for the water and methylene molecules as a function of geometry. A large contracted gaussian basis set is used and the multiconfiguration wave functions, optimized by the iterative natural orbital procedure, include 277 and 617 configurations for H2O and CH2 respectively. The method of selecting configurations, yielding “first-order” wave functions, is discussed in some detail. For H2O, the SCF geometry is r=0,942 Å, θ=105,8°, the correlated result is r=0,968 Å, θ=103,2°, and the experimental r=0,957 Å, θ=104,5°. The water stretching force constants, in millidynes/Å, are 8,72 (SCF), 8,75 (CI), and 8,4 (experiment). Bending force constants are 0,88 (SCF), 0,83 (CI), and 0,76 (experiment). For methylene the SCF geometry is r=1,072 Å, θ=129,5°, while the result from first-order wave functions is r=1,088 Å, θ=134°. The predicted CH2 force constants are 6,16 (SCF) and 6,13 (CI) for stretching and 0,44 (SCF) and 0,33 (CI) for bending.

Zusammenfassung

Es wird über ab intito-Rechnungen mit Berücksichtigung der Elektronenkorrelation berichtet, die an Wasser- und Methylenmolekülen als Funktion der Geometrie durchgeführt worden sind. Dazu benutzt man einen großen kontrahierten Gauß-Basissatz. Die Multikonfigurationswellenfunktionen, die unter Benutzung von natürlichen Orbitalen nach der iterativen Prozedur optimiert werden, enthalten für H2O 277 Konfigurationen und für CH2 617. Die Auswahlmethode, die zu Wellenfunktionen 1. Ordnung führt, wird diskutiert. Im Falle des Wassers erhält man die SCF-Geometrie zu r=0,942 Å, θ=105,8°, das korrelierte Resultat ist: r=0,968 Å, θ=103,2° und das experimentelle r=0,957 Å, θ=104,5°. Für Wasser ergeben sich die Valenzkraftkonstanten (in Millidyn Å−1) 8,72 (SCF), 8,75 (CI) und 8,4 (Experiment). Die Deformationskonstanten sind 0,88 (SCF), 0,83 (CI) und 0,76 (Experiment). Im Falle des Methylens ist die SCF-Geometrie r=1,072 Å, θ=129,5°, während man mit Wellenfunktionen 1. Ordnung r=1,088 Å und θ=134° erhält. Die CH2-Kraftkonstanten werden für die Valenzschwingung zu 6,16 (SCF) und 6,13 (CI) bzw. für die Deformationsschwingung zu 0,44 (SCF) und 0,33 (CI) vorausgesagt.

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Author notes

  1. Donald R. McLaughlin

    Present address: Department of Chemistry, University of New Mexico, Albuquerque, New Mexico

Authors and Affiliations

  1. Lawrence Radiation Laboratory, University of California, 94550, Livermore, California, USA

    Donald R. McLaughlin & Charles F. Bender

  2. Department of Chemistry, University of California, 94720, Berkeley, California, USA

    Henry F. Schaefer III

Authors
  1. Donald R. McLaughlin
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  2. Charles F. Bender
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  3. Henry F. Schaefer III
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Work performed under the auspices of the U.S. Atomic Energy Commision.

Supported by the grants from the Research Corporation and the University of California Committee on Research.

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McLaughlin, D.R., Bender, C.F. & Schaefer, H.F. Geometry and force constant determination from correlated wave functions for polyatomic molecules: Ground states of H2O and CH2 . Theoret. Chim. Acta 25, 352–359 (1972). https://doi.org/10.1007/BF00526567

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