Scaled quantum chemical force fields for 1,1-difluorocyclopropane and the influence of vibrational anharmonicity

Donald C. McKean, Norman C. Craig, Mark M. Law

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Potential functions and harmonic (omega(i)) and anharmonic (nu(i)) fundamental frequencies have been calculated for 1,1-difluorocyclopropane (DFCP) and its d(4) and d(2) isotopomers using the program Gaussian 03. B3LYP and MP2 models were employed, each with the bases 6-311++G** and cc-pVTZ. Anharmonicity corrections Delta(i) = omega(i) - nu(i) are listed and shown to be different for symmetric and antisymmetric CH stretching modes in situations where Fermi resonance appears to be absent. The same effect is missing in C2H4, for which similar calculations were made. The quadratic force fields for DFCP have been scaled in symmetry coordinate space with 15 scale factors both to observed frequencies nu(obsd) and also to omega(obsd), where omega(obsd) = nu(obsd) + Delta. With nu(obsd) especially, different scale factors are needed for the symmetric and antisymmetric CH stretching force constants due to their differing anharmonicities. The source of the latter in the quartic and cubic force field is explored. MP2 calculations of valence interaction force constants involving the stretching of bonds on a common carbon atom are preferred to those from a B3LYP model. In either model, scaling to omega(obsd) rather than to nu(obsd) does not remove the necessity of varying scale factors for differing types of motion in the same group. Theoretical values of the five quartic centrifugal distortion constants are listed for the normal species and compared with new experimental data. The predictions are sufficiently good to be useful in fitting pure rotational transitions. A weakness is identified in the current Gaussian 03 code for the calculation of vibration-rotation quantities, and limitations are noted in the manner in which Fermi resonance is handled.

Original languageEnglish
Pages (from-to)6760-6771
Number of pages12
JournalJournal of Physical Chemistry A
Volume112
Issue number29
Early online date27 Jun 2008
DOIs
Publication statusPublished - 24 Jul 2008

Keywords

  • correlated molecular calculations
  • Gaussian-basis sets
  • local mode
  • centrifugal-distortion
  • equilibrium structures
  • electrical-properties
  • infrared-spectra
  • constants
  • ethylene
  • abinitio

Cite this

Scaled quantum chemical force fields for 1,1-difluorocyclopropane and the influence of vibrational anharmonicity. / McKean, Donald C.; Craig, Norman C.; Law, Mark M.

In: Journal of Physical Chemistry A, Vol. 112, No. 29, 24.07.2008, p. 6760-6771.

Research output: Contribution to journalArticle

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T1 - Scaled quantum chemical force fields for 1,1-difluorocyclopropane and the influence of vibrational anharmonicity

AU - McKean, Donald C.

AU - Craig, Norman C.

AU - Law, Mark M.

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N2 - Potential functions and harmonic (omega(i)) and anharmonic (nu(i)) fundamental frequencies have been calculated for 1,1-difluorocyclopropane (DFCP) and its d(4) and d(2) isotopomers using the program Gaussian 03. B3LYP and MP2 models were employed, each with the bases 6-311++G** and cc-pVTZ. Anharmonicity corrections Delta(i) = omega(i) - nu(i) are listed and shown to be different for symmetric and antisymmetric CH stretching modes in situations where Fermi resonance appears to be absent. The same effect is missing in C2H4, for which similar calculations were made. The quadratic force fields for DFCP have been scaled in symmetry coordinate space with 15 scale factors both to observed frequencies nu(obsd) and also to omega(obsd), where omega(obsd) = nu(obsd) + Delta. With nu(obsd) especially, different scale factors are needed for the symmetric and antisymmetric CH stretching force constants due to their differing anharmonicities. The source of the latter in the quartic and cubic force field is explored. MP2 calculations of valence interaction force constants involving the stretching of bonds on a common carbon atom are preferred to those from a B3LYP model. In either model, scaling to omega(obsd) rather than to nu(obsd) does not remove the necessity of varying scale factors for differing types of motion in the same group. Theoretical values of the five quartic centrifugal distortion constants are listed for the normal species and compared with new experimental data. The predictions are sufficiently good to be useful in fitting pure rotational transitions. A weakness is identified in the current Gaussian 03 code for the calculation of vibration-rotation quantities, and limitations are noted in the manner in which Fermi resonance is handled.

AB - Potential functions and harmonic (omega(i)) and anharmonic (nu(i)) fundamental frequencies have been calculated for 1,1-difluorocyclopropane (DFCP) and its d(4) and d(2) isotopomers using the program Gaussian 03. B3LYP and MP2 models were employed, each with the bases 6-311++G** and cc-pVTZ. Anharmonicity corrections Delta(i) = omega(i) - nu(i) are listed and shown to be different for symmetric and antisymmetric CH stretching modes in situations where Fermi resonance appears to be absent. The same effect is missing in C2H4, for which similar calculations were made. The quadratic force fields for DFCP have been scaled in symmetry coordinate space with 15 scale factors both to observed frequencies nu(obsd) and also to omega(obsd), where omega(obsd) = nu(obsd) + Delta. With nu(obsd) especially, different scale factors are needed for the symmetric and antisymmetric CH stretching force constants due to their differing anharmonicities. The source of the latter in the quartic and cubic force field is explored. MP2 calculations of valence interaction force constants involving the stretching of bonds on a common carbon atom are preferred to those from a B3LYP model. In either model, scaling to omega(obsd) rather than to nu(obsd) does not remove the necessity of varying scale factors for differing types of motion in the same group. Theoretical values of the five quartic centrifugal distortion constants are listed for the normal species and compared with new experimental data. The predictions are sufficiently good to be useful in fitting pure rotational transitions. A weakness is identified in the current Gaussian 03 code for the calculation of vibration-rotation quantities, and limitations are noted in the manner in which Fermi resonance is handled.

KW - correlated molecular calculations

KW - Gaussian-basis sets

KW - local mode

KW - centrifugal-distortion

KW - equilibrium structures

KW - electrical-properties

KW - infrared-spectra

KW - constants

KW - ethylene

KW - abinitio

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DO - 10.1021/jp800628x

M3 - Article

VL - 112

SP - 6760

EP - 6771

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 29

ER -