### Abstract

The orbital valency force field (OVFF) is applied to the fifteen hexafluorides whose vibrational frequencies are known, and the best-fit force constants are calculated. The OVFF showed definite advantages over the more widely used UBFF model in that (a) the angular coordinates contain no redundancy; (b) the agreement with the observed frequencies in the angle deformation modes is far superior; and (c) the least squares calculation procedure yields rapidly-converging sets of force constants for all fifteen hexafluorides. The f_{1u} force constants of some of the hexafluorides are determined from their infrared band envelopes and are compared with the calculated values. The angle distortion constant D and the repulsion constant F are found to have strong dependence upon the number of nonbonding electrons in the 4d and 5d transition metal series. This effect is discussed in terms of the repulsion between the nonbonding and bonding electrons and the Coulombic forces between partially ionic fluorine atoms.

Original language | English (US) |
---|---|

Pages (from-to) | 46-66 |

Number of pages | 21 |

Journal | Journal of Molecular Spectroscopy |

Volume | 26 |

Issue number | 1 |

State | Published - May 1968 |

Externally published | Yes |

### Fingerprint

### ASJC Scopus subject areas

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

### Cite this

*Journal of Molecular Spectroscopy*,

*26*(1), 46-66.

**Molecular force fields of octahedral XF6 molecules.** / Kim, Hyunyong; Souder, Paul A; Claassen, Howard H.

Research output: Contribution to journal › Article

*Journal of Molecular Spectroscopy*, vol. 26, no. 1, pp. 46-66.

}

TY - JOUR

T1 - Molecular force fields of octahedral XF6 molecules

AU - Kim, Hyunyong

AU - Souder, Paul A

AU - Claassen, Howard H.

PY - 1968/5

Y1 - 1968/5

N2 - The orbital valency force field (OVFF) is applied to the fifteen hexafluorides whose vibrational frequencies are known, and the best-fit force constants are calculated. The OVFF showed definite advantages over the more widely used UBFF model in that (a) the angular coordinates contain no redundancy; (b) the agreement with the observed frequencies in the angle deformation modes is far superior; and (c) the least squares calculation procedure yields rapidly-converging sets of force constants for all fifteen hexafluorides. The f1u force constants of some of the hexafluorides are determined from their infrared band envelopes and are compared with the calculated values. The angle distortion constant D and the repulsion constant F are found to have strong dependence upon the number of nonbonding electrons in the 4d and 5d transition metal series. This effect is discussed in terms of the repulsion between the nonbonding and bonding electrons and the Coulombic forces between partially ionic fluorine atoms.

AB - The orbital valency force field (OVFF) is applied to the fifteen hexafluorides whose vibrational frequencies are known, and the best-fit force constants are calculated. The OVFF showed definite advantages over the more widely used UBFF model in that (a) the angular coordinates contain no redundancy; (b) the agreement with the observed frequencies in the angle deformation modes is far superior; and (c) the least squares calculation procedure yields rapidly-converging sets of force constants for all fifteen hexafluorides. The f1u force constants of some of the hexafluorides are determined from their infrared band envelopes and are compared with the calculated values. The angle distortion constant D and the repulsion constant F are found to have strong dependence upon the number of nonbonding electrons in the 4d and 5d transition metal series. This effect is discussed in terms of the repulsion between the nonbonding and bonding electrons and the Coulombic forces between partially ionic fluorine atoms.

UR - http://www.scopus.com/inward/record.url?scp=3342957163&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=3342957163&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:3342957163

VL - 26

SP - 46

EP - 66

JO - Journal of Molecular Spectroscopy

JF - Journal of Molecular Spectroscopy

SN - 0022-2852

IS - 1

ER -