### Abstract

Vibrational energies and eigenfunctions of Ar_{3}, including some pertaining to highly excited states, are computed, and insights into their dynamical and structural properties are obtained. The method used employs the vibrational self-consistent-field (SCF) theory in hyperspherical coordinates as a first approximation. Exact results are obtained by configuration interaction, using the SCF states as an efficient basis. A focal point of the study is the effect of three-body potentials on the vibrational spectrum. Axilrod-Teller and other three-body potentials are used to examine this. It is found that the effect of three-body forces on the spectrum is substantial, and larger than effects due to uncertainties in the presently known two-body Ar-Ar potentials. This suggests that experimental spectroscopy of Ar_{3} may be used to determine reliable three-body forces among Ar atoms. It is also shown that the three-body double-dipole-quadrupole interaction, while less important than the Axilrod-Teller one, has a significant effect on the vibrational spectrum. Finally, a detailed analysis is made of the Ar-Ar distance distributions in the various states, of the structural distributions of Ar_{3}, and of the properties of the wave functions. We find that the wave functions show well-ordered nodal patterns even for the highly excited large-amplitude states. Thus, these states do not correspond qualitatively to "liquid-like" behavior of the cluster.

Original language | English |
---|---|

Pages (from-to) | 6728-6736 |

Number of pages | 9 |

Journal | Journal of Chemical Physics |

Volume | 94 |

Issue number | 10 |

Publication status | Published - 1991 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

_{3}: The role of three-body forces.

*Journal of Chemical Physics*,

*94*(10), 6728-6736.

**Vibrational states and structure of Ar _{3} : The role of three-body forces.** / Horn, T. R.; Gerber, R. B.; Valentini, J. J.; Ratner, Mark A.

Research output: Contribution to journal › Article

_{3}: The role of three-body forces',

*Journal of Chemical Physics*, vol. 94, no. 10, pp. 6728-6736.

_{3}: The role of three-body forces. Journal of Chemical Physics. 1991;94(10):6728-6736.

}

TY - JOUR

T1 - Vibrational states and structure of Ar3

T2 - The role of three-body forces

AU - Horn, T. R.

AU - Gerber, R. B.

AU - Valentini, J. J.

AU - Ratner, Mark A

PY - 1991

Y1 - 1991

N2 - Vibrational energies and eigenfunctions of Ar3, including some pertaining to highly excited states, are computed, and insights into their dynamical and structural properties are obtained. The method used employs the vibrational self-consistent-field (SCF) theory in hyperspherical coordinates as a first approximation. Exact results are obtained by configuration interaction, using the SCF states as an efficient basis. A focal point of the study is the effect of three-body potentials on the vibrational spectrum. Axilrod-Teller and other three-body potentials are used to examine this. It is found that the effect of three-body forces on the spectrum is substantial, and larger than effects due to uncertainties in the presently known two-body Ar-Ar potentials. This suggests that experimental spectroscopy of Ar3 may be used to determine reliable three-body forces among Ar atoms. It is also shown that the three-body double-dipole-quadrupole interaction, while less important than the Axilrod-Teller one, has a significant effect on the vibrational spectrum. Finally, a detailed analysis is made of the Ar-Ar distance distributions in the various states, of the structural distributions of Ar3, and of the properties of the wave functions. We find that the wave functions show well-ordered nodal patterns even for the highly excited large-amplitude states. Thus, these states do not correspond qualitatively to "liquid-like" behavior of the cluster.

AB - Vibrational energies and eigenfunctions of Ar3, including some pertaining to highly excited states, are computed, and insights into their dynamical and structural properties are obtained. The method used employs the vibrational self-consistent-field (SCF) theory in hyperspherical coordinates as a first approximation. Exact results are obtained by configuration interaction, using the SCF states as an efficient basis. A focal point of the study is the effect of three-body potentials on the vibrational spectrum. Axilrod-Teller and other three-body potentials are used to examine this. It is found that the effect of three-body forces on the spectrum is substantial, and larger than effects due to uncertainties in the presently known two-body Ar-Ar potentials. This suggests that experimental spectroscopy of Ar3 may be used to determine reliable three-body forces among Ar atoms. It is also shown that the three-body double-dipole-quadrupole interaction, while less important than the Axilrod-Teller one, has a significant effect on the vibrational spectrum. Finally, a detailed analysis is made of the Ar-Ar distance distributions in the various states, of the structural distributions of Ar3, and of the properties of the wave functions. We find that the wave functions show well-ordered nodal patterns even for the highly excited large-amplitude states. Thus, these states do not correspond qualitatively to "liquid-like" behavior of the cluster.

UR - http://www.scopus.com/inward/record.url?scp=0001046012&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001046012&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001046012

VL - 94

SP - 6728

EP - 6736

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 10

ER -