### Abstract

A study is made of the vibrational energy levels and the corresponding oscillation dynamics of the clusters Xe^{4}He_{2}, Xe ^{3}He_{2}, and I_{2}^{4}He. XeHe_{2} is a representative of the "three ball" clusters, while I_{2}He is a prototype of the "stick and ball" systems. The treatment is based on the vibrational self-consistent field (SCF) method, which introduces an approximate separation of the modes involved. Success of the method depends on an adequate choice of the coordinates that are being mutually separated. We use physical arguments, based on mass ratios and potential function considerations, as well as comparative SCF calculations in different coordinate systems, to determine the appropriate modes for each system. Numerically exact results are also obtained by configuration interaction (CI) calculations using a basis of SCF states. The SCF and CI calculations include all modes and employ realistic potentials. Several states that are both rotationally and vibrationally excited are also calculated. The main conclusions are: (1) Hyperspherical coordinates are the best modes for XeHe_{2}; ellipsoidal coordinates are best for I_{2}He. In each case, the "good modes" SCF gives energies in remarkable agreement with the exact (CI) ones. (2) XeHe_{2} resembles a quantum liquid drop: Even in the ground state, it is delocalized over and between the (two) classical equilibrium structures. (3) Structural distributions, rather than rigid geometry, are essential for the description of such floppy clusters. The single-mode SCF wave functions offer a highly accurate description of the structural distributions. (4) There is a sequence of bound, excited rotational states of I_{2}He in which the He precesses around the I_{2} axis. The amplitude of the I_{2}He bending vibrations are very large (θ_{A} <20°), but none of the bound states involves a full rotational motion around the I_{2} stick (with angular momentum normal to the axis). The SCF method with the "good coordinates" proposed here is expected to yield results of similar high accuracy for any cluster of the "three balls" or "stick and ball" types.

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

Pages (from-to) | 1813-1823 |

Number of pages | 11 |

Journal | Journal of Chemical Physics |

Volume | 96 |

Issue number | 3 |

Publication status | Published - 1991 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

_{2}, l

_{2}He.

*Journal of Chemical Physics*,

*96*(3), 1813-1823.

**Vibrational states of very floppy clusters : Approximate separability and the choice of good curvilinear coordinates for XeHe _{2}, l_{2}He.** / Horn, T. R.; Gerber, R. B.; Ratner, Mark A.

Research output: Contribution to journal › Article

_{2}, l

_{2}He',

*Journal of Chemical Physics*, vol. 96, no. 3, pp. 1813-1823.

_{2}, l

_{2}He. Journal of Chemical Physics. 1991;96(3):1813-1823.

}

TY - JOUR

T1 - Vibrational states of very floppy clusters

T2 - Approximate separability and the choice of good curvilinear coordinates for XeHe2, l2He

AU - Horn, T. R.

AU - Gerber, R. B.

AU - Ratner, Mark A

PY - 1991

Y1 - 1991

N2 - A study is made of the vibrational energy levels and the corresponding oscillation dynamics of the clusters Xe4He2, Xe 3He2, and I24He. XeHe2 is a representative of the "three ball" clusters, while I2He is a prototype of the "stick and ball" systems. The treatment is based on the vibrational self-consistent field (SCF) method, which introduces an approximate separation of the modes involved. Success of the method depends on an adequate choice of the coordinates that are being mutually separated. We use physical arguments, based on mass ratios and potential function considerations, as well as comparative SCF calculations in different coordinate systems, to determine the appropriate modes for each system. Numerically exact results are also obtained by configuration interaction (CI) calculations using a basis of SCF states. The SCF and CI calculations include all modes and employ realistic potentials. Several states that are both rotationally and vibrationally excited are also calculated. The main conclusions are: (1) Hyperspherical coordinates are the best modes for XeHe2; ellipsoidal coordinates are best for I2He. In each case, the "good modes" SCF gives energies in remarkable agreement with the exact (CI) ones. (2) XeHe2 resembles a quantum liquid drop: Even in the ground state, it is delocalized over and between the (two) classical equilibrium structures. (3) Structural distributions, rather than rigid geometry, are essential for the description of such floppy clusters. The single-mode SCF wave functions offer a highly accurate description of the structural distributions. (4) There is a sequence of bound, excited rotational states of I2He in which the He precesses around the I2 axis. The amplitude of the I2He bending vibrations are very large (θA <20°), but none of the bound states involves a full rotational motion around the I2 stick (with angular momentum normal to the axis). The SCF method with the "good coordinates" proposed here is expected to yield results of similar high accuracy for any cluster of the "three balls" or "stick and ball" types.

AB - A study is made of the vibrational energy levels and the corresponding oscillation dynamics of the clusters Xe4He2, Xe 3He2, and I24He. XeHe2 is a representative of the "three ball" clusters, while I2He is a prototype of the "stick and ball" systems. The treatment is based on the vibrational self-consistent field (SCF) method, which introduces an approximate separation of the modes involved. Success of the method depends on an adequate choice of the coordinates that are being mutually separated. We use physical arguments, based on mass ratios and potential function considerations, as well as comparative SCF calculations in different coordinate systems, to determine the appropriate modes for each system. Numerically exact results are also obtained by configuration interaction (CI) calculations using a basis of SCF states. The SCF and CI calculations include all modes and employ realistic potentials. Several states that are both rotationally and vibrationally excited are also calculated. The main conclusions are: (1) Hyperspherical coordinates are the best modes for XeHe2; ellipsoidal coordinates are best for I2He. In each case, the "good modes" SCF gives energies in remarkable agreement with the exact (CI) ones. (2) XeHe2 resembles a quantum liquid drop: Even in the ground state, it is delocalized over and between the (two) classical equilibrium structures. (3) Structural distributions, rather than rigid geometry, are essential for the description of such floppy clusters. The single-mode SCF wave functions offer a highly accurate description of the structural distributions. (4) There is a sequence of bound, excited rotational states of I2He in which the He precesses around the I2 axis. The amplitude of the I2He bending vibrations are very large (θA <20°), but none of the bound states involves a full rotational motion around the I2 stick (with angular momentum normal to the axis). The SCF method with the "good coordinates" proposed here is expected to yield results of similar high accuracy for any cluster of the "three balls" or "stick and ball" types.

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M3 - Article

VL - 96

SP - 1813

EP - 1823

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 3

ER -