Abstract
The van der Waals cluster molecule ArCO2 is studied computationally by using the vibrational self-consistent field (SCF) approximation, with an approximate but reasonable potential function. Calculations are carried out both for the full six-dimensional motion and for a reduced two-dimensional problem in which the CO2 is held rigid. An interesting dynamical transition is found in the motion of the Ar atom. Its equilibrium geometry is a symmetric T-shape, and for low excitations both the radial and the angular motions in the CO2 plane resemble the states of anharmonic oscillators (smaller intervals with higher excitations). Above the sixth state of the bend in the angle θ, however, the bend spectrum changes to that of a rigid rotor, with spacings of 2Bnθ for quantum number nθ. The one-dimensional effective SCF potentials along the θ coordinate and plots of the wave function both show a dynamical transition, in which, above nθ = 6, the motion of the Ar in the CO2 plane is essentially that of a rigid rotor in the θ coordinate. Calculations of the principal moments of inertia support this interpretation.
| Original language | English |
|---|---|
| Pages (from-to) | 3151-3156 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry |
| Volume | 97 |
| Issue number | 13 |
| Publication status | Published - 1993 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Vibrational states of ArCO2 : Analysis of an internal dynamical transition using self-consistent field techniques. / Horn, T. R.; Gerber, R. B.; Ratner, Mark A.
In: Journal of Physical Chemistry, Vol. 97, No. 13, 1993, p. 3151-3156.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Vibrational states of ArCO2
T2 - Analysis of an internal dynamical transition using self-consistent field techniques
AU - Horn, T. R.
AU - Gerber, R. B.
AU - Ratner, Mark A
PY - 1993
Y1 - 1993
N2 - The van der Waals cluster molecule ArCO2 is studied computationally by using the vibrational self-consistent field (SCF) approximation, with an approximate but reasonable potential function. Calculations are carried out both for the full six-dimensional motion and for a reduced two-dimensional problem in which the CO2 is held rigid. An interesting dynamical transition is found in the motion of the Ar atom. Its equilibrium geometry is a symmetric T-shape, and for low excitations both the radial and the angular motions in the CO2 plane resemble the states of anharmonic oscillators (smaller intervals with higher excitations). Above the sixth state of the bend in the angle θ, however, the bend spectrum changes to that of a rigid rotor, with spacings of 2Bnθ for quantum number nθ. The one-dimensional effective SCF potentials along the θ coordinate and plots of the wave function both show a dynamical transition, in which, above nθ = 6, the motion of the Ar in the CO2 plane is essentially that of a rigid rotor in the θ coordinate. Calculations of the principal moments of inertia support this interpretation.
AB - The van der Waals cluster molecule ArCO2 is studied computationally by using the vibrational self-consistent field (SCF) approximation, with an approximate but reasonable potential function. Calculations are carried out both for the full six-dimensional motion and for a reduced two-dimensional problem in which the CO2 is held rigid. An interesting dynamical transition is found in the motion of the Ar atom. Its equilibrium geometry is a symmetric T-shape, and for low excitations both the radial and the angular motions in the CO2 plane resemble the states of anharmonic oscillators (smaller intervals with higher excitations). Above the sixth state of the bend in the angle θ, however, the bend spectrum changes to that of a rigid rotor, with spacings of 2Bnθ for quantum number nθ. The one-dimensional effective SCF potentials along the θ coordinate and plots of the wave function both show a dynamical transition, in which, above nθ = 6, the motion of the Ar in the CO2 plane is essentially that of a rigid rotor in the θ coordinate. Calculations of the principal moments of inertia support this interpretation.
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M3 - Article
VL - 97
SP - 3151
EP - 3156
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 13
ER -