Abstract
The self-consistent field (SCF) approximation for coupled anharmonic vibrations is applied to the calculation of vibrational energy levels (predissociation resonances) of collinear models of I2(v)He and I2(v)Ne, with vibrational quantum number v between 5 and 30. The predissociation lifetimes of these same states are obtained from a distorted wave Born approximation calculation with self-consistent field states taken as the initial states of the complex, and with correlation between the modes taken as the interactions leading to decay. Although the binding energies of the van der Waals complex are very small (order of several cm-1), the SCF eigenvalues are in remarkable agreement with the exact numerical values. The lifetimes obtained from the SCF-distorted wave Born approximation (DWBA) are compared with calculations in which the initial state is treated more simply, assuming separability of the modes involved. Results then show that the DWBA with SCF initial states is considerably more accurate than with the more primitive initial state choice. We conclude from these results that the self-consistent field method offers a very accurate description of large-amplitude vibrational motions in van der Waals clusters, with good quantitative results for both the energy levels and predissociation dynamics of these species.
| Original language | English |
|---|---|
| Pages (from-to) | 3709-3714 |
| Number of pages | 6 |
| Journal | Journal of Chemical Physics |
| Volume | 88 |
| Issue number | 6 |
| Publication status | Published - 1988 |
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
Cite this
Energies and lifetimes of predissociative states of van der Waals molecules : Self-consistent field calculations for I2(v)He, I 2(v)Ne. / Schatz, George C; Gerber, R. B.; Ratner, Mark A.
In: Journal of Chemical Physics, Vol. 88, No. 6, 1988, p. 3709-3714.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Energies and lifetimes of predissociative states of van der Waals molecules
T2 - Self-consistent field calculations for I2(v)He, I 2(v)Ne
AU - Schatz, George C
AU - Gerber, R. B.
AU - Ratner, Mark A
PY - 1988
Y1 - 1988
N2 - The self-consistent field (SCF) approximation for coupled anharmonic vibrations is applied to the calculation of vibrational energy levels (predissociation resonances) of collinear models of I2(v)He and I2(v)Ne, with vibrational quantum number v between 5 and 30. The predissociation lifetimes of these same states are obtained from a distorted wave Born approximation calculation with self-consistent field states taken as the initial states of the complex, and with correlation between the modes taken as the interactions leading to decay. Although the binding energies of the van der Waals complex are very small (order of several cm-1), the SCF eigenvalues are in remarkable agreement with the exact numerical values. The lifetimes obtained from the SCF-distorted wave Born approximation (DWBA) are compared with calculations in which the initial state is treated more simply, assuming separability of the modes involved. Results then show that the DWBA with SCF initial states is considerably more accurate than with the more primitive initial state choice. We conclude from these results that the self-consistent field method offers a very accurate description of large-amplitude vibrational motions in van der Waals clusters, with good quantitative results for both the energy levels and predissociation dynamics of these species.
AB - The self-consistent field (SCF) approximation for coupled anharmonic vibrations is applied to the calculation of vibrational energy levels (predissociation resonances) of collinear models of I2(v)He and I2(v)Ne, with vibrational quantum number v between 5 and 30. The predissociation lifetimes of these same states are obtained from a distorted wave Born approximation calculation with self-consistent field states taken as the initial states of the complex, and with correlation between the modes taken as the interactions leading to decay. Although the binding energies of the van der Waals complex are very small (order of several cm-1), the SCF eigenvalues are in remarkable agreement with the exact numerical values. The lifetimes obtained from the SCF-distorted wave Born approximation (DWBA) are compared with calculations in which the initial state is treated more simply, assuming separability of the modes involved. Results then show that the DWBA with SCF initial states is considerably more accurate than with the more primitive initial state choice. We conclude from these results that the self-consistent field method offers a very accurate description of large-amplitude vibrational motions in van der Waals clusters, with good quantitative results for both the energy levels and predissociation dynamics of these species.
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M3 - Article
VL - 88
SP - 3709
EP - 3714
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 6
ER -