Total and partial decay widths in vibrational predissociation of the HeI2 van der Waals complex for lower initial vibrational excitations

Daren Guan, Xian Zhao, Conghao Deng, John Zhang

Research output: Contribution to journalArticle

Abstract

We presented a calculation of the total and partial decay widths of vibrational predissociation (VP) of the HeI2 molecule for low initial vibrational excitations from the lowest van der Waals (vdW) state with total angular momentum J = 0. A time-dependent golden rule wave-packet method was employed in our numerical calculations for the decay widths. The computed total decay widths, lifetimes, and rates of VP are in fairly good agreement with those extrapolated from the experimental data available. Predicted total decay widths as a function of initial vibrational levels exhibit a highly nonlinear behavior. These results demonstrate that a quantum mechanical decay mode for low vibrational excitation remains as well. The total propagation time needed in the time-dependent golden rule wave-packet calculations is much shorter than is the lifetime of the predissociation of HeI2. It is shown that the final-state interaction between the fragments is important for determining the final rotational-state distribution (partial decay width). We find that the major peak position in the final rotational-state distribution shifts to lower rotational energy levels with increase of the initial vibrational quantum number, which is evidently different from that for higher vibrational levels. This fact can be clearly explained by the dependence of the amount of kinetic energy released to the product degrees of freedom on the initial vibrational state.

Original languageEnglish (US)
Pages (from-to)89-96
Number of pages8
JournalInternational Journal of Quantum Chemistry
Volume62
Issue number1
StatePublished - 1997

Fingerprint

Wave packets
decay
excitation
Angular momentum
Degrees of freedom (mechanics)
rotational states
Kinetic energy
wave packets
Electron energy levels
life (durability)
Molecules
vibrational states
quantum numbers
angular momentum
degrees of freedom
kinetic energy
energy levels
fragments
propagation
shift

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Total and partial decay widths in vibrational predissociation of the HeI2 van der Waals complex for lower initial vibrational excitations. / Guan, Daren; Zhao, Xian; Deng, Conghao; Zhang, John.

In: International Journal of Quantum Chemistry, Vol. 62, No. 1, 1997, p. 89-96.

Research output: Contribution to journalArticle

@article{7bf46ca70cff48d39025bbe9152bd707,
title = "Total and partial decay widths in vibrational predissociation of the HeI2 van der Waals complex for lower initial vibrational excitations",
abstract = "We presented a calculation of the total and partial decay widths of vibrational predissociation (VP) of the HeI2 molecule for low initial vibrational excitations from the lowest van der Waals (vdW) state with total angular momentum J = 0. A time-dependent golden rule wave-packet method was employed in our numerical calculations for the decay widths. The computed total decay widths, lifetimes, and rates of VP are in fairly good agreement with those extrapolated from the experimental data available. Predicted total decay widths as a function of initial vibrational levels exhibit a highly nonlinear behavior. These results demonstrate that a quantum mechanical decay mode for low vibrational excitation remains as well. The total propagation time needed in the time-dependent golden rule wave-packet calculations is much shorter than is the lifetime of the predissociation of HeI2. It is shown that the final-state interaction between the fragments is important for determining the final rotational-state distribution (partial decay width). We find that the major peak position in the final rotational-state distribution shifts to lower rotational energy levels with increase of the initial vibrational quantum number, which is evidently different from that for higher vibrational levels. This fact can be clearly explained by the dependence of the amount of kinetic energy released to the product degrees of freedom on the initial vibrational state.",
author = "Daren Guan and Xian Zhao and Conghao Deng and John Zhang",
year = "1997",
language = "English (US)",
volume = "62",
pages = "89--96",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "John Wiley and Sons Inc.",
number = "1",

}

TY - JOUR

T1 - Total and partial decay widths in vibrational predissociation of the HeI2 van der Waals complex for lower initial vibrational excitations

AU - Guan, Daren

AU - Zhao, Xian

AU - Deng, Conghao

AU - Zhang, John

PY - 1997

Y1 - 1997

N2 - We presented a calculation of the total and partial decay widths of vibrational predissociation (VP) of the HeI2 molecule for low initial vibrational excitations from the lowest van der Waals (vdW) state with total angular momentum J = 0. A time-dependent golden rule wave-packet method was employed in our numerical calculations for the decay widths. The computed total decay widths, lifetimes, and rates of VP are in fairly good agreement with those extrapolated from the experimental data available. Predicted total decay widths as a function of initial vibrational levels exhibit a highly nonlinear behavior. These results demonstrate that a quantum mechanical decay mode for low vibrational excitation remains as well. The total propagation time needed in the time-dependent golden rule wave-packet calculations is much shorter than is the lifetime of the predissociation of HeI2. It is shown that the final-state interaction between the fragments is important for determining the final rotational-state distribution (partial decay width). We find that the major peak position in the final rotational-state distribution shifts to lower rotational energy levels with increase of the initial vibrational quantum number, which is evidently different from that for higher vibrational levels. This fact can be clearly explained by the dependence of the amount of kinetic energy released to the product degrees of freedom on the initial vibrational state.

AB - We presented a calculation of the total and partial decay widths of vibrational predissociation (VP) of the HeI2 molecule for low initial vibrational excitations from the lowest van der Waals (vdW) state with total angular momentum J = 0. A time-dependent golden rule wave-packet method was employed in our numerical calculations for the decay widths. The computed total decay widths, lifetimes, and rates of VP are in fairly good agreement with those extrapolated from the experimental data available. Predicted total decay widths as a function of initial vibrational levels exhibit a highly nonlinear behavior. These results demonstrate that a quantum mechanical decay mode for low vibrational excitation remains as well. The total propagation time needed in the time-dependent golden rule wave-packet calculations is much shorter than is the lifetime of the predissociation of HeI2. It is shown that the final-state interaction between the fragments is important for determining the final rotational-state distribution (partial decay width). We find that the major peak position in the final rotational-state distribution shifts to lower rotational energy levels with increase of the initial vibrational quantum number, which is evidently different from that for higher vibrational levels. This fact can be clearly explained by the dependence of the amount of kinetic energy released to the product degrees of freedom on the initial vibrational state.

UR - http://www.scopus.com/inward/record.url?scp=3342946123&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=3342946123&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:3342946123

VL - 62

SP - 89

EP - 96

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 1

ER -