### Abstract

We report rigorous quantum dynamics studies of the Li + HF reaction using the time-dependent wavepacket approach. The dynamics study is carried out on a recent ab initio potential energy surface, and state-selected reaction probabilities and cross sections are calculated up to 0.4 eV of collision energy. Many long-lived resonances (as long as 10 ps) at low collision energies (below 0.1 eV) are uncovered from the dynamics calculation. These long-lived resonances play a dominant role in the title reaction at low collision energies (below 0.1 eV). At higher energies, the direct reaction process becomes very important. The reaction probabilities from even rotational states exhibit a different energy dependence than those from odd rotational states. Our calculated integral cross section exhibits a broad maximum near the collision energy of 0.26 eV with small oscillations superimposed on the broad envelope which is reminiscent of the underlying resonance structures in reaction probabilities. The energy dependence of the present CS cross section is qualitatively different from the simple J-shifting approximation, in which a monotonic increase of cross section with collision energy was obtained.

Original language | English (US) |
---|---|

Pages (from-to) | 31-38 |

Number of pages | 8 |

Journal | Theoretical Chemistry Accounts |

Volume | 96 |

Issue number | 1 |

State | Published - Apr 1997 |

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### Keywords

- Atom-diatom reactive scattering
- Coupled state approximation
- Integral cross section
- Time-dependent approach
- Wavepacket propagation

### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

*Theoretical Chemistry Accounts*,

*96*(1), 31-38.

**Quantum dynamics study of Li + HF reaction.** / Zhu, Wei; Wang, Dunyou; Zhang, John.

Research output: Contribution to journal › Article

*Theoretical Chemistry Accounts*, vol. 96, no. 1, pp. 31-38.

}

TY - JOUR

T1 - Quantum dynamics study of Li + HF reaction

AU - Zhu, Wei

AU - Wang, Dunyou

AU - Zhang, John

PY - 1997/4

Y1 - 1997/4

N2 - We report rigorous quantum dynamics studies of the Li + HF reaction using the time-dependent wavepacket approach. The dynamics study is carried out on a recent ab initio potential energy surface, and state-selected reaction probabilities and cross sections are calculated up to 0.4 eV of collision energy. Many long-lived resonances (as long as 10 ps) at low collision energies (below 0.1 eV) are uncovered from the dynamics calculation. These long-lived resonances play a dominant role in the title reaction at low collision energies (below 0.1 eV). At higher energies, the direct reaction process becomes very important. The reaction probabilities from even rotational states exhibit a different energy dependence than those from odd rotational states. Our calculated integral cross section exhibits a broad maximum near the collision energy of 0.26 eV with small oscillations superimposed on the broad envelope which is reminiscent of the underlying resonance structures in reaction probabilities. The energy dependence of the present CS cross section is qualitatively different from the simple J-shifting approximation, in which a monotonic increase of cross section with collision energy was obtained.

AB - We report rigorous quantum dynamics studies of the Li + HF reaction using the time-dependent wavepacket approach. The dynamics study is carried out on a recent ab initio potential energy surface, and state-selected reaction probabilities and cross sections are calculated up to 0.4 eV of collision energy. Many long-lived resonances (as long as 10 ps) at low collision energies (below 0.1 eV) are uncovered from the dynamics calculation. These long-lived resonances play a dominant role in the title reaction at low collision energies (below 0.1 eV). At higher energies, the direct reaction process becomes very important. The reaction probabilities from even rotational states exhibit a different energy dependence than those from odd rotational states. Our calculated integral cross section exhibits a broad maximum near the collision energy of 0.26 eV with small oscillations superimposed on the broad envelope which is reminiscent of the underlying resonance structures in reaction probabilities. The energy dependence of the present CS cross section is qualitatively different from the simple J-shifting approximation, in which a monotonic increase of cross section with collision energy was obtained.

KW - Atom-diatom reactive scattering

KW - Coupled state approximation

KW - Integral cross section

KW - Time-dependent approach

KW - Wavepacket propagation

UR - http://www.scopus.com/inward/record.url?scp=0031285907&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0031285907&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0031285907

VL - 96

SP - 31

EP - 38

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

SN - 1432-881X

IS - 1

ER -