### Abstract

We present the results of an accurate quantum scattering study of collisional energy transfer in a bend-stretch model of the He + CS_{2} system, considering energies up to 45kcal/mol. These results are generated using a coupled channel method, with vibrational eigenfunctions obtained from a discrete variable representation method. Detailed comparisons with the results of classical trajectory calculations are performed so as to assess classical/quantum correspondence for energy transfer moments, and for the energy transfer probability distribution function. We find good agreement of the energy averaged first moments over a wide range of molecular vibrational energies. The second moments, as well as 〈ΔE〉_{up} and 〈ΔE〉_{down} show less quantitative agreement. The quantum energy transfer distribution functions show considerable mode-specific behavior, but the overall envelope is approximately exponential at large |ΔE\ with a broad spike near |ΔE| = 0. We analyze this behavior in terms of contributions from individual state-to-state transition probabilities. The corresponding classical distribution functions are very similar, showing better correspondence than was found for other models with smaller state densities.

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

Pages (from-to) | 587-594 |

Number of pages | 8 |

Journal | Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics |

Volume | 101 |

Issue number | 3 |

Publication status | Published - 1997 |

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### Keywords

- Chemical kinetics
- Computer experiments
- Energy transfer
- Quantum mechanics

### ASJC Scopus subject areas

- Chemical Engineering(all)

### Cite this

**Quantum scattering studies of collisional energy transfer from highly excited polyatomic molecules : A bend-stretch model of He + CS _{2}.** / Lendvay, György; Schatz, George C.

Research output: Contribution to journal › Article

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TY - JOUR

T1 - Quantum scattering studies of collisional energy transfer from highly excited polyatomic molecules

T2 - A bend-stretch model of He + CS2

AU - Lendvay, György

AU - Schatz, George C

PY - 1997

Y1 - 1997

N2 - We present the results of an accurate quantum scattering study of collisional energy transfer in a bend-stretch model of the He + CS2 system, considering energies up to 45kcal/mol. These results are generated using a coupled channel method, with vibrational eigenfunctions obtained from a discrete variable representation method. Detailed comparisons with the results of classical trajectory calculations are performed so as to assess classical/quantum correspondence for energy transfer moments, and for the energy transfer probability distribution function. We find good agreement of the energy averaged first moments over a wide range of molecular vibrational energies. The second moments, as well as 〈ΔE〉up and 〈ΔE〉down show less quantitative agreement. The quantum energy transfer distribution functions show considerable mode-specific behavior, but the overall envelope is approximately exponential at large |ΔE\ with a broad spike near |ΔE| = 0. We analyze this behavior in terms of contributions from individual state-to-state transition probabilities. The corresponding classical distribution functions are very similar, showing better correspondence than was found for other models with smaller state densities.

AB - We present the results of an accurate quantum scattering study of collisional energy transfer in a bend-stretch model of the He + CS2 system, considering energies up to 45kcal/mol. These results are generated using a coupled channel method, with vibrational eigenfunctions obtained from a discrete variable representation method. Detailed comparisons with the results of classical trajectory calculations are performed so as to assess classical/quantum correspondence for energy transfer moments, and for the energy transfer probability distribution function. We find good agreement of the energy averaged first moments over a wide range of molecular vibrational energies. The second moments, as well as 〈ΔE〉up and 〈ΔE〉down show less quantitative agreement. The quantum energy transfer distribution functions show considerable mode-specific behavior, but the overall envelope is approximately exponential at large |ΔE\ with a broad spike near |ΔE| = 0. We analyze this behavior in terms of contributions from individual state-to-state transition probabilities. The corresponding classical distribution functions are very similar, showing better correspondence than was found for other models with smaller state densities.

KW - Chemical kinetics

KW - Computer experiments

KW - Energy transfer

KW - Quantum mechanics

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UR - http://www.scopus.com/inward/citedby.url?scp=0011694449&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0011694449

VL - 101

SP - 587

EP - 594

JO - Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics

JF - Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics

SN - 0005-9021

IS - 3

ER -