### Abstract

The dynamics of sequential dissociation processes of the type XI _{2}(v)Y→X+I_{2}(v′)Y→X+Y+I_{2}(v″ )(X, Y=Ne, He) are studied using classical trajectory calculations and a recently presented classical version of the time-dependent self-consistent field (TDSCF) method. The results obtained indicate the presence of significant dynamical correlation effects of the rare-gas atoms on each other despite the negligible direct interaction between them; this is in qualitative agreement with experimental findings. Good agreement is found for the rate constants and the variation with rare gas as well as the branching ratios (NeI _{2}He→NeI_{2}+He vs→I_{2}He+Ne) calculated from TDSCF and from classical trajectories. Both classical trajectories and TDSCF show an essentially impulsive dissociation mechanism, in which dissociation typically follows a considerable number of vibrations, and is due to a relatively rare internal hard collision between an I atom and the rare gas. As in the three-body I_{2}X case, this mechanism differs from that in the RRKM strong coupling model. Energy- and momentum-gap relations, based on the weak-coupling picture, are found to be relatively successful but fail to describe the dynamics quantitatively.

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

Pages (from-to) | 1808-1822 |

Number of pages | 15 |

Journal | Journal of Chemical Physics |

Volume | 79 |

Issue number | 4 |

Publication status | Published - 1983 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

_{2}XY→I

_{2}+X+Y (X, Y=He, Ne).

*Journal of Chemical Physics*,

*79*(4), 1808-1822.

**Dissociation dynamics of vibrationally excited van der Waals clusters : I _{2}XY→I_{2}+X+Y (X, Y=He, Ne).** / Schatz, George C; Buch, Victoria; Ratner, Mark A; Gerber, Robert B.

Research output: Contribution to journal › Article

_{2}XY→I

_{2}+X+Y (X, Y=He, Ne)',

*Journal of Chemical Physics*, vol. 79, no. 4, pp. 1808-1822.

_{2}XY→I

_{2}+X+Y (X, Y=He, Ne). Journal of Chemical Physics. 1983;79(4):1808-1822.

}

TY - JOUR

T1 - Dissociation dynamics of vibrationally excited van der Waals clusters

T2 - I2XY→I2+X+Y (X, Y=He, Ne)

AU - Schatz, George C

AU - Buch, Victoria

AU - Ratner, Mark A

AU - Gerber, Robert B.

PY - 1983

Y1 - 1983

N2 - The dynamics of sequential dissociation processes of the type XI 2(v)Y→X+I2(v′)Y→X+Y+I2(v″ )(X, Y=Ne, He) are studied using classical trajectory calculations and a recently presented classical version of the time-dependent self-consistent field (TDSCF) method. The results obtained indicate the presence of significant dynamical correlation effects of the rare-gas atoms on each other despite the negligible direct interaction between them; this is in qualitative agreement with experimental findings. Good agreement is found for the rate constants and the variation with rare gas as well as the branching ratios (NeI 2He→NeI2+He vs→I2He+Ne) calculated from TDSCF and from classical trajectories. Both classical trajectories and TDSCF show an essentially impulsive dissociation mechanism, in which dissociation typically follows a considerable number of vibrations, and is due to a relatively rare internal hard collision between an I atom and the rare gas. As in the three-body I2X case, this mechanism differs from that in the RRKM strong coupling model. Energy- and momentum-gap relations, based on the weak-coupling picture, are found to be relatively successful but fail to describe the dynamics quantitatively.

AB - The dynamics of sequential dissociation processes of the type XI 2(v)Y→X+I2(v′)Y→X+Y+I2(v″ )(X, Y=Ne, He) are studied using classical trajectory calculations and a recently presented classical version of the time-dependent self-consistent field (TDSCF) method. The results obtained indicate the presence of significant dynamical correlation effects of the rare-gas atoms on each other despite the negligible direct interaction between them; this is in qualitative agreement with experimental findings. Good agreement is found for the rate constants and the variation with rare gas as well as the branching ratios (NeI 2He→NeI2+He vs→I2He+Ne) calculated from TDSCF and from classical trajectories. Both classical trajectories and TDSCF show an essentially impulsive dissociation mechanism, in which dissociation typically follows a considerable number of vibrations, and is due to a relatively rare internal hard collision between an I atom and the rare gas. As in the three-body I2X case, this mechanism differs from that in the RRKM strong coupling model. Energy- and momentum-gap relations, based on the weak-coupling picture, are found to be relatively successful but fail to describe the dynamics quantitatively.

UR - http://www.scopus.com/inward/record.url?scp=0000004482&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000004482&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000004482

VL - 79

SP - 1808

EP - 1822

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 4

ER -