### Abstract

A general theoretical treatment employing a time-independent algebraic variational method (S-matrix Kohn variational method) for dissociative adsorption of a diatomic molecule on a smooth metal surface is presented. The time-independent scattering treatment using the S-matrix Kohn variational method naturally enables one to obtain accurate state-to-state reaction probabilities for dissociative adsorption of molecules on surfaces. In this paper, the S-matrix Kohn variational method is adapted to the 3D dissociative adsorption of H_{2} on Ni(100) surface treated as a flat surface, and the state-to-state transition probabilities are obtained. The dependence of the dissociation probabilities on the initial rovibrational state of H _{2}(vjm) is examined. As a result of flat surface approximation, which conserves the rotation quantum number j_{z}=m, the exchange symmetry of H_{2} has an important consequence on the vibrations of the adsorbates. Specially if the rotational state of H_{2} satisfies the condition j+m=odd, the vibrational quantum number of two adsorbed hydrogen atoms must be different. The orientational effect of rotation is such that the in-plane rotation (m=j) is more favorable for molecular dissociation on surface than the out-of-plane rotation (m=0).

Original language | English (US) |
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Pages (from-to) | 6784-6791 |

Number of pages | 8 |

Journal | The Journal of Chemical Physics |

Volume | 97 |

Issue number | 9 |

DOIs | |

State | Published - Jan 1 1992 |

### ASJC Scopus subject areas

- Physics and Astronomy(all)
- Physical and Theoretical Chemistry