### 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) |
---|---|

Pages (from-to) | 6784-6791 |

Number of pages | 8 |

Journal | The Journal of chemical physics |

Volume | 97 |

Issue number | 9 |

State | Published - 1992 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*The Journal of chemical physics*,

*97*(9), 6784-6791.

**An algebraic variational approach to dissociative adsorption of a diatomic molecule on a smooth metal surface.** / Sheng, Jia; Zhang, John.

Research output: Contribution to journal › Article

*The Journal of chemical physics*, vol. 97, no. 9, pp. 6784-6791.

}

TY - JOUR

T1 - An algebraic variational approach to dissociative adsorption of a diatomic molecule on a smooth metal surface

AU - Sheng, Jia

AU - Zhang, John

PY - 1992

Y1 - 1992

N2 - 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 H2 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 jz=m, the exchange symmetry of H2 has an important consequence on the vibrations of the adsorbates. Specially if the rotational state of H2 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).

AB - 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 H2 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 jz=m, the exchange symmetry of H2 has an important consequence on the vibrations of the adsorbates. Specially if the rotational state of H2 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).

UR - http://www.scopus.com/inward/record.url?scp=0000713256&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000713256&partnerID=8YFLogxK

M3 - Article

VL - 97

SP - 6784

EP - 6791

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 9

ER -