Computation of curve-crossing diagrams by approximate valence bond method

Abstract:

Avoided crossing diagram parameters for the radical exchange reaction and the concerted exchange of two and three bonds are computed by using the approximated valence bond method, which is a nonorthogonal configuration interaction (CI) semiempirical method among the valence bond configuration functions. Here, each valence bond configuration function is a spin-adapted combination of Slater determinants constructed from the Heitler-London or Coulson-Fischer hybrid orbitals. Atomic orbitals integrals are evaluated using semiempirical philosophy, and these provide considerable saving of computer time compared with the most standard ab initio mulristrucrure valence bond methods. The results indicate that the approximate valence bond method is capable of yielding reasonable results for the avoided crossing diagram parameters. These results also indicate that the diagram gap (G) is the decisive factor for the stability of symmetric clusters, Xn, although no clear correlation between the gap G and the geometric distortion is found for different values of n. © 1996 John Wiley & Sons, Inc.

Año de publicación:

1996

Keywords:

Fuente:

scopus

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