| Autor: |
Tschumper, G. S., Heaven, M. C., Morokuma, K. |
| Zdroj: |
The Journal of Physical Chemistry - Part A; September 2002, Vol. 106 Issue: 36 p8453-8460, 8p |
| Abstrakt: |
A series of state-averaged complete active space self-consistent field (SA-CASSCF) computations were carried out in search of low-energy self-annihilation pathways for two NCl molecules in their first excited state (a1Δ). Numerous scans of the lowest 18 electronic surfaces that correlate with the interaction of two NCl molecules in the X3Σ-, a1Δ, and b1Σ+ states are reported. Eight long-range, low-energy pathways were located (four in C2v and eight in C2h symmetry) that connect NCl(a1Δ) + NCl(a1Δ) to NCl(X3Σ-) + NCl(b1Σ+) and NCl(X3Σ-) + NCl(a1Δ). It was possible to rigorously characterize the minima on four of these seams of crossings (MSXs). The MSXs between the a + a manifold and the X + b manifold are only 1.8−4.5 kcal mol-1 above the a + a asymptote and therefore energetically accessible. Additional scans suggest these MSXs are planar but, to some extent, prefer to distort from C2v cis and C2h trans structures to Cs orientations, which would lower the MSX energies slightly. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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