Abstract
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 is 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.
Recommended Citation
G. S. Tschumper et al., "An ab Initio Excursion on the Lowest 18 Electronic Surfaces of the NCl + NCl System: Some Insight into the Long-Range Self-Quenching Pathways of the First Excited State of NCl," Journal of Physical Chemistry A, vol. 106, no. 36, pp. 8453 - 8460, American Chemical Society, Sep 2002.
The definitive version is available at https://doi.org/10.1021/jp025692n
Department(s)
Chemistry
International Standard Serial Number (ISSN)
1089-5639
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2024 American Chemical Society, All rights reserved.
Publication Date
12 Sep 2002
