Ab initio calculations of autoionizing states using block diagonalization: Collinear diabatic states for dissociative recombination of electrons with N2H

[Display omitted] ► We calculate dissociating, autoionizing states using block diagonalization. ► We applied the method to the dissociative recombination of electrons with N2H+. ► Rydberg-valence coupling was distentangled from N2 bond-breaking effects. ► For N2H, the N2+H product channel appears to...

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Bibliographic Details
Published in:Chemical physics letters 2012-03, Vol.529, p.10-15
Main Authors: Kashinski, D.O., Talbi, D., Hickman, A.P.
Format: Article
Language:English
Subjects:
Astrophysics
Chemical Sciences
or physical chemistry
Physics
Sciences of the Universe
Solar and Stellar Astrophysics
Theoretical and
Online Access:Get full text
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Summary:[Display omitted] ► We calculate dissociating, autoionizing states using block diagonalization. ► We applied the method to the dissociative recombination of electrons with N2H+. ► Rydberg-valence coupling was distentangled from N2 bond-breaking effects. ► For N2H, the N2+H product channel appears to be favored. Dissociating autoionizing states for dissociative recombination of electrons with N2H+ have been calculated using block diagonalization. Multi-reference CI calculations for collinear N2H and N2H+ were performed to assess the branching ratio to the product channels. The effects of the strong Rydberg-valence mixing in the N2H excited states were disentangled from the changes in the molecular orbitals arising solely from N2 bond stretching and breaking. The results suggest that N2+H should be favored over NH+N, because of the absence of a favorable dissociating state for the N2 bond breaking.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2012.01.037