Potential energy surfaces for ion-molecule reactions. Intersection of the /sup 3/A/sub 2/ and /sup 2/B/sub 1/ surfaces of NH/sup +//sub 2 [electronic resource].
- Berkeley, Calif. : University of California, Berkeley, 1976.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
- Physical Description:
- Pages: 23 : digital, PDF file
- Additional Creators:
- University of California, Berkeley
United States. Department of Energy. Office of Scientific and Technical Information
- A theoretical study of two of the low-lying NH/sub 2//sup +/ potential energy surfaces was performed. The intersection and avoided intersection (for C/sub s/ geometries) of the lowest /sup 3/A/sub 2/ and /sup 3/B/sub 1/ surfaces allows a pathway by which the ground state of HH/sub 2//sup +/ may be accessed without a potential barrier. The electronic structure calculations employed a double zeta plus polarization basis set, and correlation effects were taken into account using the newly developed Vector Method (VM). To test the validity of this basis, additional self-consistent-field studies were performed using a very large contracted gaussian basis N(13s 8p 3d/9s 6p 3d), H(6s 2p/4s 2p). The /sup 3/A/sub 2/ surface, on which N/sup +/ and H/sub 2/ may approach, has a surprising deep potential minimum, approximately 60 kcal/mole, occurring at r/sub e/(NH) approximately 1.26 A and theta/sub e/(HNH) approximately 43/sup 0/. Electron correlation is responsible for about 15 kcal of this well depth, which appears fairly insensitive to extension of the basis set beyond the double zeta plus polarization level. The line of intersection (or seam) of the /sup 3/A/sub 2/ and /sup 3/B/sub 1/ surfaces is presented both numerically and pictorially. The minimum energy along this seam occurs at approximately 51 kcal below separated N/sup +/ + H/sub 2/. Thus for sufficiently low energies one expects N/sup +/ - H/sub 2/ collisions to provide considerable ''complex formation.'' 3 figs, 1 table, 28 refs.
- Published through SciTech Connect.
Faraday discussion on potential energy surfaces, Brighton, UK, 8 Sep 1976.
Bender, C.F.; Schaefer, H.F. III; Meadows, J.H.
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