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/

Conference · Thu Apr 01 04:00:00 EST 1976

OSTI ID:7352699

Bender, C F; Meadows, J H; Schaefer, III, H F

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.

• Research Organization: California Univ., Berkeley (USA). Lawrence Berkeley Lab.
• DOE Contract Number: W-7405-ENG-48
• OSTI ID: 7352699
• Report Number(s): LBL-5114; CONF-760901-2
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
CHARGED PARTICLES
CHEMICAL REACTIONS
COLLISIONS
CORRELATIONS
CRYOGENIC FLUIDS
ELECTRON CORRELATION
ELEMENTS
ENERGY
ENERGY LEVELS
FLUIDS
GROUND STATES
HARTREE-FOCK METHOD
HYDROGEN
INTERMOLECULAR FORCES
ION COLLISIONS
ION-MOLECULE COLLISIONS
IONS
MATHEMATICAL MODELS
MOLECULE COLLISIONS
NITROGEN IONS
NONMETALS
POTENTIAL ENERGY
SELF-CONSISTENT FIELD