Adiabatic and approximate diabatic potential energy surfaces for the B...H2 van der Waals molecule
- 15 October 1993
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 99 (8) , 6014-6026
- https://doi.org/10.1063/1.465900
Abstract
We report multireference configuration‐interaction calculations for the lowest potential energy surfaces of the B(2s22p 2P)...H2 van der Waals molecule. The degeneracy of the 2p orbital implies that there exist three adiabatic potential energy surfaces (two of A’ symmetry and one of A‘ symmetry in Cs geometry) which become degenerate at large B–H2 separation. By assuming that the two adiabatic states of A’ symmetry correspond primarily to an orthogonal transformation of the in‐plane B 2p orbitals, one can use calculated matrix elements of the electronic orbital angular momentum to transform to an approximate diabatic representation, which involves four potential energy functions. The proper angular expansion of these functions in terms of reduced rotation matrix elements is discussed and an analytic representation of the calculated points is obtained. The minimum energy of the B(2s22p 2P)...H2 van der Waals molecule is predicted to occur in C2v geometry with an electronic symmetry of 2B2, at a B–H2 distance of 3.11 Å, and a dissociation energy De of 121 cm−1. For the interaction of B(2P) with p‐H2, assumed spherical in j=0, the zero‐point corrected dissociation energy is D0=25 cm−1.Keywords
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