Accurate diabatization based on combined-hyperbolic-inverse-power-representation: 1,2 2A' states of BeH2.

Abstract

A diabatic potential energy matrix (DPEM) for the two lowest states of BeH2+ has been constructed using the combined-hyperbolic-inverse-power-representation (CHIPR) method. By imposing symmetry constraints on the coefficients of polynomials, the complete nuclear permutation inversion symmetry is correctly preserved in the CHIPR functional form. The symmetrized CHIPR functional form is then used in the diabatization by ansatz procedure. The abinitio energies are reproduced with satisfactory accuracy. In addition, the CHIPR-based DPEM also reproduces the local topology of a conical intersection. Future work will focus on a complete four-state diabatic representation with emphasis on the long-range interactions and spin-orbit couplings, which will enable accurate quantum scattering calculations for the Be+(2P) + H2 → BeH+(X1Σ+) + H(2S) reaction.