N(S-4/D-2)+N-2: Accurate ab initio-based DMBE potential energy surfaces and surface-hopping dynamics

作者：Galvao B R L; Caridade P J S B; Varandas A J C^*

来源：Journal of Chemical Physics, 2012, 137(22): 22A515.

DOI：10.1063/1.4737858

This work gives a full account of the N(S-4/D-2)+N-2((1)Sigma(+)(g)) interactions via accurate electronic structure calculations and study of the involved exchange reactions. A 2 x 2 diabatic representation of the potential energy surface is suggested for N-3((2)A%26apos;), which, combined with the two previously reported adiabatic forms for (2)A %26apos;%26apos; and another for (4)A %26apos;%26apos;, completes the set of five global potentials required to study the title collisional processes. The trajectory results provide the first N(D-2)+N-2 rate constants, and allow a comparison with the ones for N(S-4)+N-2. Nonadiabatic effects are estimated by surface hopping, and the geometrical phase effect assessed by following the trajectories that encircle the crossing seam.

• 出版日期2012-12-14