Improved direct diabatization and coupled potential energy surfaces for the photodissociation of ammonia

Abstract

Diabatic potential energy surfaces are a convenient starting point for dynamics calculations of photochemical processes, and they can be calculated by the fourfold way direct diabatization scheme. Here we present an improved definition of the reference orbital for applying the fourfold way direct diabatization scheme to ammonia. The improved reference orbital is a geometry-dependent hybrid orbital that allows one to define consistent dominant configuration lists at all geometries important for photodissociation. Using diabatic energies calculated with the new reference orbital and consistent dominant configuration lists, we have refitted the analytical representations of the ground and the first electronically excited singlet-state potential energy surfaces and the diabatic coupling surface. Improved functional forms were used to reproduce the experimental dissociation energies and excitation energies, which will be important for subsequent simulations of photochemical dynamics. We find that the lowest-energy conical intersection point is at 5.16 eV, with C 2v symmetry. © Springer-Verlag 2007.