Computational determination of the (A)over-tilde state absorption spectrum of NH3 and of ND3 using a new quasi- diabatic representation of the (X)over-tilde and (A)over-tilde states and full six- dimensional quantum dynamics

A recently developed method to represent adiabatic electronic states coupled by conical intersections has been used to construct a full six-dimensional quasi-diabatic representation of the 1(1)A and 2(1)A states of NH3. This representation is expected to be appropriate to simulate the photodissociation of ammonia when it is excited to the 2(1)A electronic state. In this work, the electronic structure aspects of this quasi-diabatic representation are analyzed. This representation is then used as the basis for a simulation of the (A) over tilde <- (X) over tilde absorption spectrum, dominated by a progression in the upsilon(2) mode, using a full six-dimensional quantum mechanical treatment of the nuclear motion. Results are reported for both NH3 and ND3. This simulation provides the most accurate computational determination of this absorption spectrum reported to date. These results serve to validate the quasi-diabatic representation and set the stage for subsequent studies of vibrationally mediated photodissociation of NH3. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4725496]