Ultrafast photodissociation dynamics of pyrazole, imidazole and their deuterated derivatives using ab initio multiple cloning

Abstract

We present results obtained using the ab initio multiple cloning (AIMC) method to simulate fully quantum dynamics for imidazole and its structural isomer pyrazole along with their selectively deuterated species. We simulate the ultrafast dissociation of the N–H/D bond for these molecules along the repulsive ¹πσ* state which agrees well with previous experimental results. Our results give evidence for a two-stage dissociation of the N–H/D bond on the sub-50 fs regime for imidazole, pyrazole and their selectively deuterated species, and give evidence for the importance of the repulsive ¹πσ* state along the N–H/D bond coordinate for the relaxation of both imidazole and pyrazole. The ability of these calculations to reproduce experimental results lends confidence that larger complex systems could be explored with predictive capabilities with the AIMC method. These results also confirm the ability of the AIMC method to add detailed insights into which experiments are blind.