Photodissociation Dynamics of the Highly Stable ortho-Nitroaniline Cation

Abstract

0rtho-Nitroaniline (ONA) is a model for the insensitive high explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) that shares strong hydrogen bonding character between adjacent nitro and amino groups. This work reports femtosecond time-resolved mass spectrometry (FTRMS) measurements and theoretical calculations that explain the high stability of the ONA cation compared with related nitroaromatic molecules. Ab initio calculations found that the lowest-lying electronic excited state of the ONA cation, D 1 , lies more than 2 eV above the ground state, and the energetic barriers to rearrangement and dissociation reactions exceed this D 1 energy. These theoretical results were confirmed by FTRMS pump−probe measurements showing that (1) fragment ions represented less than 30% of the total ion yield when a 10 14 W cm −2 , 1300 nm, 20 fs pump pulse was used to ionize ONA; and (2) 3.1 eV (400 nm) photons were required to induce dissociation of the ONA cation. Stronger coupling between the ground D 0 and excited D 4 states of the ONA cation at the geometry of neutral ONA resulted in a transient enhancement of fragment ion yields at <300 fs pump−probe delay times, prior to relaxation of the ONA cation to its optimal geometry.