Unraveling the Photoelectron Spectrum of 1-Phospha-2,3,4-triazolate Anion, HCPN 3 - , A Theoretical Approach.

The first five low-lying electronic states of HCPN 3 are probed through extensive ab initio electronic structure and quantum dynamics studies to reproduce the 193 nm photoelectron spectrum. Vibronic Hamiltonian is constructed and availed for time-dependent (TD) and time-independent (TI) quantum dynamical studies. The presence of numerous conical intersections (CIs) and crossings among electronic states yielded interesting nonadiabatic effects in the photoelectron bands of the overall spectrum. Moreover, the theoretical bands corresponding to five electronic states have reproduced all three experimental spectral bands. Among these, the first two bands originated due to a combination of four electronic states as predicted by previous studies. The third band corresponds to the fifth electronic state. The results calculated via TD and TI approaches exhibited satisfying agreement with the experimental results.