Photodissociation dynamics of N3+

The photodissociation dynamics of N-3(+) excited from its (linear) (3)Sigma(-)(g)/(bent)(3)A '' ground to the first excited singlet and triplet states is investigated. Three-dimensional potential energy surfaces for the (1)A', (1)A', and (3)A' electronic states, correlating with the (1)Delta(g) and (3)Pi(u) states in linear geometry, for N-3(+) are constructed using high-level electronic structure calculations and represented as reproducing kernels. The reference ab initio energies are calculated at the MRCI+Q/aug-cc-pVTZ level of theory. For following the photodissociation dynamics in the excited states, rotational and vibrational distributions P(v') and P(j') for the N-2 product are determined from vertically excited ground state distributions. Due to the different shapes of the ground state (3)A '' potential energy surface and the excited states, appreciable angular momentum j' similar to 60 is generated in diatomic fragments. The lifetimes in the excited states extend to at least 50 ps. Notably, results from sampling initial conditions from a thermal ensemble and from the Wigner distribution of the ground state wavefunction are comparable. (C) 2022 Author(s).