Photodissociation dynamics of N3+

Abstract

The photodissociation dynamics of N3+ excited from its (linear) 3Σg- /bent 3A'ground to the first excited singlet and triplet states is investigated. Three dimensional potential energy surfaces for the 1A', 1A', and 3A' electronic states, correlating with the 1Δg and 3 Πu states in linear geometry, for N3+ 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 N2 product are determined from vertically excited ground state distributions. Due to the different shapes of the ground state 3A' PES and the excited states, appreciable angular momentum j' ∼ 60 is generated in the 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.

PyQCAMS: Python Quasi-Classical Atom–Molecule Scattering

“…Finally, the product count⃗ n f is created following Section 2.1.2. We first check each effective potential as to whether it can support bound states, then we check the final relative energies based on Equation (8). If more than one bound molecule is found, we denote it as an intermediate complex in the final output.…”

“…However, the initial and final states are chosen following the Bohr-Sommerfeld quantization rule, yielding accurate predictions at significantly less cost than quantum dynamics as long as they fall within given conditions-i.e., a high collision energy with a large number of contributing partial waves [3]. QCT has been used in a multitude of scenarios relevant to chemical physics [4][5][6][7][8][9][10] and cold and ultracold chemistry [11][12][13], ranging from the ultracold to the hyperthermal regimes. In particular, it has been used to study the relaxation and reaction dynamics of cold atom-ionic molecule [11,12] and atom-molecule collisions [14].…”