Photodissociation dynamics of N.

The photodissociation dynamics of N excited from its (linear) Σ /(bent) A″ ground to the first excited singlet and triplet states is investigated. Three-dimensional potential energy surfaces for the A', A″, and A' electronic states, correlating with the Δ and Π states in linear geometry, for N 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.

N : Full-dimensional ground state potential energy surface, vibrational energy levels, and dynamics.

The fundamental vibrational frequencies and higher vibrationally excited states for the N ion in its electronic ground state have been determined from quantum bound state calculations on three-dimensional potential energy surfaces (PESs) computed at the coupled-cluster singles and doubles with perturbative triples [CCSD(T)]-F12b/aug-cc-pVTZ-f12 and multireference configuration interaction singles and doubles with quadruples (MRCISD+Q)/aug-cc-pVTZ levels of theory. The vibrational fundamental frequencies are 1130 cm (ν, symmetric stretch), 807 cm (ν, asymmetric stretch), and 406 cm (ν, bend) on the higher-quality CCSD(T)-F12b surface. Bound state calculations based on even higher level PESs [CCSD(T)-F12b/aug-cc-pVQZ-f12 and MRCISD+Q-F12b/aug-cc-pVTZ-f12] confirm the symmetric stretch fundamental frequency as ∼1130 cm.

Detecting reactive islands using Lagrangian descriptors and the relevance to transition path sampling.

It has been known for sometime now that isomerization reactions, classically, are mediated by phase space structures called reactive islands (RI). RIs provide one possible route to correct for the nonstatistical effects in the reaction dynamics. In this work, we map out the reactive islands for the two dimensional Müller-Brown model potential and show that the reactive islands are intimately linked to the issue of rare event sampling.