4D potential energy surface of NCCN–H2 collision: Rotational dynamics by p-H2 and o-H2 at interstellar temperatures

• Published in: The Journal of chemical physics 2023-08, Vol.159 (7)
• Main Authors: Kushwaha, Apoorv, Dhilip Kumar, T. J.
• Format: Article
• Language: English
• Subjects: Approximation; Artificial neural networks; Boltzmann distribution; Collision dynamics; Computation; Data points; Energy distribution; Interstellar matter; Missing data; Potential energy; Rigid rotors; Scaling factors; Spherical harmonics
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0161335

The rotational excitation rates of NCCN species are studied for its collision with hydrogen (H2) in temperatures ranging from 1 to 100 K. Such collisions can occur in the interstellar medium with H2 in either para (p-) or ortho (o-) state, of which the p-H2 state can be approximated via its collision with He (using a scaling factor) or with a reduced rigid rotor-H2 surface (by averaging over various orientations of H2). In the current work, a four-dimensional (4D) ab initio potential energy surface (PES) is considered to study the collision dynamics of H2 in both p- and o-states and the results are compared with previous approximations. The 4D surface is constructed using the explicitly correlated coupled-cluster method CCSD(T)-F12b with the augmented triple zeta basis AVTZ and then fitted into an artificial neural networks (NN) model to augment the surface and account for missing data points. The radial coefficients are obtained from this NN fitted 4D PES via a least square fit over two spherical harmonics functions. The cross sections (σ) are computed using the close-coupling (CC) method (until 230 cm−1) for both p- and o-H2 collisions, and the rates are obtained by Boltzmann distribution over the translational energy of H2 until 100 K. The o-H2 rates are found to be higher by 25%–30% and 10%–20% compared to the p-H2 rates for Δj = 2 and higher order transitions, respectively. The coupled-state/centrifugal sudden approximated rates are also computed and found to have deviations as large as 40% when compared to CC rates, thus making quantitative descriptions unreliable.