Full Dimensional Potential Energy Function and Calculation of State-Specific Properties of the CO+N2 Inelastic Processes Within an Open Molecular Science Cloud Perspective

Abstract

A full dimensional Potential Energy Surface (PES) of the CO + N 2 system has been generated by extending an approach already reported in the literature and applied to N 2 -N 2 (Cappelletti et al., 2008 ), CO 2 -CO 2 (Bartolomei et al., 2012 ), and CO 2 -N 2 (Lombardi et al., 2016b ) systems. The generation procedure leverages at the same time experimental measurements and high-level ab initio electronic structure calculations. The procedure adopts an analytic formulation of the PES accounting for the dependence of the electrostatic and non-electrostatic components of the intermolecular interaction on the deformation of the monomers. In particular, the CO and N 2 molecular multipole moments and electronic polarizabilities, the basic physical properties controlling the behavior at intermediate and long-range distances of the interaction components, were made to depend on relevant internal coordinates. The formulated PES exhibits substantial advantages when used for structural and dynamical calculations. This makes it also well suited for reuse in Open Molecular Science Cloud services.

Advances in non-equilibrium $$\hbox {CO}_2$$ plasma kinetics: a theoretical and experimental review

“…An alternative and in principle more accurate method, balancing accuracy and computational costs, combines a more accurate quantum mechanical treatment (for selected vibrational degrees of freedom) with classical mechanics ones (for the remainder), the so-called quantum-classical method [172], so far adopted for atom-diatom and diatom-diatom collision [173], but in principle amenable of extensions to three-atom molecules.…”

Vibrational Energy Transfer in CO+N2 Collisions: A Database for V–V and V–T/R Quantum-Classical Rate Coefficients

“…For N 2 charge values q ja we adopted those reported in ref. [39], while those for CO q ja are obtained as detailed in Appendix of [18]. The extrapolation of the rigid rotor PES, in order to include the dependence on flexible monomers, has also been described and tested in [18].…”

“…[39], while those for CO q ja are obtained as detailed in Appendix of [18]. The extrapolation of the rigid rotor PES, in order to include the dependence on flexible monomers, has also been described and tested in [18]. Specifically, this is implicitly introduced by considering the dependence of molecular polarizability and of a molecular electric dipole and electric quadrupole moments on the bond length of CO and N 2 .…”

“…For this reason, the quantum-classical (QC) approach, sometimes also referred to as semiclassical, has been used over the years for the description of inelastic scattering in a variety of diatom–diatom systems: N +N [ 10 , 11 , 12 , 13 ], CO+CO [ 14 , 15 ], N +CO [ 11 , 16 , 17 , 18 ], O +O [ 19 , 20 , 21 ], etc. leading, in some cases, to the creation of large databases for V–V rate coefficients.…”

“…We recently introduced a full dimensional analytical surface [ 18 ] by using a well-established semiempirical approach and tested it to reproduce experimental values, like the second virial coefficients, and against accurate ab initio energies. In the same paper preliminary calculations for selected V–V processes, for which experimental rate coefficients are available, were carried out, which showed an overall good qualitative agreement in a wide temperature range, with some quantitative discrepancies in the low temperature regime.…”