Theoretical study of the O(3P) + CN(X2Σ+) → CO(X1Σ+) + N(2D)/N(4S) reactions.

The barrierless exothermic reactions between atomic oxygen and the cyano radical, O(3P) + CN(X2Σ+) → CO(X1Σ+) + N(2D)/N(4S), play a significant role in combustion, astrochemistry, and hypersonic environments. In this work, their dynamics and kinetics are investigated using both wave packet (WP) and quasi-classical trajectory (QCT) methods on recently developed potential energy surfaces of the 12A', 12A,″ and 14A″ states. The product state distributions in the doublet pathway obtained with the WP method for a few partial waves show extensive internal excitation in the CO product. This observation, combined with highly oscillatory reaction probabilities, signals a complex-forming mechanism. The statistical nature of the reaction is confirmed by comparing the WP results with those from phase space theory. The calculated rate coefficients using the WP (with a J-shifting approximation) and QCT methods exhibit agreement with each other near room temperature, 1.77 × 10-10 and 1.31 × 10-10 cm3 molecule-1 s-1, but both are higher than the existing experimental results. The contribution of the quartet pathway is small at room temperature due to a small entrance channel bottleneck. The QCT rate coefficients are further compared with experimental results above 3000 K, and the agreement is excellent.

High-accuracy DMBE potential energy surface for CNO(A''4) and the rate coefficients for the C + NO reaction in the A'2, A''2, and A''4 states.

An accurate potential energy surface (PES) for the lowest lying A''4 state of the CNO system is presented based on explicitly correlated multi-reference configuration interaction calculations with quadruple zeta basis set (MRCI-F12/cc-pVQZ-F12). The ab initio energies are fitted using the double many-body expansion method, thus incorporating long-range energy terms that can accurately describe the electrostatic and dispersion interactions with physically motivated decaying functions. Together with the previously fitted lowest A'2 and A''2 states using the same theoretical framework, this constitutes a new set of PESs that are suitable to predict rate coefficients for all atom-diatom reactions of the CNO system. We use this set of PESs to calculate thermal rate coefficients for the C(P3) + NO(Π2) reaction and compare the temperature dependence and product branching ratios with experimental results. The comparison between theory and experiment is shown to be improved over previous theoretical studies. We highlight the importance of the long-range interactions for low-temperature rate coefficients.

A Crossed Molecular Beams and Computational Study of the Formation of the Astronomically Elusive Thiosilaformyl Radical (HSiS, X2A').

The formation pathways to silicon- and sulfur-containing molecules are crucial to the understanding of silicon-sulfur chemistry in interstellar and circumstellar environments. While multiple silicon- and sulfur-containing species have been observed in deep space, their fundamental formation mechanisms are largely unknown. The crossed molecular beams technique combined with electronic structure and Rice-Ramsperger-Kassel-Marcus (RRKM) calculations was utilized to study the bimolecular reaction of atomic silicon (Si(3Pj)) with thiomethanol (CH3SH, X1A') leading to the thiosilaformyl radical (HSiS, X2A') via an exclusive methyl radical (CH3, X2A2″) loss via indirect scattering dynamics which involves barrierless addition and hydrogen migration in an overall exoergic reaction, indicating the possibility that HSiS can form in cold molecular clouds. The astronomically elusive thiosilaformyl radical may act as a tracer of an exotic silicon-sulfur chemistry to be deciphered toward, for example, the star-forming region SgrB2, thus leading to a better understanding of the formation of silicon-sulfur bonds in deep space.

Potential energy function information from quantum phase shift using the variable phase method.

The present work discusses quantum phase shift sensitivity analysis with respect to the potential energy function. A set of differential equations for the functional derivative of the quantum phase shift with respect to the potential energy function was established and coupled with the variable phase equation. This set of differential equations provides a simple, exact and straightforward way to establish the sensitivity matrix. The present procedure is easier to use than the finite difference approach, in which several direct problems have to be addressed. Furthermore, integration of the established equations can be used to demonstrate how the sensitivity phase shift is accumulated as a function of the interatomic distance. The potential energy function was refined to produce a better quality function. The average error on the phase shift decreased from 9.8% in the original potential function to 0.13% in the recovered potential. The present procedure is an important initial step for further work towards recovering potential energy functions in upper dimensions or to recovering this function from cross sections.