Experimental and theoretical study of the low-temperature kinetics of the reaction of CN with CH2O and implications for interstellar environments

Niclas A West; Lok Hin Desmond Li; Tom J Millar; Marie Van de Sande; Edward Rutter; Mark A Blitz; Julia H Lehman; Leen Decin; Dwayne E Heard

doi:10.1039/d2cp05043a

Experimental and theoretical study of the low-temperature kinetics of the reaction of CN with CH₂O and implications for interstellar environments

Phys Chem Chem Phys. 2023 Mar 15;25(11):7719-7733. doi: 10.1039/d2cp05043a.

Authors

Niclas A West¹, Lok Hin Desmond Li¹, Tom J Millar², Marie Van de Sande³, Edward Rutter¹, Mark A Blitz¹, Julia H Lehman¹, Leen Decin⁴, Dwayne E Heard¹

Affiliations

¹ School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK. [email protected].
² Astrophysics Research Centre, School of Mathematics and Physics, Queen's University Belfast, University Road, Belfast BT7 1NN, UK.
³ School of Physics and Astronomy, University of Leeds, Leeds, LS2 9JT, UK.
⁴ Instituut voor Sterrenkunde, KU Leuven, Celestijnenlaan 200D, 3001 Leuven, Belgium.

Abstract

Rate coefficients for the reaction of CN with CH₂O were measured for the first time below room temperature in the range 32-103 K using a pulsed Laval nozzle apparatus together with the Pulsed Laser Photolysis-Laser-Induced Fluorescence technique. The rate coefficients exhibited a strong negative temperature dependence, reaching (4.62 ± 0.84) × 10^-11 cm³ molecule^-1 s^-1 at 32 K, and no pressure dependence was observed at 70 K. The potential energy surface (PES) of the CN + CH₂O reaction was calculated at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ level of theory, with the lowest energy channel to reaction characterized by the formation of a weakly-bound van der Waals complex, bound by 13.3 kJ mol^-1, prior to two transition states with energies of -0.62 and 3.97 kJ mol^-1, leading to the products HCN + HCO or HNC + HCO, respectively. For the formation of formyl cyanide, HCOCN, a large activation barrier of 32.9 kJ mol^-1 was calculated. Reaction rate theory calculations were performed with the MESMER (Master Equation Solver for Multi Energy well Reactions) package on this PES to calculate rate coefficients. While this ab initio description provided good agreement with the low-temperature rate coefficients, it was not capable of describing the high-temperature experimental rate coefficients from the literature. However, increasing the energies and imaginary frequencies of both transition states allowed MESMER simulations of the rate coefficients to be in good agreement with data spanning 32-769 K. The mechanism for the reaction is the formation of a weakly-bound complex followed by quantum mechanical tunnelling through the small barrier to form HCN + HCO products. MESMER calculations showed that channel generating HNC is not important. MESMER simulated the rate coefficients from 4-1000 K which were used to recommend best-fit modified Arrhenius expressions for use in astrochemical modelling. The UMIST Rate12 (UDfa) model yielded no significant changes in the abundances of HCN, HNC, and HCO for a variety of environments upon inclusion of rate coefficients reported here. The main implication from this study is that the title reaction is not a primary formation route to the interstellar molecule formyl cyanide, HCOCN, as currently implemented in the KIDA astrochemical model.