biostudies-literatureUnknown4(14)Guan YHybrid and double-hybrid density functionals are employed to explore the O-NO bond dissociation mechanism of vinyl nitrite (CH₂=CHONO) into vinoxy (CH₂=CHO) and nitric monoxide (NO). In contrast to previous investigations, which point out that the O-NO bond dissociation of vinyl nitrite is barrierless, our computational results clearly reveal that a kinetic barrier (first-order saddle point) in the O-NO bond dissociation is involved. Furthermore, a radical-radical adduct is recommended to be present on the dissociation path. The activation and reaction enthalpies at 298.15 K for the vinyl nitrite dissociation are calculated to be 91 and 75 kJ mol^-1 at the M062X/MG3S level, respectively, and the calculated reaction enthalpy compares very well with the experimental result of 76.58 kJ mol^-1. The M062X/MG3S reaction energetics, gradient, Hessian, and geometries are used to estimate vinyl nitrite dissociation rates based on the multistructural canonical variational transition-state theory including contributions from hindered rotations and multidimensional small-curvature tunneling at temperatures from 200 to 3000 K, and the rate constant results are fitted to the four-parameter Arrhenius expression of 4.2 × 10⁹ (<i>T</i>/300)^4.3 exp[-87.5(<i>T</i> - 32.6)/(<i>T</i> ² + 32.6²)] s^-1.ACS omega16052-16061https://www.ebi.ac.uk/biostudies/studies/S-EPMC6777096biostudies-literatureInvestigation on the Thermal Dissociation of Vinyl Nitrite with a Saddle Point Involved.PMC6777096Guan YMa HSong JLou JfalseInvestigation on the Thermal Dissociation of Vinyl Nitrite with a Saddle Point Involved.Hybrid and double-hybrid density functionals are employed to explore the O-NO bond dissociation mechanism of vinyl nitrite (CH₂=CHONO) into vinoxy (CH₂=CHO) and nitric monoxide (NO). In contrast to previous investigations, which point out that the O-NO bond dissociation of vinyl nitrite is barrierless, our computational results clearly reveal that a kinetic barrier (first-order saddle point) in the O-NO bond dissociation is involved. Furthermore, a radical-radical adduct is recommended to be present on the dissociation path. The activation and reaction enthalpies at 298.15 K for the vinyl nitrite dissociation are calculated to be 91 and 75 kJ mol^-1 at the M062X/MG3S level, respectively, and the calculated reaction enthalpy compares very well with the experimental result of 76.58 kJ mol^-1. The M062X/MG3S reaction energetics, gradient, Hessian, and geometries are used to estimate vinyl nitrite dissociation rates based on the multistructural canonical variational transition-state theory including contributions from hindered rotations and multidimensional small-curvature tunneling at temperatures from 200 to 3000 K, and the rate constant results are fitted to the four-parameter Arrhenius expression of 4.2 × 10⁹ (<i>T</i>/300)^4.3 exp[-87.5(<i>T</i> - 32.6)/(<i>T</i> ² + 32.6²)] s^-1.2019-01-01T00:00:00Z2019 Oct2022-02-09T11:02:58.863Z2019-10-16T07:07:05ZS-EPMC67770963159247310.1021/acsomega.9b02242