title: Kinetics of Thermal Unimolecular Decomposition of Acetic Anhydride: An Integrated Deterministic and Stochastic Model.
abstract: An integrated deterministic and stochastic model within the master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) framework was first used to characterize temperature- and pressure-dependent behaviors of thermal decomposition of acetic anhydride in a wide range of conditions (i.e., 300-1500 K and 0.001-100 atm). Particularly, using potential energy surface and molecular properties obtained from high-level electronic structure calculations at CCSD(T)/CBS, macroscopic thermodynamic properties and rate coefficients of the title reaction were derived with corrections for hindered internal rotation and tunneling treatments. Being in excellent agreement with the scattered experimental data, the results from deterministic and stochastic frameworks confirmed and complemented each other to reveal that the main decomposition pathway proceeds via a 6-membered-ring transition state with the 0 K barrier of 35.2 kcal·mol-1. This observation was further understood and confirmed by the sensitivity analysis on the time-resolved species profiles and the derived rate coefficients with respect to the ab initio barriers. Such an agreement suggests the integrated model can be confidently used for a wide range of conditions as a powerful postfacto and predictive tool in detailed chemical kinetic modeling and simulation for the title reaction and thus can be extended to complex chemical reactions.
authors.affiliation: Institute for Computational Science and Technology , SBI Building, Quang Trung Software City, Tan Chanh Hiep Ward, District 12, Ho Chi Minh City, Vietnam.
authors.forename: Tam V-T
authors.initials: TV
authors.lastname: Mai
authors.affiliation: Institute for Computational Science and Technology , SBI Building, Quang Trung Software City, Tan Chanh Hiep Ward, District 12, Ho Chi Minh City, Vietnam.
authors.forename: Minh V
authors.initials: MV
authors.lastname: Duong
authors.affiliation: Institute for Computational Science and Technology , SBI Building, Quang Trung Software City, Tan Chanh Hiep Ward, District 12, Ho Chi Minh City, Vietnam.
authors.forename: Hieu T
authors.initials: HT
authors.lastname: Nguyen
authors.affiliation: Department of Mechanical and Electromechanical Engineering, National Sun Yat-Sen University , Kaohsiung, 80424, Taiwan.
authors.forename: Kuang C
authors.initials: KC
authors.lastname: Lin
authors.affiliation: International University, Vietnam National University - HCMC , Quarter 6, Linh Trung Ward, Thu Duc District, Ho Chi Minh City, Vietnam.
authors.forename: Lam K
authors.identifier: http://orcid.org/0000-0002-3683-2787
authors.initials: LK
authors.lastname: Huynh