title: A quantum Monte Carlo study of the reactions of CH with acrolein.
abstract: To assist understanding of combustion processes, we have investigated reactions of methylidyne (CH) with acrolein (CH2CHCHO) using the quantum Monte Carlo (QMC) and other computational methods. We present a theoretical study of the major reactions reported in a recent experiment on the subject system. Both DFT and MP2 computations are carried out, and the former approach is used to form the independent-particle part of the QMC trial wave function used in the diffusion Monte Carlo (DMC) variant of the QMC method. In agreement with experiment, we find that the dominant product channel leads to formation of C4H4O systems + H with leading products of furan + H and 1,3-butadienal + H. Equilibrium geometries, atomization energies, reaction barriers, transition states, and heats of reaction are computed using the DFT, MP2, and DMC approaches and compared to experiment. We find that DMC results are in close agreement with experiment. The kinetics of the subject reactions are determined by solving master equations with the MultiWell software suite.
authors.forename: Srimanta
authors.initials: S
authors.lastname: Pakhira
authors.affiliation: ⊥Laboratoire de Chimie et Physique Quantiques, CNRS-IRSAMC, Université de Toulouse, Toulouse F-31062, France.
authors.forename: Benjamin S
authors.initials: BS
authors.lastname: Lengeling
authors.forename: Olayinka
authors.initials: O
authors.lastname: Olatunji-Ojo
authors.affiliation: ⊥Laboratoire de Chimie et Physique Quantiques, CNRS-IRSAMC, Université de Toulouse, Toulouse F-31062, France.
authors.forename: Michel
authors.initials: M
authors.lastname: Caffarel
authors.affiliation: #Department of Mechanical Engineering, University of California, Berkeley, California 94720-1740, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Frenklach
authors.forename: William A
authors.initials: WA
authors.lastname: Lester
mesh_terms: D000171:Acrolein / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D009010:Monte Carlo Method; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D000475:Alkenes; D000171:Acrolein