title: Comparison of two-body and three-body decomposition of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene.
abstract: We investigated two-body (binary) and three-body (triple) dissociations of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene on the ground potential-energy surfaces using quantum-chemical and Rice-Ramsperger-Kassel-Marcus calculations; most attention is paid on the triple dissociation mechanisms. The triple dissociation includes elimination of a hydrogen molecule from a combination of two separate terminal hydrogen atoms; meanwhile, the rest part simultaneously decomposes to two stable fragments, e.g., C(2)H(4), C(2)H(2), or CO. Transition structures corresponding to the concerted triple dissociation were identified using the B3LYP/6-311G(d,p) level of theory and total energies were computed using the method CCSD(T)/6-311+G(3df, 2p). The forward barrier height of triple dissociation has a trend of ethanedial < propanal < propenal < n-butane < 1-butene < 1,3-butadiene, pertaining to the reaction enthalpy. Ratios of translational energies of three separate fragments could be estimated from the transition structure of triple dissociation. The synchronous concerted dissociation of propanal, propenal, and 1-butene leading to three different types of molecular fragments by breaking nonequivalent chemical bonds is rare. The triple dissociation of propanal, n-butane, 1-butene, and 1,3-butadiene were investigated for the first time. To outline a whole picture of dissociation mechanisms, some significant two-body dissociation channels were investigated for the calculations of product branching ratios. The triple dissociation plays an important role in the three carbonyl compounds, but plays a minor or negligible role in the three hydrocarbons.
authors.affiliation: National Synchrotron Radiation Research Center (NSRRC), 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan.
authors.forename: Chih-Hao
authors.initials: CH
authors.lastname: Chin
authors.forename: Shih-Huang
authors.initials: SH
authors.lastname: Lee
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D002070:Butadienes / Q000737:chemistry*; D002073:Butanes / Q000737:chemistry*; D006037:Glyoxal / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D000447:Aldehydes; D000475:Alkenes; D002070:Butadienes; D002073:Butanes; D006037:Glyoxal; C046888:butane; C005556:propionaldehyde; C013658:propylene; C031763:1,3-butadiene; C058602:1-butene