Quasiclassical Trajectory Studies of the O(P-3)+CX4(v(k)=0, 1) -> OX(v)+CX3(n(1)n(2)n(3)n(4)) [X = H and D] Reactions on an Ab Initio Potential Energy Surface

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	Quasiclassical Trajectory Studies of the O(P-3)+CX4(v(k)=0, 1) -> OX(v)+CX3(n(1)n(2)n(3)n(4)) [X = H and D] Reactions on an Ab Initio Potential Energy Surface
	Czako, Gabor 1; Liu, Rui 2; Yang, Minghui 2; Bowman, Joel M.3,4; Guo, Hua 5
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2013-08-01
卷号	117 期号:30 页码:6409-6420
英文摘要	We report quasiclassical trajectory calculations of the integral and differential cross sections and the mode-specific product state distributions for the "central-barrier" O(P-3) + CH4/CD4(v(k) = 0, 1) [k = 1, 2, 3, 4] reactions using a full-dimensional ab initio potential energy surface. The mode-specific vibrational distributions for the polyatomic methyl products are obtained by doing a normal-mode analysis in the Eckart frame, followed by standard histogram binning (HB) and energy-based Gaussian binning (1GB). The reactant bending excitations slightly enhance the reactivity, whereas stretching excitations activate the reaction more efficiently. None of the reactant vibrational excitations is as efficient as an equivalent amount of translational energy to promote the reactions. The excitation functions without product zero-point energy (ZPE) constraint are in good agreement with previous 8-dimensional quantum mechanical (QM) results for the ground-state and stretching-excited O + CH4 reactions, whereas for the bending-excited reactions the soft ZPE constraint, which is applied to the sum of the product vibrational energies, provides better agreement with the QM cross sections. All angular distributions show the dominance of backward scattering indicating a direct rebound mechanism, in agreement with experiment. The title reactions produce mainly OH/OD(v = 0) products for all the initial states. HB significantly overestimates the populations of OH/OD(v = 1), especially in the energetic threshold regions, whereas 1GB provides physically correct results. The CH3/CD3 vibrational distributions show dominant populations for ground (v = 0), umbrella-excited (v(2) = 1, 2), in-plane-bending-excited (v(4) = 1), and v(2) + v(4) methyl product states. Neither translational energy nor reactant vibrational excitation transfers significantly into product vibrations.
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
研究领域[WOS]	Chemistry ; Physics
关键词[WOS]	CHLORINE ATOM ; DYNAMICS ; O(P-3) ; QUANTUM ; METHANE ; EXCITATION ; CH4+O(P-3) ; STATE ; MODEL ; BOND
收录类别	SCI
语种	英语
WOS记录号	WOS:000322807300003
公开日期	2015-07-14
内容类型	期刊论文
源URL	[http://ir.wipm.ac.cn/handle/112942/938]
专题	武汉物理与数学研究所_理论与交叉研究部
作者单位	1.Eotvos Lorand Univ, Inst Chem, Lab Mol Struct & Dynam, H-1518 Budapest 112, Hungary 2.Chinese Acad Sci, Wuhan Inst Phys & Math, Wuhan Ctr Magnet Resonance, Key Lab Magnet Resonance Biol Syst,State Key Lab, Wuhan 430071, Peoples R China 3.Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA 4.Emory Univ, Dept Chem, Atlanta, GA 30322 USA 5.Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA
推荐引用方式 GB/T 7714	Czako, Gabor,Liu, Rui,Yang, Minghui,et al. Quasiclassical Trajectory Studies of the O(P-3)+CX4(v(k)=0, 1) -> OX(v)+CX3(n(1)n(2)n(3)n(4)) [X = H and D] Reactions on an Ab Initio Potential Energy Surface[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2013,117(30):6409-6420.
APA	Czako, Gabor,Liu, Rui,Yang, Minghui,Bowman, Joel M.,&Guo, Hua.(2013).Quasiclassical Trajectory Studies of the O(P-3)+CX4(v(k)=0, 1) -> OX(v)+CX3(n(1)n(2)n(3)n(4)) [X = H and D] Reactions on an Ab Initio Potential Energy Surface.JOURNAL OF PHYSICAL CHEMISTRY A,117(30),6409-6420.
MLA	Czako, Gabor,et al."Quasiclassical Trajectory Studies of the O(P-3)+CX4(v(k)=0, 1) -> OX(v)+CX3(n(1)n(2)n(3)n(4)) [X = H and D] Reactions on an Ab Initio Potential Energy Surface".JOURNAL OF PHYSICAL CHEMISTRY A 117.30(2013):6409-6420.