Gaussian-2 calculations of the thermochemistry of Criegee intermediates in gas phase reactions

doi:10.3866/PKU.WHXB19981114

	Gaussian-2 calculations of the thermochemistry of Criegee intermediates in gas phase reactions
	Qi, B ; Su, KH ; Wang, YB ; Wen, ZY ; Tang, XY
刊名	ACTA PHYSICO-CHIMICA SINICA
	1998-11-01
卷号	14 页码:1033-1039
关键词	Criegee atmospheric chemistry thermodynamics G2 G2(fu1)
ISSN号	1000-6818
DOI	10.3866/PKU.WHXB19981114
英文摘要	Criegee intermediate is believed to play an important role in the atmospheric chemistry. Because of its short life and the difficulty in experimental study, we carried out ab initio calculations on the thermochemistry of the Criegee involving reactions in this study. Thermochemistry data of reaction enthalpies and Gibbs free energies for four different stable structures of the Criegee intermediates (singlet CH2OO 1 (1)A(1) in C-2v, triplet CH2OO 2 B-3(1) in C-2v, singlet CH2OO 3 (1)A' in C-s and triplet CH2OO 4 in C-1 symmetry) involved in some of the gas-phase reactions were calculated at the standard Gaussian-2 [G2(MP2) and G2] and a modified G2, G2(fu1)([10]), levels of theory. Relative energies among those Criegees and formic acid were compared. Chemical reactions include the formation of Criegees, re-arrangement from Criegee to formic acid, dissociations (producing CH2(B-3(1))+O-2, CH2((1)A(1))+O-2, CO2+H-2, CO2+2H, CO+H2O, OH+HCO) and the reactions between Criegee and NO/H2O. Standard equilibrium constants for some reactions were investigated and may be obtained for all of the rest reactions involved in this study by the standard Gibbs free energies. It is shown that the formation of Criegee 1 - 4 by ethylene and ozone, the re-arrangement from any Criegee to formic acid, the dissociation in producing CO2+O-2 and CO+H2O and the reactions between any Criegee and NO/H2O are all favourable thermodynamicaly, The dissociation in forming CO2+2H and OH+HCO is less favourable. While the dissociation in forming carbene (either in B-3(1) or (1)A(1) state) is not allowed by Delta(r)G(m)(-) values. Standard enthalpies of formation at 298 K for the four Criegees were predicted at the G2(fu1) level of theory. Each value is the average value from ten of the above reactions and they are -4.3, 74.8, 98.0 and 244.6 kJ . mol(-1) at the G2(fu1) level for Criegee 1 to Criegee 4, respectively. In addition, the standard enthalpy of formation at 298 K for HOCH2OOH is further predicted to be -315.6 kJ . mol(-1) at the G2(MP2) level.
WOS关键词	ENERGIES ; DISSOCIATION ; OZONOLYSIS ; OZONE
WOS研究方向	Chemistry
语种	英语
出版者	PEKING UNIV PRESS
WOS记录号	WOS:000077400300014
内容类型	期刊论文
源URL	[http://119.78.100.186/handle/113462/35742]
专题	中国科学院近代物理研究所
通讯作者	Su, KH
作者单位	1.Northwestern Polytech Univ, Dept Chem Engn, Xian 710072, Peoples R China 2.Shaanxi Normal Univ, Dept Chem, Xian 710062, Peoples R China 3.Peking Univ, Ctr Environm Sci, State Key Lab Environm Simulat & Pollut Control, Beijing 100871, Peoples R China 4.NW Univ Xian, Inst Modern Phys, Xian 710068, Peoples R China
推荐引用方式 GB/T 7714	Qi, B,Su, KH,Wang, YB,et al. Gaussian-2 calculations of the thermochemistry of Criegee intermediates in gas phase reactions[J]. ACTA PHYSICO-CHIMICA SINICA,1998,14:1033-1039.
APA	Qi, B,Su, KH,Wang, YB,Wen, ZY,&Tang, XY.(1998).Gaussian-2 calculations of the thermochemistry of Criegee intermediates in gas phase reactions.ACTA PHYSICO-CHIMICA SINICA,14,1033-1039.
MLA	Qi, B,et al."Gaussian-2 calculations of the thermochemistry of Criegee intermediates in gas phase reactions".ACTA PHYSICO-CHIMICA SINICA 14(1998):1033-1039.