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Theoretical study on the ClO/ClO- system electron-transfer reactivity by the golden-rule
Yan, SH; Bu, YX; Qin, M; Sun, LX; Han, K
KeywordElectron-transfer Reactivity Golden-rule Ub3ylp Encounter-complex Electron Coupling Matrix Element clo+clo- System
Source PublicationJOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
2003-07-04
DOI10.1016/S0166-1280(03)00131-3
Volume629Pages:105-115
Indexed BySCI
SubtypeArticle
Department1101
Funding Project1101
Contribution Rank3;2
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Physical
WOS Research AreaChemistry
WOS KeywordX = 1-4 ; AB-INITIO ; CHLORINE OXIDES ; OZONE DEPLETION ; CLO ; MECHANISM ; DIMER ; CL2O2 ; DESTRUCTION ; SPECTRA
AbstractThe structures, properties and electron transfer reactivity of the ClO/ClO- coupling system are studied in this paper at ab initio (UHF and UMP2) levels and the Density Functional Theory (DFT: UB3LYP, UB3P86, UB3PW91) levels employing 6311 + G(3df) basis set and on the basis of the Golden-rule of the time-dependent perturbation theory. Investigations indicate that the results obtained using the UB3LYP method employing 6-311 + G(3df) basis set is in excellent agreement with the experiment. For this coupling system, six stable coupling modes have been found which correspond to six different encounter complexes and denote six different electron transfer mechanism: four O-O directly linked structures (one collinear: D-h, one anti-parallel: C-s, two twist: C-2) and two Cl-O linked structures (cis- and anti- C-s structures). The activation energies, the stabilization energies and the electronic coupling matrix elements have also been calculated for the electron transfer reactions via these six different mechanism at the UB3LYP/6-311 + G(3df) level, and then the electron transfer rates are determined at the same level. The most favorable coupling mode to the electron transfer is the anti-parallel mechanism. The averaged electron transfer rate is about 5.58 X 10(11) M-1 s(-1). It is also implied that the B3LYP method can give more reasonable results for the electron transfer reactivity of this system. (C) 2003 Elsevier B.V. All rights reserved.
Language英语
URL查看原文
WOS IDWOS:000184895300013
Citation statistics
Cited Times:2[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/83369
Collection中国科学院大连化学物理研究所
Affiliation1.Shandong Univ, Inst Theoret Chem, Jinan 250100, Peoples R China
2.Qufu Normal Univ, Dept Chem, Qufu 273165, Peoples R China
3.Acad China, Dalian Inst Chem Phys, Key State Lab Mol React Dynam, Dalian 116023, Peoples R China
Recommended Citation
GB/T 7714
Yan, SH,Bu, YX,Qin, M,et al. Theoretical study on the ClO/ClO- system electron-transfer reactivity by the golden-rule[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2003,629:105-115.
APA Yan, SH,Bu, YX,Qin, M,Sun, LX,&Han, K.(2003).Theoretical study on the ClO/ClO- system electron-transfer reactivity by the golden-rule.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,629,105-115.
MLA Yan, SH,et al."Theoretical study on the ClO/ClO- system electron-transfer reactivity by the golden-rule".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 629(2003):105-115.
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