Atmospheric reaction of OH radicals with 2-methyl-3-buten-2-ol (MBO): Quantum chemical investigation on the reaction mechanism

被引：7

作者：

Du, Benni

Zhang, Weichao ^{[1
]}

机构：

[1] Jiangsu Normal Univ, Coll Chem & Chem Engn, Jiangsu Key Lab Green Synthet Chem Funct Mat, Xuzhou 221116, Jiangsu, Peoples R China

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2012年 / 999卷

关键词：

OH radicals; MBO; Reaction mechanism; CCSD(T); GAS-PHASE REACTIONS; QUADRATIC CONFIGURATION-INTERACTION; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; RATE CONSTANTS; UNSATURATED ALCOHOLS; RATE COEFFICIENTS; METHYL BUTENOL; AB-INITIO; PRODUCTS;

D O I：

10.1016/j.comptc.2012.08.023

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The reaction mechanisms of OH radicals with MBO in the presence of O-2 and NO have been extensively investigated at the CCSD(T) method with geometries optimized at the MP2(full)/6-311+G(d,p) level. The ab initio calculations show that the title reaction occurs predominantly via initial additions of OH radicals to the two unsaturated C atoms of MBO. Under atmospheric conditions, the primary product pathway for OH + MBO is the formation of CH2OHCHO (P9) + CH3COCH3 (P10), and HCHO + (CH3)(2)COHCHO (P8) is the secondary one, which are in agreement with the experimental results. The reaction mechanism of yielding these products established in this study is different from previous expectation and the reason for this discrepancy has been discussed. (C) 2012 Elsevier B.V. All rights reserved.

引用

页码：109 / 120

页数：12

共 46 条

[1] Products and mechanisms of the gas-phase reactions of OH radicals and O3 with 2-methyl-3-buten-2-ol [J].

Alvarado, A ;

Tuazon, EC ;

Aschmann, SM ;

Arey, J ;

Atkinson, R .

ATMOSPHERIC ENVIRONMENT, 1999, 33 (18) :2893-2905

[2] Approach to the atmospheric chemistry of methyl nitrate and methylperoxy nitrite.: Chemical mechanisms of their formation and decomposition reactions in the gas phase [J].

Arenas, Juan F. ;

Avila, Francisco J. ;

Otero, Juan C. ;

Pelaez, Daniel ;

Soto, Juan .

JOURNAL OF PHYSICAL CHEMISTRY A, 2008, 112 (02) :249-255

[3] Gas-phase tropospheric chemistry of volatile organic compounds .1. Alkanes and alkenes [J].

Atkinson, R .

JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1997, 26 (02) :215-290

[4] Atmospheric degradation of volatile organic compounds [J].

Atkinson, R ;

Arey, J .

CHEMICAL REVIEWS, 2003, 103 (12) :4605-4638

[5]

Atkinson R., 1989, J. Phys. Chem. Ref. Data, V1, P1

[6] Rate constants for the atmospheric reactions of alkoxy radicals: An updated estimation method [J].

Atkinson, Roger .

ATMOSPHERIC ENVIRONMENT, 2007, 41 (38) :8468-8485

[7] Experimental and theoretical studies of the kinetics of the reactions of OH and OD with 2-methyl-3-buten-2-ol between 300 and 415 K at low pressure [J].

Baasandorj, Munkhbayar ;

Stevens, Philip S. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (04) :640-649

[8] Photooxidation of 2-Methyl-3-Buten-2-ol (MBO) as a Potential Source of Secondary Organic Aerosol [J].

Chan, Arthur W. H. ;

Galloway, Melissa M. ;

Kwan, Alan J. ;

Chhabra, Puneet S. ;

Keutsch, Frank N. ;

Wennberg, Paul O. ;

Flagan, Richard C. ;

Seinfeld, John H. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2009, 43 (13) :4647-4652

[9] Mechanism and dynamics of the CH2OH+O2 reaction [J].

Dibble, TS .

CHEMICAL PHYSICS LETTERS, 2002, 355 (1-2) :193-200

[10] GAUSSIAN-BASIS SETS FOR USE IN CORRELATED MOLECULAR CALCULATIONS .1. THE ATOMS BORON THROUGH NEON AND HYDROGEN [J].

DUNNING, TH .

JOURNAL OF CHEMICAL PHYSICS, 1989, 90 (02) :1007-1023

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