Browsing by Author "Xu, ZF"

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Ab initio studies of ClOx reactions. 3. Kinetics and mechanism for the OH plus OClO reaction
(2003-02-20)
Xu, ZF
;
Zhu, RS
;
Lin, MC
;
交大名義發表
;
National Chiao Tung University
The mechanism for the OH + OClO reaction on the singlet and triplet surfaces and its rate constants for formation of various products have been investigated by means of ab initio molecular orbital theory and variational RRKM theory calculations. The geometric parameters of stationary points were optimized at the B3LYP level of theory with the 6-311G(d,p) and 6-311+G(3df,2p) basis sets, and the potential energy surfaces were evaluated at the G2M(CC2)//B3LYP/6-311+G(3df,2p) level of theory. Three main product channels, all located on the singlet PES, have been identified: (1) HOO + ClO, (2) HOCl + O-1(2), and (3) HOClO2, the association product. The predicted results show that the rate constants for channels 1 and 2 are pressure-independent up to 1000 atm and that for channel 3 is strongly pressure dependent. Below 1000 K, all rate constants were found to vary negatively with temperature. The individual and total rate constants in the temperature range from 200 to 1000 K at 1 Torr He pressure can be represented by k(1)(T) = 1.22 x 10(-22)T(2.75) exp(1682/T), k(2)(T) = 5.47 x 10(-20)T(2.07) exp(2064/T), k(3)(T) = 1.37 x 10(4)T(-6.61) exp(-536/T) (200-500 K) and 4.99 x 10(54)T(-22.36) exp(-9807/T) (500-1000 K), and k(tot)(T) = 1.78 x 10(-20)T(2.25) exp(2100/T) in units of cm(3) molecule(-1) s(-1). The predicted rate constant, with the HOCl + O-1(2) as the major products in the 300-500 K range, agrees well with available experimental data obtained at 1 Torr He pressure. The high- and low- pressure limits of k(3) can be effectively given by k(3)(infinity)(T) = 3.24 x 10(-11) T-0.28 exp(- 18/T) cm(3) molecule(-1) s(-1) in 200-2500 K and k(3)degrees(T) = 1.28 x 10(-13)T(-6.36) exp(-635/T) for 200-800 K, 7.37 x 10(84)T(-36.02) exp(-22134/T) for 800-1000 K, and 2.91 x 10(-13)T(-8.42) exp(11500/T) for 1000-2500 K in units of cm(6) molecule(-2) s(-1) with N-2 as the third body.
Experimental and theoretical studies of rate coefficients for the reaction O(P-3)+CH3OH at high temperatures
(2005-06-22)
Lu, CW
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Chou, SL
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Lee, YP
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Xu, SC
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Xu, ZF
Rate coefficients of the reaction O(P-3)+CH3OH in the temperature range of 835-1777 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO2 with a KrF excimer laser at 248 nm or an ArF excimer laser at 193 nm; their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O-2 and He. The rate coefficients determined for the temperature range can be represented by the Arrhenius equation, k(T)=(2.29 +/- 0.18)x10(-10) exp[-(4210 +/- 100)/T] cm(3) molecule(-1) s(-1); unless otherwise noted, all the listed errors represent one standard deviation in fitting. Combination of these and previous data at lower temperature shows a non-Arrhenius behavior described as the three-parameter equation, k(T)=(2.74 +/- 0.07)x10(-18)T(2.25 +/- 0.13) exp[-(1500 +/- 90)/T] cm(3)molecule(-1) s(-1). Theoretical calculations at the Becke-3-Lee-Yang-Parr (B3LYP)/6-311+G(3df,2p) level locate three transition states. Based on the energies computed with coupled clusters singles, doubles (triples) [CCSD(T)]/6-311+G(3df,2p)//B3LYP/6-311+G(3df,2p), the rate coefficients predicted with canonical variational transition state theory with small curvature tunneling corrections agree satisfactorily with the experimental observations. The branching ratios of two accessible reaction channels forming OH+CH2OH (1a) and OH+CH3O (1b) are predicted to vary strongly with temperature. At 300 K, reaction (1a) dominates, whereas reaction (1b) becomes more important than reaction (1a) above 1700 K. (c) 2005 American Institute of Physics.