Pd催化甲醇裂解制氢的反应机理

基于密度泛函理论(DFT), 研究了甲醇在Pd(111)面上首先发生O—H键断裂的反应历程(CH3OH(s)→CH3O(s)+H(s)→CH2O(s)+2H(s)→CHO(s)+3H(s)→CO(s)+4H(s)). 优化了裂解过程中各反应物、中间体、过渡态和产物的几何构型, 获得了反应路径上各物种的吸附能及各基元反应的活化能数据. 另外, 对甲醇发生C—O键断裂生成CH3(s)和OH(s)的分解过程也进行了模拟计算. 计算结果表明, O—H键的断裂(活化能为103.1 kJ·mol-1)比C—O键的断裂(活化能为249.3 kJ·mol-1)更容易; 甲醇在Pd(111)面上裂解的主要反应历程是: 甲醇首先发生O—H键的断裂, 生成甲氧基中间体(CH3O(s)), 然后甲氧基中间体再逐步脱氢生成CO(s)和H(s). 甲醇发生O—H键断裂的活化能为103.1 kJ·mol-1, 甲氧基上脱氢的活化能为106.7 kJ·mol-1, 两者均有可能是整个裂解反应的速控步骤.     

Addition of water, methanol, and ammonia to Al3O3- clusters: reaction products, transition states, and electron detachment energies

Products of reactions between the book and kite isomers of Al3O3- and three important molecules are studied with electronic structure calculations. Dissociative adsorption of H2O or CH3OH is highly exothermic and proton-transfer barriers between anion-molecule complexes and the products of these reactions are low. For NH3, the reaction energies are less exothermic and the corresponding barriers are higher. Depending on experimental conditions, Al3O3- (NH3) coordination complexes or products of dissociative adsorption may be prepared. Vertical electron detachment energies of stable anions are predicted with ab initio electron propagator calculations and are in close agreement with experiments on Al3O3- and its products with H2O and CH3OH. Changes in the localization properties of two Al-centered Dyson orbitals account for the differences between the photoelectron spectra of Al3O3- and those of the product anions.     

Ni／Al2O3催化剂上CH4／CO2重整的脉冲反应研究

报道了用脉冲反应研究Ｎｉ／Ａｌ２Ｏ３催化剂上ＣＨ４／ＣＯ２重整反应的结果。脉冲反应显示，在还原的Ｎｉ／Ａｌ２Ｏ３催化剂上，ＣＨ４在６７３Ｋ就开始发生分解，并有Ｃ２Ｈ６、Ｃ２Ｈ４生成，１０２３Ｋ下，ＣＨ４几乎完全分解，单纯的ＣＯ２则很难在还原的催化剂上发生反应，在９７３Ｋ以上的高温下才会有少量Ｃ胜成ＣＯ．ＣＨＣＯ２的脉冲反应表明，当ＣＨ４在较低温度下开始分解时，ＣＯ２也会发生分解，并生成ＣＯ。脉冲反     

Kinetic mechanism of methanol decomposition on Ni(111) surface: a theoretical study

The decomposition of methanol on the Ni(111) surface has been studied with the pseudopotential method of density functional theory-generalized gradient approximation (DFT-GGA) and with the repeated slab models. The adsorption energies of possible species and the activation energy barriers of the possible elementary reactions involved are obtained in the present work. The major reaction path on Ni surfaces involves the O-H bond breaking in CH(3)OH and the further decomposition of the resulting methoxy species to CO and H via stepwise hydrogen abstractions from CH(3)O. The abstraction of hydrogen from methoxy itself is the rate-limiting step. We also confirm that the C-O and C-H bond-breaking paths, which lead to the formation of surface methyl and hydroxyl and hydroxymethyl and atom hydrogen, respectively, have higher energy barriers. Therefore, the final products are the adsorbed CO and H atom.     

Partial oxidation of propylene catalyzed by VO3 clusters: a density functional theory study

Density functional theory (DFT) calculations are carried out to investigate partial oxidation of propylene over neutral VO 3 clusters. C=C bond cleavage products CH 3CHO + VO 2CH 2 and HCHO + VO 2CHCH 3 can be formed overall barrierlessly from the reaction of propylene with VO 3 at room temperature. Formation of hydrogen transfer products H 2O + VO 2C 3H 4, CH 2=CHCHO + VO 2H 2, CH 3CH 2CHO + VO 2, and (CH 3) 2CO + VO 2 is subject to tiny (0.01 eV) or small (0.06 eV, 0.19 eV) overall free energy barriers, although their formation is thermodynamically more favorable than the formation of C=C bond cleavage products. These DFT results are in agreement with recent experimental observations. VO 3 regeneration processes at room temperature are also investigated through reaction of O 2 with the CC bond cleavage products VO 2CH 2 and VO 2CHCH 3. The following barrierless reaction channels are identified: VO 2CH 2 + O 2 --> VO 3 + CH 2O; VO 2CH 2 + O 2 --> VO 3C + H 2O, VO 3C + O 2 --> VO 3 + CO 2; VO 2CHCH 3 + O 2 --> VO 3 + CH 3CHO; and VO 2CHCH 3 + O 2 --> VO 3C + CH 3OH, VO 3C + O 2 --> VO 3 + CO 2. The kinetically most favorable reaction products are CH 3CHO, H 2O, and CO 2 in the gas phase model catalytic cycles. The results parallel similar behavior in the selective oxidation of propylene over condensed phase V 2O 5/SiO 2 catalysts.     

Kinetics and mechanism of the reactions of CH3CO and CH3C(O)CH2 radicals with O2. Low-pressure discharge flow experiments and quantum chemical computations

The reactions CH(3)CO + O(2)--> products (1), CH(3)CO + O(2)--> OH +other products (1b) and CH(3)C(O)CH(2) + O(2)--> products (2) have been studied in isothermal discharge flow reactors with laser induced fluorescence monitoring of OH and CH(3)C(O)CH(2) radicals. The experiments have been performed at overall pressures between 1.33 and 10.91 mbar of helium and 298 +/- 1 K reaction temperature. OH formation has been found to be the dominant reaction channel for CH(3)CO + O(2): the branching ratio, Gamma(1b) = k(1b)/k(1), is close to unity at around 1 mbar, but decreases rapidly with increasing pressure. The rate constant of the overall reaction, k(2), has been found to be pressure dependent: the fall-off behaviour has been analysed in comparison with reported data. Electronic structure calculations have confirmed that at room temperature the reaction of CH(3)C(O)CH(2) with O(2) is essentially a recombination-type process. At high temperatures, the further reactions of the acetonyl-peroxyl adduct may yield OH radicals, but the most probable channel seems to be the O(2)-catalysed keto-enol transformation of acetonyl. Implications of the results for atmospheric modelling studies have been discussed.     

Magnesium monocationic complexes: a theoretical study of metal ion binding energies and gas-phase association kinetics

Bond dissociation energies (BDEs) for complexes of ground state Mg+ (2S) with several small oxygen- and nitrogen-containing ligands (H2O, CO, CO2, H2CO, CH3OH, HCOOH, H2CCO, CH3CHO, c-C2H4O, H2CCHOH, CH3CH2OH, CH3OCH3, NH3, HCN, H2CNH, CH3NH2, CH3CN, CH3CH2NH2, (CH3)2NH, H2NCN, and HCONH2) have been calculated at the CP-dG2thaw level of theory. These BDE values, as well as counterpoise-corrected MP2(thaw)/6-311+G(2df,p) calculations on the Mg+ complexes of several larger ligands, augment and complement existing experimental or theoretical determinations of gas-phase Mg+/ligand bond strengths. The reaction kinetics of complex formation are also investigated via variational transition state theory (VTST) calculations using the computed ligand and molecular ion parameters. Radiative association rate coefficients for most of these systems increase by approximately 1 order of magnitude with every 3-fold reduction in temperature from 300 to 10 K. Several of the largest molecules surveyed-notably, CH3COOH, (CH3)2CO, and CH3CH2CN-exhibit comparatively efficient radiative association with Mg+ (k(RA) > or = 1.0 x 10(-10) cm3 molecule(-1) s(-1)) at temperatures as high as 100 K, implying that these processes may have a considerable influence on the metal ion chemistry of warm molecular astrophysical environments known to contain these potential ligands. Our calculations also identify the infrared chromophoric brightness of various functional groups as a significant factor influencing the efficiency of the radiative association process.     

Theoretical Study on Gas Phase Reactions of OH Hydrogen-Abstraction from Formyl Fluoride with Di erent Catalysts

The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl uoride (FCHO) abstracted by OH in the presence of water, formic acid (FA), or sulfuric acid (SA) are theoretically investigated at the CCSD(T)/6-311++G(3df, 3pd)//M06-2X/6-311++G(3df, 3pd) level of theory. The calculated results show that the barriers of the transition states involving catalysts are lowered to -2.89, -6.25, and -7.76 kcal/mol from 3.64 kcal/mol with respect to the separate reactants, respectively, which re ects that those catalysts play an important role in reducing the barrier of the hydrogen abstraction reaction of FCHO with OH. Additionally, using conventional transition state theory with Eckart tun-neling correction, the kinetic data demonstrate that the entrance channel X FCHO+OH (X=H₂O, FA, or SA) is signi cantly more favorable than the pathway X OH+FCHO. More-over, the rate constants of the reactions of FCHO with OH radical with H₂O, FA, or SA introduced are computed to be smaller than that of the naked OH+FCHO reaction because the concentration of the formed X FCHO or X OH complex is quite low in the atmosphere.     

Thermal decomposition of methyl butanoate: ab initio study of a biodiesel fuel surrogate

In this paper, we report a detailed analysis of the breakdown kinetic mechanism for methyl butanoate (MB) using theoretical approaches. Electronic structures and structure-related molecular properties of reactants, intermediates, products, and transition states were explored at the BH&HLYP/cc-pVTZ level of theory. Rate constants for the unimolecular and bimolecular reactions in the temperature range of 300-2500 K were calculated using Rice-Ramsperger-Kassel-Marcus and transition state theories, respectively. Thirteen pathways were identified leading to the formation of small compounds such as CH(3), C(2)H(3), CO, CO(2), and H(2)CO. For the initial formation of MB radicals, H, CH(3), and OH were considered as reactive radicals participating in hydrogen abstraction reactions. Kinetic simulation results for a high temperature pyrolysis environment show that MB radicals are mainly produced through hydrogen abstraction reactions by H atoms. In addition, the C(O)OCH(3) = CO + CH(3)O reaction is found to be the main source of CO formation. The newly computed kinetic sub-model for MB breakdown is recommended as a core component to study the combustion of oxygenated species.     

Keto-enol/enolate equilibria in the N-acetylamino-p-methylacetophenone system. Effect of a beta-nitrogen substituent

The cis-enol of N-acetylamino-p-methylacetophenone was generated flash photolytically and its rates of ketonization in aqueous HClO(4) and NaOH solutions as well as in HCO(2)H, CH(3)CO(2)H, H(2)PO(4)(-), (CH(2)OH)(3)CNH(3)(+), and NH(4)(+) buffers were measured. Rates of enolization of N-acetylamino-p-methylacetophenone to the cis-enol were also measured by hydrogen exchange of its methylene protons, and combination of the enolization and ketonization data gave the keto-enol equilibrium constant pK(E) = 5.33, the acidity constant of the enol ionizing as an oxygen acid pQ(a)(E)= 9.12, and the acidity constant of the ketone ionizing as a carbon acid pQ(a)(K)= 14.45. Comparison of these results with corresponding values for p-methylacetophenone itself shows that the N-acetylamino substituent raises all three of these equilibrium constants: K(E) by 3 orders of magnitude, Q(a)(E) by 1 order of magnitude, and Q(a)(K)by 4 orders of magnitude. This substituent also retards the rate of H+ catalyzed enol ketonization by 4 orders of magnitude. The origins of these substituent effects are discussed.     

Supramolecular silanol chemistry in the gas phase. Topological (AIM) and population (NBO) analyses of hydrogen-bonded complexes between H3SiOH and selected O- and N-acceptor molecules

Hydrogen bonding of the type SiO-H...A (A = O, N) has been studied in the gas phase for simple H3SiOH.acceptor complexes with the acceptor molecules being O(H)SiH3, OH2, O(H)CH3, O(CH3)2, O(CH3)SiH3, O(SiH3)2, NH3, N(CH3)H2, N(CH3)2H, N(CH3)3, N(CH3)2C6H5, and NC5H5, respectively, at the B3LYP/6-311+(2d,p) level of theory, using Bader's atoms in molecules (AIM) and Weinhold's natural bond orbital (NBO) methodology. For all complexes (except H3SiOH.N(CH3)2C6H5) the complex energy Eadd. is a good estimate for the hydrogen bond energy EHB, which is generally higher in N-acceptor complexes (-5.52 to -7.17 kcal mol-1) than in O-acceptor complexes (-2.09 to -5.06 kcal mol-1). In case of H3SiOH.N(CH3)2C6H5, EHB and Eadd. differ by the energy associated with the loss of n(N)-->pi conjugation in N(CH3)2C6H5 upon complex formation. EHB shows no correlation with O...A distances and the red shifts Deltanu(OH) of the OH-stretching vibrations when different acceptors are compared, although both parameters are commonly used to estimate the strength of the hydrogen bond from spectroscopic and diffraction data. A good linear correlation of the hydrogen bond energy EHB has been established with parameters derived from the AIM and NBO analyses, namely, the electron densities rho(HA) and rho(OH) at the H...A and O-H bond critical points (BCPs) and the NLMO bond orders BONLMO(HA) of the H...A bonds of the H3SiOH.acceptor complexes as well as the change of natural charges DeltaqNPA(O) at the O-donor atom upon H3SiOH.acceptor complex formation. Hydrogen bonding of the type SiO-H...A (A = O, N) has been also studied in the related cyclic multiple H3SiOH.acceptor complexes (H3SiOH)3, (H3SiOH)2.NC5H5, and (H3SiOH)4, respectively, at the same level of theory. Cooperative hydrogen bonding is evident for all cyclic multiple H3SiOH.acceptor complexes, whereby the strongest concomitant strengthening of the hydrogen bonds is observed for (H3SiOH)4 and (H3SiOH)2.NC5H5.     

Theoretical study of the reactions CF3CH2OCHF2 + OH/Cl and its product radicals and parent ether(CH3CH2OCH3) with OH

A dual-level direct dynamic method is employed to study the reaction mechanisms of CF3CH2OCHF2 (HFE-245fa2; HFE-245mf) with the OH radicals and Cl atoms. Two hydrogen abstraction channels and two displacement processes are found for each reaction. For further study, the reaction mechanisms of its products (CF3CH2OCF2 and CF3CHOCHF2) and parent ether CH3CH2OCH3 with OH radical are investigated theoretically. The geometries and frequencies of all the stationary points and the minimum energy paths (MEPs) are calculated at the B3LYP/6-311G(d,p) level. The energetic information along the MEPs is further refined at the G3(MP2) level of theory. For reactions CF3CH2OCHF2 + OH/Cl, the calculation indicates that the hydrogen abstraction from --CH2-- group is the dominant reaction channel, and the displacement processes may be negligible because of the high barriers. The standard enthalpies of formation for the reactant CF3CH2OCHF2, and two products CF3CH2OCHF2 and CF3CHOCHF2 are evaluated via group-balanced isodesmic reactions. The rate constants of reactions CF3CH2OCHF2 + OH/Cl and CH3CH2OCH3 + OH are estimated by using the variational transition state theory over a wide range of temperature (200-2000 K). The agreement between the theoretical and experimental rate constants is good in the measured temperature range. From the comparison between the rate constants of the reactions CF3CH2OCHF2 and CH3CH2OCH3 with OH, it is shown that the fluorine substitution decreases the reactivity of the C--H bond.     

Criegee中间体RCHOO(R=H,CH_3)与NCO的反应机理

采用CCSD(T)/aug-cc-p VTZ//B3LYP/6-311+G(2df,2p)方法对Criegee中间体RCHOO(R=H,CH_3)与NCO反应的机理进行了研究,利用经典过渡态理论(TST)并结合Eckart校正模型计算了标题反应在298~500 K范围内优势通道的速率常数.结果表明,上述反应包含亲核加成、氧化和抽氢3类机理,其中每类又包括NCO中N和O分别进攻的两种形式.亲核加成反应中O端进攻为优势通道,氧化和抽氢反应则是N端进攻为优势通道;甲基取代使CH_3CHOO反应活性高于CH2OO;anti-CH_3CHOO的加成及氧化反应活性高于syn-CH_3CHOO,而抽氢反应则是syn-CH_3CHOO的活性高于anti-CH_3CHOO.anti-构象对总速率常数的贡献大于syn-构象,且总速率常数具有显著的负温度效应.     

Unimolecular dissociation of the CH3OCO radical: an intermediate in the CH3O + CO reaction

This work investigates the unimolecular dissociation of the methoxycarbonyl, CH(3)OCO, radical. Photolysis of methyl chloroformate at 193 nm produces nascent CH(3)OCO radicals with a distribution of internal energies, determined by the velocities of the momentum-matched Cl atoms, that spans the theoretically predicted barriers to the CH(3)O + CO and CH(3) + CO(2) product channels. Both electronic ground- and excited-state radicals undergo competitive dissociation to both product channels. The experimental product branching to CH(3) + CO(2) from the ground-state radical, about 70%, is orders of magnitude larger than Rice-Ramsperger-Kassel-Marcus (RRKM)-predicted branching, suggesting that previously calculated barriers to the CH(3)OCO --> CH(3) + CO(2) reaction are dramatically in error. Our electronic structure calculations reveal that the cis conformer of the transition state leading to the CH(3) + CO(2) product channel has a much lower barrier than the trans transition state. RRKM calculations using this cis transition state give product branching in agreement with the experimental branching. The data also suggest that our experiments produce a low-lying excited state of the CH(3)OCO radical and give an upper limit to its adiabatic excitation energy of 55 kcal/mol.     

Methane oxidation mechanism on Pt(111): a cluster model DFT study

The electronic energy barriers of surface reactions pertaining to the mechanism of the electrooxidation of methane on Pt (111) were estimated with density functional theory calculations on a 10-atom Pt cluster, using both the B3LYP and PW91 functionals. Optimizations of initial and transition states were performed for elementary steps that involve the conversion of CH(4) to adsorbed CO at the Pt/vacuum interface. As a first approximation we do not include electrolyte effects in our model. The reactions include the dissociative chemisorption of CH(4) on Pt, dehydrogenation reactions of adsorbed intermediates (*CH(x) --> *CH(x-1) + *H and *CH(x)O --> *CH(x-1)O + *H), and oxygenation reactions of adsorbed CH(x) species (*CH(x) + *OH --> *CH(x)OH). Many pathways were investigated and it was found that the main reaction pathway is CH(4) --> *CH(3) --> *CH(2) --> *CH --> *CHOH --> *CHO --> *CO. Frequency analysis and transition-state theory were employed to show that the methane chemisorption elementary step is rate-limiting in the above mechanism. This conclusion is in agreement with published experimental electrochemical studies of methane oxidation on platinum catalysts that have shown the absence of an organic adlayer at electrode potentials that allow the oxidation of adsorbed CO. The mechanism of the electrooxidation of methane on Pt is discussed.     

Energetics, transition states, and intrinsic reaction coordinates for reactions associated with O(3P) processing of hydrocarbon materials

Electronic structure calculations based on multiconfiguration wave functions are used to investigate a set of archetypal reactions relevant to O(3P) processing of hydrocarbon molecules and surfaces. These include O(3P) reactions with methane and ethane to give OH plus methyl or ethyl radicals, O(3P) + ethane to give CH3O + CH3, and secondary reactions of the OH product radical with ethane and the ethyl radical. Geometry optimization is carried out with CASSCF/cc-pVTZ for all reactions, and with CASPT2/cc-pVTZ for O(3P) + methane/ethane. Single-point energy corrections are applied with CASPT2, CASPT3, and MRCI + Q with the cc-pVTZ and cc-pVQZ basis sets, and the energies extrapolated to the complete basis set limit (CBL). Where comparison of computed barriers and energies of reaction with experiment is possible, the agreement is good to excellent. The best agreement (within experimental error) is found for MRCI + Q/CBL applied to O(3P) + methane. For the other reactions, CASPT2/CBL and MRCI + Q/CBL predictions differ from experiment by 1-5 kcal/mol for 0 K enthalpies of reaction, and are within 1 kcal/mol of the best-estimate experimental range of 0 K barriers for O(3P) + ethane and OH + ethane. The accuracy of MRCI + Q/CBL is limited mainly by the quality of the active space. CASPT2/CBL barriers are consistently lower than MRCI + Q/CBL barriers with identical reference spaces.     

13C, 18O, and D fractionation effects in the reactions of CH3OH isotopologues with Cl and OH radicals

A relative rate experiment is carried out for six isotopologues of methanol and their reactions with OH and Cl radicals. The reaction rates of CH2DOH, CHD2OH, CD3OH, (13)CH3OH, and CH3(18)OH with Cl and OH radicals are measured by long-path FTIR spectroscopy relative to CH3OH at 298 +/- 2 K and 1013 +/- 10 mbar. The OH source in the reaction chamber is photolysis of ozone to produce O((1)D) in the presence of a large excess of molecular hydrogen: O((1)D) + H2 --> OH + H. Cl is produced by the photolysis of Cl2. The FTIR spectra are fitted using a nonlinear least-squares spectral fitting method with measured high-resolution infrared spectra as references. The relative reaction rates defined as alpha = k(light)/k(heavy) are determined to be: k(OH + CH3OH)/k(OH + (13)CH3OH) = 1.031 +/- 0.020, k(OH + CH3OH)/k(OH + CH3(18)OH) = 1.017 +/- 0.012, k(OH + CH3OH)/k(OH + CH2DOH) = 1.119 +/- 0.045, k(OH + CH3OH)/k(OH + CHD2OH) = 1.326 +/- 0.021 and k(OH + CH3OH)/k(OH + CD3OH) = 2.566 +/- 0.042, k(Cl + CH3OH)/k(Cl + (13)CH3OH) = 1.055 +/- 0.016, k(Cl + CH3OH)/k(Cl + CH3(18)OH) = 1.025 +/- 0.022, k(Cl + CH3OH)/k(Cl + CH2DOH) = 1.162 +/- 0.022 and k(Cl + CH3OH)/k(Cl + CHD2OH) = 1.536 +/- 0.060, and k(Cl + CH3OH)/k(Cl + CD3OH) = 3.011 +/- 0.059. The errors represent 2sigma from the statistical analyses and do not include possible systematic errors. Ground-state potential energy hypersurfaces of the reactions were investigated in quantum chemistry calculations at the CCSD(T) level of theory with an extrapolated basis set. The (2)H, (13)C, and (18)O kinetic isotope effects of the OH and Cl reactions with CH3OH were further investigated using canonical variational transition state theory with small curvature tunneling and compared to experimental measurements as well as to those observed in CH4 and several other substituted methane species.     

Generation and reactivity of rhodium(IV) complexes in aqueous solutions

At pH = 1 and 25 degrees C, the Fenton-like reactions of Fe(aq)(2+) with hydroperoxorhodium complexes LRh(III)OOH(2+) (L = (H(2)O)(NH(3))(4), k = 30 M(-1) s(-1), and L = L(2) = (H(2)O)(meso-Me(6)-[14]aneN(4)), k = 31 M(-1) s(-1)) generate short-lived, reactive intermediates, believed to be the rhodium(IV) species LRh(IV)O(2+). In the rapid follow-up steps, these transients oxidize Fe(aq)(2+), and the overall reaction has the standard 2:1 [Fe(aq)(2+)]/[LRhOOH(2+)] stoichiometry. Added substrates, such as alcohols, aldehydes, and (NH(3))(4)(H(2)O)RhH(2+), compete with Fe(aq)(2+) for LRh(IV)O(2+), causing the stoichiometry to change to <2:1. Such competition data were used to determine relative reactivities of (NH(3))(4)RhO(2+) toward CH(3)OH (1), CD(3)OH (0.2), C(2)H(5)OH (2.7), 2-C(3)H(7)OH (3.4), 2-C(3)D(7)OH (1.0), CH(2)O (12.5), C(2)H(5)CHO (45), and (NH(3))(4)RhH(2+) (125). The kinetics and products suggest hydrogen atom abstraction for (NH(3))(4)RhO(2+)/alcohol reactions. A short chain reaction observed with C(2)H(5)CHO is consistent with both hydrogen atom and hydride transfer. The rate constant for the reaction between Tl(aq)(III) and L(2)Rh(2+) is 2.25 x 10(5) M(-1) s(-1).     

Computational study on the kinetics and mechanisms for the reactions of HCO with HONO and HNOH

The kinetics and mechanisms of the HCO reactions with HONO and HNOH have been studied at the G2M level of theory based on the geometric parameters optimized at BH&HLYP/6‐311G(d,p). The rate constants in the temperature range 200–3000 K at different pressures have been predicted by microcanonical RRKM and/or variational transition state theory calculations with Eckart tunneling corrections. For the HCO + HONO reaction, hydrogen abstraction from trans‐HONO and cis‐HONO by HCO produces H₂CO + NO₂, with the latter being dominant. Two other channels involving cis‐HONO by the association/decomposition mechanism via the HC(O)N(O)OH intermediate, which could fragment to give H₂O + CO + NO at high temperatures, were also found to be important. For the HCO + HNOH reaction, three reaction channels were identified: one association reaction giving a stable intermediate, HC(O)N(H)OH (LM2), and two hydrogen abstraction channels producing H₂CO and H₂NOH. The dominant products were predicted to be the formation of LM2 at low temperatures and H₂NOH + CO at middle and high temperatures. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 178–187 2004     

Theoretical Investigation of CH3CF2O2+HOO Reaction

The reactions of CH3CF2O2 with HOO are important chemical cyclic processes of photochemical contamination. In this paper, the reaction pathways and reaction mechanism of CH3CF2O2+HOO are investigated extensively with the Gaussian 98 package at the B3LYP/6-311++G** basis sets. The use of vibrational mode analysis and electron population analysis to reveal the reaction mechanism is firstly reported. The study shows that CH3CF2CO2+HOO→IM1→TS1→CH3CF2O2H+O2 channel is the energetically most favorable, CH3CF2CO2H and O2 are the principal products, and the formation of CH3OH and CF2O is also possible.