Kinetics and mechanisms of the allyl + allyl and allyl + propargyl recombination reactions

The kinetics and mechanisms of the self-reaction of allyl radicals and the cross-reaction between allyl and propargyl radicals were studied both experimentally and theoretically. The experiments were carried out over the temperature range 295-800 K and the pressure range 20-200 Torr (maintained by He or N(2)). The allyl and propargyl radicals were generated by the pulsed laser photolysis of respective precursors, 1,5-hexadiene and propargyl chloride, and were probed by using a cavity ring-down spectroscopy technique. The temperature-dependent absorption cross sections of the radicals were measured relative to that of the HCO radical. The rate constants have been determined to be k(C(3)H(5) + C(3)H(5)) = 1.40 × 10(-8)T(-0.933) exp(-225/T) cm(3) molecule(-1) s(-1) (Δ log(10)k = ± 0.088) and k(C(3)H(5) + C(3)H(3)) = 1.71 × 10(-7)T(-1.182) exp(-255/T) cm(3) molecule(-1) s(-1) (Δ log(10)k = ± 0.069) with 2σ uncertainty limits. The potential energy surfaces for both reactions were calculated with the CBS-QB3 and CASPT2 quantum chemical methods, and the product channels have been investigated by the steady-state master equation analyses based on the Rice-Ramsperger-Kassel-Marcus theory. The results indicated that the reaction between allyl and propargyl radicals produces five-membered ring compounds in combustion conditions, while the formations of the cyclic species are unlikely in the self-reaction of allyl radicals. The temperature- and pressure-dependent rate constant expressions for the important reaction pathways are presented for kinetic modeling.     

Reaction of phenyl radical with propylene as a possible source of indene and other polycyclic aromatic hydrocarbons: an ab initio/RRKM-ME study

Ab initio G3(MP2,CC)//B3LYP/6-311G** calculations have been performed to investigate the potential energy surface (PES) and mechanism of the reaction of phenyl radical with propylene followed by kinetic RRKM-ME calculations of rate constants and product branching ratios at various temperatures and pressures. The reaction can proceed either by direct hydrogen abstraction producing benzene and three C(3)H(5) radicals [1-propenyl (CH(3)CHCH), 2-propenyl (CH(3)CCH(2)), and allyl (CH(2)CHCH(2))] or by addition of phenyl to the CH or CH(2) units of propylene followed by rearrangements on the C(9)H(11) PES producing nine different products after H or CH(3) losses. The H abstraction channels are found to be kinetically preferable at temperatures relevant to combustion and to contribute 55-75% to the total product yield in the 1000-2000 K temperature range, with the allyl radical being the major product (~45%). The relative contributions of phenyl addition channels are calculated to be ~35% at 1000 K, decreasing to ~15% at 2000 K, with styrene + CH(3) and 3-phenylpropene + H being the major products. Collisional stabilization of C(6)H(5) + C(3)H(6) addition complexes is computed to be significant only at temperatures up to 1000-1200 K, depending on the pressure, and maximizes at low temperatures of 300-700 K reaching up to 90% of the total product yield. At T > 1200 K collisional stabilization becomes negligible, whereas the dissociation products, styrene plus methyl and 3-phenylpropene + H, account for up to 45% of the total product yield. The production of bicyclic aromatic species including indane C(9)H(10) is found to be negligible at all studied conditions indicating that the phenyl addition to propylene cannot be a source of polycyclic aromatic hydrocarbons (PAH) on the C(9)H(11) PES. Alternatively, the formation of a PAH molecule, indene C(9)H(8), can be accomplished through secondary reactions after activation of a major product of the C(6)H(5) + C(3)H(6) addition reaction, 3-phenylpropene, by direct hydrogen abstraction by small radicals, such as H, OH, CH(3), etc. It is shown that at typical combustion temperatures 77-90% of C(9)H(9) radicals formed by H-abstraction from 3-phenylpropene undergo a closure of a cyclopentene ring via low barriers and then lose a hydrogen atom producing indene. This results in 7.0-14.5% yield of indene relative to the initial C(6)H(5) + C(3)H(6) reactants within the 1000-2000 K temperature range.     

Gas-phase reactions of organic radicals and diradicals with ions

Reactions of polyatomic organic radicals with gas phase ions have been studied at thermal energy using a flowing afterglow-selected ion flow tube (FA-SIFT) instrument. A supersonic pyrolysis nozzle produces allyl radical (CH2CHCH2) and ortho-benzyne diradical (o-C6H4) for reaction with ions. We have observed: [CH2CHCH2 + H3O+ --> C3H6+ + H2O], [CH2CHCH2 + HO- --> no ion products], [o-C6H4 + H3O+ --> C6H5+ + H2O], and [o-C6H4 + HO- --> C6H3- + H2O]. The proton transfer reactions with H3O+ occur at nearly every collision (kII approximately with 10(-9) cm3 s(-1)). The exothermic proton abstraction for o-C6H4 + HO- is unexpectedly slow (kII approximately with 10(-10) cm3 s(-1)). This has been rationalized by competing associative detachment: o-C6H4 + HO- --> C6H5O + e-. The allyl + HO- reaction proceeds presumably via similar detachment pathways.     

Computational study on the mechanism and rate constant for the C6H5 + C6H5NO reaction

The reaction mechanism of C6H5 + C6H5NO involving four product channels on the doublet-state potential energy surface has been studied at the B3LYP/6-31+G(d, p) level of theory. The first reaction channel occurs by barrierless association forming (C6H5)2NO (biphenyl nitroxide), which can undergo isomerization and decomposition. The second channel takes place by substitution reaction producing C12H10 (biphenyl) and NO. The third and fourth channels involve direct hydrogen abstraction reactions producing C6H4NO + C6H6 and C6H5NOH + C6H4, respectively. Bimolecular rate constants of the above four product channels have been calculated in the temperature range 300-2000 K by the microcanonical Rice-Ramsperger-Kassel-Marcus theory and/or variational transition-state theory. The result shows the dominant reactions are channel 1 at lower temperatures (T < 800 K) and channel 3 at higher temperatures (T > 800 K). The total rate constant at 7 Torr He is predicted to be k(t) = 3.94 x 10(21) T(-3.09) exp(-699/T) for 300-500 K, 2.09 x 10(20) T(-3.56) exp(2315/T) for 500-1000 K, and 1.51 x 10(2) T(3.30) exp(-3043/T) for 1000-2000 K (in units of cm3 mol(-1) s(-1)), agreeing reasonably with the experimental data within their reported errors. The heats of formation of key products including biphenyl nitroxide, hydroxyl phenyl amino radical, and N-hydroxyl carbazole have been estimated.     

Kinetics of the reaction C2H5 + HO2 by time-resolved mass spectrometry

The overall rate constant for the radical-radical reaction C2H5 + HO2 --> products has been determined at room temperature by means of time-resolved mass spectrometry using a laser photolysis/flow reactor combination. Excimer laser photolysis of gas mixtures containing ethane, hydrogen peroxide, and oxalyl chloride was employed to generate controlled concentrations of C2H5 and HO2 radicals by the fast H abstraction reactions of the primary radicals Cl and OH with C2H6 and H2O2, respectively. By careful adjustments of the radical precursor concentrations, the title reaction could be measured under almost pseudo-first-order conditions with the concentration of HO2 in large excess over that of C2H5. From detailed numerical simulations of the measured concentration-time profiles of C2H5 and HO2, the overall rate constant for the reaction was found to be k1(293 K) = (3.1 +/- 1.0) x 10(13) cm3 mol(-1) s(-1). C2H5O could be confirmed as a direct reaction product.     

Determination of the rate constant and product channels for the radical-radical reaction NCO(X 2Pi) + C2H5(X 2A') at 293 K

The rate constant and product branching ratios for the reaction of the cyanato radical, NCO(X (2)Pi), with the ethyl radical, C(2)H(5)(X (2)A'), have been measured over the pressure range of 0.28 to 0.59 kPa and at a temperature of 293 +/- 2 K. The total rate constant, k(1), increased with pressure, P(kPa), described by k(1) = (1.25 +/- 0.16) x 10(-10) + (4.22 +/- 0.35) x 10(-10)P cm(3) molecule(-1) s(-1). Three product channels were observed that were not pressure dependent: (1a) HNCO + C(2)H(4), k(1a) = (1.1 +/- 0.16) x 10(-10), (1b) HONC + C(2)H(4), k(1b) = (2.9 +/- 1.3) x 10(-11), (1c) HCN + C(2)H(4)O, k(1c) = (8.7 +/- 1.5) x 10(-13), with units cm(3) molecule(-1) s(-1) and uncertainties of one-standard deviation in the scatter of the data. The pressure dependence was attributed to a forth channel, (1d), forming recombination products C(2)H(5)NCO and/or C(2)H(5)OCN, with pressure dependence: (1d) k(1d) = (0.090 +/- 1.3) x 10(-11) + (3.91 +/- 0.27) x 10(-10)P cm(3) molecule(-1) s(-1). The radicals were generated by the 248 nm photolysis of ClNCO in an excess of C(2)H(6). Quantitative infrared time-resolved absorption spectrophotometry was used to follow the temporal dependence of the reactants and the appearance of the products. Five species were monitored, HCl, NCO, HCN, HNCO, and C(2)H(4), providing a detailed picture of the chemistry occurring in the system. Other rate constants were also measured: ClNCO + C(2)H(5), k(10) = (2.3 +/- 1.2) x 10(-13) , NCO + C(2)H(6), k(2) = (1.6 +/- 0.11) x 10(-14), NCO + C(4)H(10), k(4) = (5.3 +/- 0.51) x 10(-13), with units cm(3) molecule(-1) s(-1) and uncertainties of one-standard deviation in the scatter of the data.     

Calculational and experimental investigations of the pressure effects on radical-radical cross combination reactions: C2H5+C2H3

Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5+C2H3-->1-butene, (2c) C2H5 + C2H5-->n-butane, and (3c) C2H3+C2H3-->1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [1-C4H8]/[C4H10] ratio was reduced from approximately 1.2 at 760 Torr (101 kPa) to approximately 0.5 at 100 Torr (13.3 kPa) and approximately 0.1 at pressures lower than about 5 Torr (approximately 0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3-->C3H5+CH3. This reaction occurs even at moderate pressures of approximately 200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(-3)-10(5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3+/-0.1.     

High-temperature thermal decomposition of benzyl radicals

The thermal decomposition of the benzyl radical was studied in shock tube experiments using ultraviolet laser absorption at 266 nm for detection of benzyl. Test gas mixtures of 50 and 100 ppm of benzyl iodide dilute in argon were heated in reflected shock waves to temperatures ranging from 1430 to 1730 K at total pressures around 1.5 bar. The temporal behavior of the 266 nm absorption allowed for determination of the benzyl absorption cross-section at 266 nm and the rate coefficient for benzyl decomposition, C6H5CH2 --> C7H6 + H. The rate coefficient for benzyl decomposition at 1.5 bar can be described using a two-parameter Arrhenius expression by k1(T) = 8.20 x 10(14) exp(-40 600 K/T) [s(-1)], and the benzyl absorption cross-section at 266 nm was determined to be sigma(benzyl) = 1.9 x 10(-17) cm2 molecule(-1) with no discernible temperature dependence over the temperature range of the experiments.     

The reaction of phenyl radical with molecular oxygen: a G2M study of the potential energy surface

Ab initio G2M calculations have been performed to investigate the potential energy surface for the reaction of C6H5 with O2. The reaction is shown to start with an exothermic barrierless addition of O2 to the radical site of C6H5 to produce phenylperoxy (1) and, possibly, 1,2-dioxaspiro[2.5]octadienyl (dioxiranyl, 8) radicals. Next, 1 loses the terminal oxygen atom to yield the phenoxy + O products (3) or rearranges to 8. The dioxiranyl can further isomerize to a seven-member ring 2-oxepinyloxy radical (10), which can give rise to various products including C5H5 + CO2, pyranyl + CO, o-benzoquinone + H, and 2-oxo-2,3-dihydrofuran-4-yl + C2H2. Once 10 is produced, it is unlikely to go back to 8 and 1, because the barriers separating 10 from the products are much lower than the reverse barrier from 10 to 8. Thus, the branching ratio of C6H5O + O against the other products is mostly controlled by the critical transition states between 1 and 3, 1 and 8, and 8 and 10. According to the calculated barriers, the most favorable product channel for the decomposition of 10 is C5H5 + CO2, followed by pyranyl + CO and o-benzoquinone + H. Since C6H5O + O and C5H5 + CO2 are expected to be the major primary products of the C6H5 + O2 reaction and thermal decomposition of C6H5O leads to C5H5 + CO, cyclopentadienyl radicals are likely to be the major product of phenyl radical oxidation, and so it results in degradation of the six-member aromatic ring to the five-member cyclopentadienyl ring. Future multichannel RRKM calculations of reaction rate constants are required to support these conclusions and to quantify the product branching ratios at various combustion conditions.     

Study of benzylperoxy radical using laser photolysis: ultraviolet spectrum, self-reaction, and reaction with HO2 kinetics

The ultraviolet absorption spectrum of benzylperoxy radical and the kinetics of the reactions 2C(6)H(5)CH(2)O(2) --> products (I) and C(6)H(5)CH(2)O(2) + HO(2) --> products (II) are studied. Experiments are carried out using the laser photolysis technique with time-resolved UV-visible absorption spectroscopy over the temperature range 298-353 K and the pressure range 50-200 Torr. The UV spectrum is determined relative to the known cross section of the ethylperoxy radical C(2)H(5)O(2) at 250 nm. Using factor analysis, the spectrum obtained is refined and the concentrations of the main absorbing species are extracted. The kinetic parameters are determined by analyzing and simulating the temporal profiles of the species concentrations and the experimental optical densities in the spectral region 220-280 nm. These are obtained using the recent UV spectra of the absorbing species existing in our mechanism. The Arrhenius expressions for reactions I and II are (cm(3).molecule(-1).s(-1)) k(I) = 2.50 x 10(-14)e(1562/)(T) and k(II) = 5.70 x 10(-14)e(1649/)(T). Our results are discussed and compared to literature data.     

Determination of the rate constant for the radical-radical reaction NCO(X2Pi) + CH3(X2A2 ') at 293 K and an estimate of possible product channels

The rate constant for the reaction of the cyanato radical, NCO(X2Pi), with the methyl radical, CH3(X2A2' '), has been measured to be (2.1 +/- 1.3(-0.80)) x 10(-10) cm3 molecule(-1) s(-1), where the uncertainty includes both random and systematic errors at the 68% confidence level. The measurements were conducted over a pressure range of 2.8-4.3 Torr of CH4 and at a temperature of 293 +/- 2 K. The radicals were generated by the 248-nm photolysis of ClNCO in a large excess of CH4. The subsequent rapid reaction, Cl + CH4, generated the CH3 radical. The rate constant for the Cl + CH4 reaction was measured to be (9.2 +/- 0.2) x 10(-14) cm3 molecule(-1) s(-1), where the uncertainty is the scatter of one standard deviation in the data. The progress of the reaction was followed by time-resolved infrared absorption spectroscopy on single rovibrational transitions from the ground vibrational level. Multiple species were detected in these experiments, including NCO, CH3, HCl, C2H6, HCN, HNC, NH, and HNCO. Temporal concentration profiles of the observed species were simulated using a kinetic model, and rate constants were determined by minimizing the sum of the squares of the residuals between experimental observations and model calculations. Both HCN and HNC seem to be minor products (<0.3% each) of the NCO + CH3 reaction. The peak concentrations of NH and HNCO were small, accounting for <1% of the initial NCO concentration; however, their temporal profiles could not be fit by the model kinetics. The observed C2H6 temporal profile always peaked at significantly higher concentrations than the model predictions, and several reaction models were constructed to help explain these observations. The most likely product channel seems to be the recombination channels, producing CH3NCO and CH3OCN.     

Model studies of DNA C5' radicals. Selective generation and reactivity of 2'-deoxyadenosin-5'-yl radical

The reaction of hydrated electrons (e(aq)(-)) with 8-bromo-2'-deoxyadenosine has been investigated by radiolytic methods coupled with product studies and addressed computationally by means of DFT-B3LYP calculations. Pulse radiolysis revealed that this reaction was complete in approximately 0.3 mus, and, at this time, no significant absorption was detected. The spectrum of a transient developed in 20 mus has an absorbance in the range 300-500 nm (epsilon(max) congruent with 9600 M(-1) cm(-1) at 360 nm), and it was assigned to aromatic aminyl radical 3. Computed vertical transitions (TD-UB3LYP/6-311+G) are in good agreement with the experimental observations. Radical 3 is obtained by the following reaction sequence: one-electron reductive cleavage of the C-Br bond that gives the C8 radical, a fast radical translocation from the C8 to C5' position, and an intramolecular attack of the C5' radical at the C8,N7 double bond of the adenine moiety. The rate constant for the cyclization is 1.6 x 10(5) s(-1). On the basis of the theoretical findings, the cyclization step is highly stereospecific. The rate constants for the reactions of C5' and aminyl 3 radicals with different oxidants were determined by pulse radiolysis methods. The respective rate constants for the reaction of 2'-deoxyadenosin-5'-yl radical with dioxygen, Fe(CN)(6)(3)(-), and MV(2+) in water at ambient temperature are 1.9 x 10(9), 4.2 x 10(9), and 2.2 x 10(8) M(-1) s(-1). The value for the reaction of aminyl radical 3 with Fe(CN)(6)(3-) is 8.3 x 10(8) M(-1) s(-1), whereas the reaction with dioxygen is reversible. Tailored experiments allowed the reaction mechanism to be defined in some detail. A synthetically useful radical cascade process has also been developed that allows in a one-pot procedure the conversion of 8-bromo-2'-deoxyadenosine to 5',8-cyclo-2'-deoxyadenosine in a diastereoisomeric ratio (5'R):(5'S) = 6:1 and in high yield, by reaction with hydrated electrons in the presence of K(4)Fe(CN)(6).     

Kinetics of the HCCO + NO2 reaction

The kinetics of the HCCO + NO2 reaction were investigated using a laser photolysis/infrared diode laser absorption technique. Ethyl ethynyl ether (C2H5OCCH) was used as the HCCO radical precursor. Transient infrared detection of the HCCO radical was used to determine a total rate constant fit to the following expression: k1= (2.43 +/- 0.26) x 10(-11) exp[(171.1 +/- 36.9)/T] cm3 molecule(-1) s(-1) over the temperature range of 298-423 K. Transient infrared detection of CO, CO2, and HCNO products was used to determine the following branching ratios at 298 K: phi(HCO + NO + CO) = 0.60 +/- 0.05 and phi(HCNO + CO2) = 0.40 +/- 0.05.     

Experimental and theoretical studies of the phenyl radical reaction with propene

The kinetics for the reaction of C6H5 with propene has been measured by cavity ring-down spectrometry (CRDS) at temperatures 296-496 K under an Ar pressure of 40 Torr. The total rate constant can be given by the following Arrhenius expression (in units of cm3 mol(-1) s(-1)): k(C6H5 + C3H6) = 10(11.93+/-0.06) exp[-(1512 +/- 51)/T]. Density functional and higher level of theory calculations (up to the G2M level) have been carried out to provide additional insights about the mechanism of this reaction, and we also performed transition state theory (TST) calculation for the rate constant prediction. Our theoretical kinetic calculations predict that the C6H5 addition to the terminal =CH2 site in propene is dominant at the temperature range of our CRDS measurements. However, the H-abstraction channel forming benzene and the allyl radical becomes increasingly important at higher temperatures. The total high-pressure limiting rate constant calculated on the basis of the G2M reaction barriers is in reasonable agreement with the experimental values.     

Tunneling chemical reactions in solid parahydrogen: direct measurement of the rate constants of R + H2 --> RH + H (R = CD3,CD2H,CDH2,CH3) at 5 K

Tunneling chemical reactions between deuterated methyl radicals and the hydrogen molecule in a parahydrogen crystal have been studied by Fourier transform infrared spectroscopy. The tunneling rates of the reactions R + H2 --> RH + H (R = CD3,CD2H,CDH2) in the vibrational ground state were determined directly from the temporal change in the intensity of the rovibrational absorption bands of the reactants and products in each reaction in solid parahydrogen observed at 5 K. The tunneling rate of each reaction was found to differ definitely depending upon the degree of deuteration in the methyl radicals. The tunneling rates were determined to be 3.3 x 10(-6) s(-1), 2.0 x 10(-6) s(-1), and 1.0 x 10(-6) s(-1) for the systems of CD3, CD2H, and CDH2, respectively. Conversely, the tunneling reaction between a CH3 radical and the hydrogen molecule did not proceed within a week's time. The upper limit of the tunneling rate of the reaction of the CH3 radical was estimated to be 8 x 10(-8) s(-1).     

Theoretical study of the benzyl+O2 reaction: kinetics, mechanism, and product branching ratios

Ab initio calculations at the level of CBS-QB3 theory have been performed to investigate the potential energy surface for the reaction of benzyl radical with molecular oxygen. The reaction is shown to proceed with an exothermic barrierless addition of O2 to the benzyl radical to form benzylperoxy radical (2). The benzylperoxy radical was found to have three dissociation channels, giving benzaldehyde (4) and OH radical through the four-centered transition states (channel B), giving benzyl hydroperoxide (5) through the six-centered transition states (channel C), and giving O2-adduct (8) through the four-centered transition states (channel D), in addition to the backward reaction forming benzyl radical and O2 (channel E). The master equation analysis suggested that the rate constant for the backward reaction (E) of C6H5CH2OO-->C6H5CH2+O2 was several orders of magnitude higher that those for the product dissociation channels (B-D) for temperatures 300-1500 K and pressures 0.1-10 atm; therefore, it was also suggested that the dissociation of benzylperoxy radicals proceeded with the partial equilibrium between the benzyl+O2 and benzylperoxy radicals. The rate constants for product channels B-D were also calculated, and it was found that the rate constant for each dissociation reaction pathway was higher in the order of channel D>channel C>channel B for all temperature and pressure ranges. The rate constants for the reaction of benzyl+O2 were computed from the equilibrium constant and from the predicted rate constant for the backward reaction (E). Finally, the product branching ratios forming CH2O molecules and OH radicals formed by the reaction of benzyl+O2 were also calculated using the stationary state approximation for each reaction intermediate.     

An ignored but most favorable channel for NCO+C2H2 reaction

The NCO+C(2)H(2) reaction has been considered as a prototype for understanding the chemical reactivity of the isocyanate radical towards unsaturated hydrocarbons in fuel-rich combustion. It has also been proposed to provide an effective route for formation of oxazole-containing compounds in organic synthesis, and might have potential applications in interstellar processes. Unfortunately, this reaction has met mechanistic controversy both between experiments and between experiments and theoretical calculations. In this paper, detailed theoretical investigations at the Becke's three parameter Lee-Yang-Parr-B3LYP6-31G(d), B3LYP6-311++G(d,p), quadratic configuration interaction with single and double excitations QCISD6-31G(d), and Gaussian-3 levels are performed for the NCO+C(2)H(2) reaction, covering various entrance, isomerization, and decomposition channels. Also, the highly cost-expensive coupled-cluster theory including single and double excitations and perturbative inclusion of triple excitations CCSD(T)/aug-cc-pVTZ single-point energy calculation is performed for the geometries obtained at the Becke's three parameter Lee-Yang-Parr-B3LYP6-311++G(d,p) level. A previously ignored yet most favorable channel via a four-membered ring intermediate with allyl radical character is found. However, formation of P(3) H+HCCNCO and the five-membered ring channel predicted by previous experimental and theoretical studies is kinetically much less competitive. With the new channel, master equation rate constant calculations over a wide range of temperatures (298-1500 K) and pressures (10-560 Torr) show that the predicted total rate constants exhibit a positive-temperature dependence and no distinct pressure dependence effect. This is in qualitative agreement with available experimental results. Under the experimental conditions, the predicted values are about 50% lower than the latest experimental results. Also, the branching ratio variations of the fragments P(2) HCN+HCCO and P(5) OCCHCN+H as well as the intermediates L1 HCHCNCO, r4 cCHCHNC-O, and L5 NCHCHCO are discussed with respect to the temperature and pressure. Future experimental reinvestigations are strongly desired to test the newly predicted channel for the model NCO+C(2)H(2) reaction. Implications of the present results in various fields are discussed.     

Kinetics and mechanism of the C6H5 + CH3CHO reaction: experimental measurement and theoretical prediction of the reactivity toward four molecular sites.

The kinetics and mechanism of the reaction of C6H5 with CH3CHO have been investigated experimentally and theoretically. The total rate constant for the reaction has been measured by means of the cavity ring-down spectrometry (CRDS) in the temperature range 299-501 K at pressures covering 20-75 Torr. The overall bimolecular rate constant can be represented by the expression k = (2.8 +/- 0.2) x 10(11) exp[-(700 +/- 30)/T] cm3 mol-1 s-1, which is slightly faster than for the analogous C6H5 + CH2O reaction determined with the same method in the same temperature range. The reaction mechanism for the C6H5 + CH3CHO reaction was also explored with quantum-chemical calculations at various hybrid density functional theories (DFTs) and using ab initio high-level composite methods. The theories predict that the reaction may occur by two hydrogen-abstraction and two addition channels with the aldehydic hydrogen-abstraction reaction being dominant. The rate constant calculated by the transition state theory for the aldehydic hydrogen-abstraction reaction is in good agreement with the experimental result after a very small adjustment of the predicted reaction barrier (+0.3 kcal mol-1). Contributions from other product channels are negligible under our experimental conditions. For combustion applications, we have calculated the rate constants for key product channels in the temperature range of 298-2500 K under atmospheric-pressure conditions; they can be represented by the following expressions in units of cm 3mol-1 s-1: k1,cho = 8.8 x 10(3)T2.6 exp(-90/T), k2,ch3 = 6.0 x 10(1)T3.3 exp(-950/T), k3a(C6H5COCH3 + H) = 4.2 x 10(5)T0.6 exp(-410/T) and k3b(C6H5CHO + CH3) = 6.6 x 10(9)T-0.5 exp(-310/T).     

Kinetic and product study of the gas-phase reactions of OH radicals, NO(3) radicals, and O(3) with (C(2)H(5)O)(2)P(S)CH(3) and (C(2)H(5)O)(3)PS

Rate constants for the reactions of OH radicals and NO3 radicals with O,O-diethyl methylphosphonothioate [(C(2)H(5)O)(2)P(S)CH(3); DEMPT] and O,O,O-triethyl phosphorothioate [(C(2)H(5)O)(3)PS; TEPT] have been measured using relative rate methods at atmospheric pressure of air over the temperature range 296-348 K for the OH radical reactions and at 296 +/- 2 K for the NO(3) radical reactions. At 296 +/- 2 K, the rate constants obtained for the OH radical reactions (in units of 10(-11) cm(3) molecule(-1) s(-1)) were 20.4 +/- 0.8 and 7.92 +/- 0.27 for DEMPT and TEPT, respectively, and those for the NO(3) radical reactions (in units of 10(-15) cm(3) molecule(-1) s(-1)) were 2.01 +/- 0.20 and 1.03 +/- 0.10, respectively. Upper limits to the rate constants for the reactions of O(3) with DEMPT and TEPT of <6 x 10(-20) cm(3) molecule(-1) s(-1) were determined in each case. Rate constants for the OH radical reactions, measured relative to k(OH + alpha-pinene) = 1.21 x 10(-11) e(436/T) cm(3) molecule(-1) s(-1), resulted in the Arrhenius expressions k(OH + DEMPT) = 1.08 x 10(-11) e(871+/-25)/T cm(3) molecule(-1) s(-1) and k(OH + TEPT) = 8.21 x 10(-13) e(1353+/-49)/T cm(3) molecule(-1) s(-1) over the temperature range 296-348 K, where the indicated errors are two least-squares standard deviations and do not include the uncertainties in the reference rate constant. Diethyl methylphosphonate was identified and quantified from the OH radical and NO(3) radical reactions with DEMPT, with formation yields of 21 +/- 4%, independent of temperature, from the OH radical reaction and 62 +/- 11% from the NO(3) radical reaction at 296 +/- 2 K. Similarly, triethyl phosphate was identified and quantified from the OH radical and NO(3) radical reactions with TEPT, with formation yields of 56 +/- 9%, independent of temperature, from the OH radical reaction and 78 +/- 15% from the NO(3) radical reaction at 296 +/- 2 K.     

Kinetic study of IO radical with RO2 (R = CH(3), C2H5, and CF3) using cavity ring-down spectroscopy

The reactions of iodine monoxide radical, IO, with alkyl peroxide radicals, RO(2) (R = CH(3), C(2)H(5), and CF(3)), have been studied using cavity ring-down spectroscopy. The rate constant of the reaction of IO with CH(3)O(2) was determined to be (7.0 +/- 3.0) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K and 100 Torr of N(2) diluent. The quoted uncertainty is two standard deviations. No significant pressure dependence of the rate constant was observed at 30-130 Torr total pressure of N(2) diluent. The temperature dependence of the rate constants was also studied at 213-298 K. The upper limit of the branching ratio of OIO radical formation from IO + CH(3)O(2) was estimated to be <0.1. The reaction rate constants of IO + C(2)H(5)O(2) and IO + CF(3)O(2) were determined to be (14 +/- 6) x 10(-11) and (6.3 +/- 2.7) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K, 100 Torr of N(2) diluent, respectively. The upper limit of the reaction rate constant of IO with CH(3)I was <4 x 10(-14) cm(3) molecule(-1) s(-1).