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ABSTRACT: The photolysis of glyoxal has been investigated in the 355-414 nm region by dye laser photolysis coupled with cavity ring-down spectroscopy. Absolute quantum yields of HCO, ΦHCO, were determined using the reaction of chlorine atoms with formaldehyde as an actinometer. The dependence of the quantum yield on pressure was investigated in 3-400 Torr of nitrogen buffer gas and at four temperatures: 233 K, 268 K, 298 K and 323 K. For 355 nm ≤ λ < 395 nm the HCO quantum yield is pressure dependent with linear Stern-Volmer (SV) plots (1/ΦHCOvs. pressure). The zero pressure quantum yield, obtained by extrapolation of the SV plots, rises from 1.6 to 2 between 355 and 382 nm and remains at 2 up to 395 nm. For λ ≥ 395 nm ΦHCO shows a stronger pressure dependence and non-linear SV plots, compatible with formation of HCO by dissociation from two electronic states of glyoxal with significantly different lifetimes. These observations are used to develop a mechanism for the photolysis of glyoxal over the wavelength range studied.
Physical Chemistry Chemical Physics 03/2013; · 3.57 Impact Factor
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ABSTRACT: The formation of HCO and of H in the photolysis of glyoxal have been investigated over the wavelength ranges 310-335 nm for HCO and 193-340 nm for H. Dye laser photolysis was coupled with cavity ring-down spectroscopy for HCO, and with laser induced fluorescence spectroscopy for H. Absolute quantum yields were determined using actinometers based on (a) Cl(2) photolysis and the Cl + HCHO reaction for HCO and (b) N(2)O photolysis (and O(1)D + H(2)) and CH(2)CO photolysis (and CH(2) + O(2)) for H. The quantum yields were found to be pressure independent in this wavelength region. Quantum yields for all product channels under atmospheric conditions were calculated and compared with literature values. Differences between this work and previously published work and their atmospheric implications are discussed.
Physical Chemistry Chemical Physics 02/2013; · 3.57 Impact Factor
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ABSTRACT: Bimolecular reactions in Earth's atmosphere are generally assumed to proceed between reactants whose internal quantum states are fully thermally relaxed. Here, we highlight a dramatic role for vibrationally excited bimolecular reactants in the oxidation of acetylene. The reaction proceeds by preliminary adduct formation between the alkyne and OH radical, with subsequent O(2) addition. Using a detailed theoretical model, we show that the product-branching ratio is determined by the excited vibrational quantum-state distribution of the adduct at the moment it reacts with O(2). Experimentally, we found that under the simulated atmospheric conditions O(2) intercepts ~25% of the excited adducts before their vibrational quantum states have fully relaxed. Analogous interception of excited-state radicals by O(2) is likely common to a range of atmospheric reactions that proceed through peroxy complexes.
Science 08/2012; 337(6098):1066-9. · 31.20 Impact Factor
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ABSTRACT: In this paper, the time resolution for kinetic studies of reactions with mass spectrometric detection is characterized in detail, and it is shown how this allows faster kinetic processes to be determined. The time-resolved technique used pulsed laser photolysis to initiate reaction and a time-of-flight mass spectrometer (TOFMS) to monitor progress, where the reactant gas was sampled by a sampling orifice and photoionized using pulsed, laser vacuum ultraviolet light before being analyzed by the TOFMS. Characterization of this setup has been carried out to identify the parameters that affect the time for “sampling,” which limits the fastest reactions that can be measured. A simple mathematical equation has been developed to correct for “sampling” delays (ksampling∼25, 000 s−1), which extends the range of rate coefficients to be measured in a kinetic mass spectrometry reactor to k′ < 7000 s−1. This method could be applied to any other kinetic mass spectrometry system where ksampling can be measured; an important advantage since it allows the study of reactions over a wider range of conditions (e.g., larger concentrations of reagents/products can be used to minimize the contribution from wall losses). The system can produce reliable kinetic data whether monitoring reactant decay or product growth even when the reaction and sampling processes are occurring on a similar timescale (k′ < 7000 s−1). Reproducible and reliable kinetic data have been obtained for the following reactions: SO + NO2 → products (R1), ClSO + NO2 → products (R2), where SO and ClSO were monitored under pseudo-first-order conditions, and HCO + O2 → CO + HO2 (R3), where CO was monitored by a [1+1] resonance enhanced ionization multiphoton ionization (REMPI) scheme with HCO reacting under pseudo–first-order conditions. The limitations and potential developments of this setup are described
International Journal of Chemical Kinetics 11/2011; 44(8):532. · 1.01 Impact Factor
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ABSTRACT: The rate coefficients for reactions of OH with ethanol and partially deuterated ethanols have been measured by laser flash photolysis/laser-induced fluorescence over the temperature range 298-523 K and 5-100 Torr of helium bath gas. The rate coefficient, k(1.1), for reaction of OH with C(2)H(5)OH is given by the expression k(1.1) = 1.06 × 10(-22)T(3.58) exp(1126/T) cm(3) molecule(-1) s(-1), and the values are in good agreement with previous literature. Site-specific rate coefficients were determined from the measured kinetic isotope effects. Over the temperature region 298-523 K abstraction from the hydroxyl site is a minor channel. The reaction is dominated by abstraction of the α hydrogens (92 ± 8)% at 298 K decreasing to (76 ± 9)% with the balance being abstraction at the β position where the errors are 2σ. At higher temperatures decomposition of the CH(2)CH(2)OH product from β abstraction complicates the kinetics. From 575 to 650 K, biexponential decays were observed, allowing estimates to be made for k(1.1) and the fractional production of CH(2)CH(2)OH. Above 650 K, decomposition of the CH(2)CH(2)OH product was fast on the time scale of the measured kinetics and removal of OH corresponds to reaction at the α and OH sites. The kinetics agree (within ±20%) with previous measurements. Evidence suggests that reaction at the OH site is significant at our higher temperatures: 47-53% at 865 K.
The Journal of Physical Chemistry A 03/2011; 115(15):3335-45. · 2.95 Impact Factor
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ABSTRACT: The acetyl + O(2) reaction has been studied by observing the time dependence of OH by laser-induced fluorescence (LIF) and by electronic structure/master equation analysis. The experimental OH time profiles were analyzed to obtain the kinetics of the acetyl + O(2) reaction and the relative OH yields over the temperature range of 213-500 K in helium at pressures in the range of 5-600 Torr. More limited measurements were made in N(2) and for CD(3)CO + O(2). The relative OH yields were converted into absolute yields by assuming that the OH yield at zero pressure is unity. Electronic structure calculations of the stationary points of the potential energy surface were used with a master equation analysis to fit the experimental data in He using the high-pressure limiting rate coefficient for the reaction, k(∞)(T), and the energy transfer parameter, (ΔE(d)), as variable parameters. The best-fit parameters obtained are k(∞) = 6.2 × 10(-12) cm(-3) molecule(-1) s(-1), independent of temperature over the experimental range, and (ΔE(d))(He) = 160(T/298 K) cm(-1). The fits in N(2), using the same k(∞)(T), gave (ΔE(d))(N(2)) = 270(T/298 K) cm(-1). The rate coefficients for formation of OH and CH(3)C(O)O(2) are provided in parametrized form, based on modified Troe expressions, from the best-fit master equation calculations, over the pressure and temperature ranges of 1 ≤ p/Torr ≤ 1.5 × 10(5) and 200 ≤ T/K ≤ 1000 for He and N(2) as the bath gas. The minor channels, leading to HO(2) + CH(2)CO and CH(2)C(O)OOH, generally have yields <1% over this range.
The Journal of Physical Chemistry A 02/2011; 115(6):1069-85. · 2.95 Impact Factor
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ABSTRACT: The photolysis of acetylene at 193 nm has been investigated as a source of the ethynyl radical, C 2 H, for product branching ratio studies, particularly the formation of H atom product as the photolysis, producing a 1:1 ratio of C 2 H and H, provides an internal calibration. Previous literature had suggested that C 2 H and H may only be a minor component of acetylene photolysis at 193 nm. Acetylene was photolyzed at low laser energy densities (<7 mJ cm -2), with H atoms being observed as a function of time by VUV laser induced fluorescence. When C 2 H was reacted with C 2 H 2 , a reaction that is known to produce H atoms with unit yield, the ratio of photolytic H atom production to chemical production was 0.96 (0.03. The rate coefficient for the reaction of C 2 H with C 2 H 2 could accurately be retrieved from the time evolution of the H atom signal. The results suggest that acetylene photolysis at low laser energies is a good source of C 2 H for product branching studies, and the technique has been applied to the reactions of C 2 H with ethene and propene. For the reaction with ethene between 23 and 81 Torr, the yield of H is 0.94 (0.06, suggesting that an addition elimination mechanism dominates with the formation of vinylacetylene and H atoms. For the reaction of C 2 H with propene, no H atom product was observed, putting a lower limit of <5% for H atom production. Possible explanations for the low H atom yield are discussed. The implications of these results in combustion and planetary atmospheres are briefly considered.
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ABSTRACT: The photolysis of acetylene at 193 nm has been investigated as a source of the ethynyl radical, C(2)H, for product branching ratio studies, particularly the formation of H atom product as the photolysis, producing a 1:1 ratio of C(2)H and H, provides an internal calibration. Previous literature had suggested that C(2)H and H may only be a minor component of acetylene photolysis at 193 nm. Acetylene was photolyzed at low laser energy densities (<7 mJ cm(-2)), with H atoms being observed as a function of time by VUV laser induced fluorescence. When C(2)H was reacted with C(2)H(2), a reaction that is known to produce H atoms with unit yield, the ratio of photolytic H atom production to chemical production was 0.96 +/- 0.03. The rate coefficient for the reaction of C(2)H with C(2)H(2) could accurately be retrieved from the time evolution of the H atom signal. The results suggest that acetylene photolysis at low laser energies is a good source of C(2)H for product branching studies, and the technique has been applied to the reactions of C(2)H with ethene and propene. For the reaction with ethene between 23 and 81 Torr, the yield of H is 0.94 +/- 0.06, suggesting that an addition elimination mechanism dominates with the formation of vinylacetylene and H atoms. For the reaction of C(2)H with propene, no H atom product was observed, putting a lower limit of <5% for H atom production. Possible explanations for the low H atom yield are discussed. The implications of these results in combustion and planetary atmospheres are briefly considered.
The Journal of Physical Chemistry A 04/2010; 114(14):4735-41. · 2.95 Impact Factor
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ABSTRACT: Laboratory studies of gas-phase chemical processes are a key tool in understanding the chemistry of our atmosphere and hence tackling issues such as climate change and air quality. Laboratory techniques have improved considerably with greater emphasis on product detection, allowing the measurement of site-specific rate coefficients. Radical chemistry lies at the heart of atmospheric chemistry. In this review we consider issues around radical generation and recycling from the oxidation of isoprene and from the chemical reactions and photolysis of carbonyl species. Isoprene is the most globally significant hydrocarbon, but uncertainties exist about its oxidation in unpolluted environments. Recent experiments and calculations that cast light on radical generation are reviewed. Carbonyl compounds are the dominant first-generation products from hydrocarbon oxidation. Chemical oxidation can recycle radicals, or photolysis can be a net radical source. Studies have demonstrated that high-resolution and temperature-dependent studies are important for some significant species.
Annual Review of Physical Chemistry 04/2010; 62:351-73. · 14.13 Impact Factor
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ABSTRACT: The temperature dependence of the branching ratios for H atom production from the reactions of the first excited state of methylene (a1A1 1CH2) with acetylene and ethene have been measured at approximately 1 Torr total pressure and temperatures of 195, 250 and 298 K by monitoring the production of H atoms using laser induced fluorescence, comparing the signal to that observed from a calibration reaction. For the reaction with acetylene the yield of H increases from 0.28 (195 K) to 0.53 (250 K) to 0.88 at 298 K. The H atom yield from the reaction of 1CH2 with ethene shows similar behaviour, the yields being 0.35 (195 K), 0.51 (250 K) and 0.71 (298 K). The co-products, propargyl (C3H3) and allyl (C3H5) are formed from the dissociation of chemically activated C3H4 and C3H6 intermediates respectively, and are important species in the formation of higher hydrocarbons, including benzene, in the atmospheres of the outer planets and Titan. H atom production is in competition with electronic relaxation to form ground state methylene (X3B1, 3CH2) and collisional stabilization to form C3H4 and C3H6. Master equation calculations have been carried out to demonstrate that for the reaction of 1CH2 with acetylene, collisional stabilization is insignificant under experimental conditions and hence the balance of reaction is due to electronic relaxation. Non-adiabatic transition state theory has been applied to the reaction of 1CH2 with acetylene. The calculations show reasonable agreement with experiment, generally being within the combined errors, and reproduce the negative temperature dependence for electronic relaxation. The implications of the temperature dependence of the absolute rate coefficients for 1CH2 reactions with inert gases, hydrogen, acetylene and ethene and of the branching ratios between chemical reaction and electronic relaxation are discussed.
Faraday Discussions 01/2010; 147:173-88; discussion 251-82. · 5.00 Impact Factor
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ABSTRACT: By comparing H-atom yields from the reactions of CN with C(2)H(2) and NH(3), it has been confirmed that the latter reaction produces insignificant amounts of H-atoms, implying that it proceeds exclusively to HCN + NH(2).
Physical Chemistry Chemical Physics 12/2009; 11(46):10824-6. · 3.57 Impact Factor
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ABSTRACT: The technique of excimer laser excitation/Lyman alpha H atom laser induced fluorescence was used to investigate the formation of H atoms from the 248 nm photoexcitation of benzene and toluene. The H atom signal dependence on laser excitation energy demonstrated that it is produced from two photon photolysis of the aromatics; absorption of the first photon populates the bound (1)B(2u) level followed by absorption from this level to a dissociative level, which produces H atoms, among other potential channels. Analysis of the data yields the second photon absorption cross section to produce H and is equal to 1.0 and 5.2x10(-19) cm(2) for benzene and toluene, respectively. In addition, the yield of H atoms was observed to be pressure dependent. This is because at sufficiently high pressures the nanosecond lifetime of the (1)B(2u) state can be pressure quenched and hence may compete with the absorption of the second photon. The yields of H atoms were determined as a function of pressure for a range of the laser energies and with various collider gases. The analysis of these data allowed the total absorption cross section for the second photon to be determined and is equal to 2.8 and 1.7x10(-17) cm(2) for benzene and toluene, respectively. In addition, the rate constants for quenching (1)B(2u) with various gases (He, Ar, N(2), and O(2)) were determined. This large absorption coefficient for the second photon implies that with a pulsed laser source of 248 nm it is difficult to avoid aromatic photodissociation. We highlight a few previous studies that may need to be reevaluated in the light of the results from this study.
The Journal of chemical physics 11/2009; 131(20):204304. · 3.09 Impact Factor
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ABSTRACT: Photoexcitation of glyoxal at wavelengths over the range of 395-414 nm was observed to initiate a chemical reaction that produces the HCO radical in addition to the photolytic production of HCO. The technique of dye laser flash photolysis coupled to cavity ring-down spectroscopy was used to determine the time dependence of the HCO radical signal, analysis of which suggests that the chemical source of HCO is the self-reaction of triplet glyoxal (HCO)2(T1) + (HCO)2(T1) --> 2 HCO + (HCO)2. As the photoexcitation wavelength increases, the production from the triplet glyoxal reaction increases relative to that of HCO from direct photolysis, and at 414 nm, the dominant source of HCO in the system is from the self-reaction of the triplet. The formation of HCO via this process complicates the assignment of the photolysis quantum yield at longer wavelengths and may have been overlooked in some previous glyoxal photolysis studies.
The Journal of Physical Chemistry A 07/2009; 113(29):8278-85. · 2.95 Impact Factor
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ABSTRACT: The design of and initial results obtained from a multipass matrix system (MMS) for mid-infrared spectroscopy that operates in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) recently constructed in the School of Chemistry at the University of Leeds, is described. HIRAC is an evacuable, temperature variable, photochemical atmospheric reaction chamber. The MMS design is a modified Chernin cell, utilizing three objective mirrors and two field mirrors. In addition to providing the paraxial equations required for design of a throughput matched multipass cell and throughput matched transfer optics, advanced ray tracing simulations have been performed for the Chernin design described herein. The simulations indicate that, for this MMS, which features small off-axis angles and preserves perfectly the focal properties of the original White design, the paraxial equations are nearly exact, throughput losses due to astigmatism are insignificant, and the system has zero theoretical geometric loss. Measurements of the signal incident on the detector at different matrix arrangements confirm the ray trace results, suggesting that geometric loss in this system is insignificant. The MMS described herein provides adequate stability to permit measurements while the chamber mixing fans are on, gives very good detection limits for some representative species, and is easy to align.
Applied Optics 12/2007; 46(32):7872-83. · 1.41 Impact Factor
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ABSTRACT: Experimental studies have been conducted to determine the rate coefficient and mechanism of the reaction between methylglyoxal (CH(3)COCHO, MGLY) and the OH radical over a wide range of temperatures (233-500 K) and pressures (5-300 Torr). The rate coefficient is pressure independent with the following temperature dependence: k(3)(T) = (1.83 +/- 0.48) x 10(-12) exp((560 +/- 70)/T) cm(3) molecule(-1) s(-1) (95% uncertainties). Addition of O(2) to the system leads to recycling of OH. The mechanism was investigated by varying the experimental conditions ([O(2)], [MGLY], temperature and pressure), and by modelling based on a G3X potential energy surface, rovibrational prior distribution calculations and master equation RRKM calculations. The mechanism can be described as follows: Addition of oxygen to the system shows that process (4) is fast and that CH(3)COCO completely dissociates. The acetyl radical formed from reaction (4) reacts with oxygen to regenerate OH radicals (5a). However, a significant fraction of acetyl radical formed by reaction (R4) is sufficiently energised to dissociate further to CH(3) + CO (R4b). Little or no pressure quenching of reaction (R4b) was observed. The rate coefficient for OD + MGLY was measured as k(9)(T) = (9.4 +/- 2.4) x 10(-13) exp((780 +/- 70)/T) cm(3) molecule(-1) s(-1) over the temperature range 233-500 K. The reaction shows a noticeable inverse (k(H)/k(D) < 1) kinetic isotope effect below room temperature and a slight normal kinetic isotope effect (k(H)/k(D) > 1) at high temperature. The potential atmospheric implications of this work are discussed.
Physical Chemistry Chemical Physics 08/2007; 9(31):4114-28. · 3.57 Impact Factor
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ABSTRACT: The kinetics and H atom channel yield at both 298 and 195 K have been determined for reactions of CN radicals with C2H2 (1.00+/-0.21, 0.97+/-0.20), C2H4 (0.96+/-0.032, 1.04+/-0.042), C3H6 (pressure dependent), iso-C4H8 (pressure dependent), and trans-2-C4H8 (0.039+/-0.019, 0.029+/-0.047) where the first figure in each bracket is the H atom yield at 298 K and the second is that at 195 K. The kinetics of all reactions were studied by monitoring both CN decay and H atom growth by laser-induced fluorescence at 357.7 and 121.6 nm, respectively. The results are in good agreement with previous studies where available. The rate coefficients for the reaction of CN with trans-2-butene and iso-butene have been measured at 298 and 195 K for the first time, and the rate coefficients are as follows: k298K=(2.93+/-0.23)x10(-10) cm3 molecule(-1) s(-1), k195K=(3.58+/-0.43)x10(-10) cm3 molecule(-1) s(-1) and k298K=(3.17+/-0.10)x10(-10) cm3 molecule(-1) s(-1), k195K=(4.32+/-0.35)x10(-10) cm3 molecule(-1) s(-1), respectively, where the errors represent a combination of statistical uncertainty (2sigma) and an estimate of possible systematic errors. A potential energy surface for the CN+C3H6 reaction has been constructed using G3X//UB3LYP electronic structure calculations identifying a number of reaction channels leading to either H, CH3, or HCN elimination following the formation of initial addition complexes. Results from the potential energy surface calculations have been used to run master equation calculations with the ratio of primary:secondary addition, the average amount of downward energy transferred in a collision DeltaEd, and the difference in barrier heights between H atom elimination and an H atom 1, 2 migration as variable parameters. Excellent agreement is obtained with the experimental 298 K H atom yields with the following parameter values: secondary addition complex formation equal to 80%, DeltaEd=145 cm(-1), and the barrier height for H atom elimination set 5 kJ mol(-1) lower than the barrier for migration. Finally, very low temperature master equation simulations using the best fit parameters have been carried out in an increased precision environment utilizing quad-double and double-double arithmetic to predict H and CH3 yields for the CN+C3H6 reaction at temperatures and pressures relevant to Titan. The H and CH3 yields predicted by the master equation have been parametrized in a simple equation for use in modeling.
The Journal of Physical Chemistry A 08/2007; 111(29):6679-92. · 2.95 Impact Factor
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ABSTRACT: The kinetics of the reaction OH + C2H2 have been studied using laser flash photolysis at 248 nm to generate OH radicals and laser-induced fluorescence to monitor OH removal. An attempt was made to use the rate coefficients OH (v = 1,2) + C2H2 to determine the limiting high-pressure rate coefficient, k(1a)(infinity), over the temperature range of 195-823 K. This method is usually applicable if the reaction samples the potential energy well of the adduct, HOC2H2, and if intramolecular vibrational relaxation is fast. In the present case, however, the rate coefficients for loss of the vibrationally excited states by reaction with C2H2 also contain a substantial contribution from nonreactive vibrational relaxation, which occurs via a mechanism that does not sample the adduct potential energy well but involves, at least at low temperatures, collisions that access a shallower, longer range van der Waals well. The data were analyzed using a composite mechanism that incorporates both reactive and nonreactive energy transfer mechanisms, which allows the determination of k(1a)(infinity)(T) for OH + C2H2 with satisfactory accuracy over the temperature range 195-823 K. The kinetics of the reaction OH (v = 0) + C2H2 were also studied in He over the range of conditions: 210-373 K and 5-760 Torr. A one-dimensional master equation (ME) analysis of the experimental data provided a further determination of k(1a)(infinity)(T) and also (down) for He. Combining the two sets of results gives a consistent dataset for k(1a)(infinity) and the Arrhenius parameters A1ainfinity = 7.3 x 10(-12) cm(3) molecule(-1) s(-1) and E(1a)(infinity) = 5.3 kJ mol(-1), with (down) = 150(T/300 K) cm(-1). Additional experiments were conducted at room temperature in N(2) and SF(6) by laser flash photolysis with cavity ring down spectroscopy, and ME calculations were then optimized for the pressure falloff in N(2) by varying the average downward energy transfer parameter ( (down)). The output from the best fit ME was parametrized using a modified Troe expression to provide rate data for use in atmospheric modeling.
The Journal of Physical Chemistry A 05/2007; 111(19):4043-55. · 2.95 Impact Factor
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ABSTRACT: The pressure and temperature dependence for the reaction of OH + C(2)H(4) was studied over the range of conditions: 200-400 K and 5-600 Torr by laser flash photolysis, laser-induced fluorescence (FP-LIF). Additional experiments were conducted at room temperature by laser flash photolysis, cavity ring-down spectroscopy to facilitate determination of the high pressure limit. One-dimensional master equation calculations were conducted to test the temperature and pressure dependence of the reaction in He and in N(2). The energetics of the reaction and geometries of intermediate species were calculated by ab initio calculations (DFT-BH&HLYP/6-311+G(3df,2p) and CBS-APNO level along DFT-IRC, respectively. An investigation into the importance of a pre-reaction van der Waals complex on the kinetics over the pressure range of the troposphere is discussed. The high pressure rate coefficient was extracted by fitting the master equation calculations to the data and yields k(infinity) = 5.01 x 10(-12) exp(148/T) cm(3) molecule(-1) s(-1). The master equation calculations were then optimized for the pressure fall-off in He and N(2) by varying the average downward energy transfer parameter (DeltaE(down)) for the different collision partners and finally fitted to a Troe expression to determine k(o) and F(cent) for use in atmospheric modeling.
Physical Chemistry Chemical Physics 12/2006; 8(48):5633-42. · 3.57 Impact Factor
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ABSTRACT: Laser flash photolysis of ketene at 308 nm, coupled with H atom vacuum ultraviolet laser induced fluo-rescence, was used to determine the branching ratio for the CH 3 + H channel (1a) in the reaction of CH 2 1 A 1 (1 CH 2) with H 2 , over the temperature range 300–500 K. This reaction channel competes with col-lision induced intersystem crossing (CIISC) to form triplet methylene, CH 2 3 B 1 (3 CH 2) (channel 1b). The branching ratio for H formation, k 1a /k 1 , was determined by measuring the relative H atom yield in three time resolved measurements of H: (i) in ketene, H 2 mixtures, where H is exclusively formed by reaction 1a, (ii) in ketene, H 2 , NO mixtures ([NO] ([H 2 ]), where H is formed at short times by 1a and at longer times by 3 CH 2 + NO, following 1b, and (iii) in ketene, He, NO mixtures ([NO] ([He]), where H is exclusively formed from 3 CH 2 + NO, following deactivation of singlet to triplet methylene by He. k 1a /k 1 was found to increase from 0.85 at 300 K to unity at 500 K, with the yield of CIISC decreasing from 0.15 to zero. This is the first measurement of the temperature dependence of the rate coefficient for CIISC in a reactive system. The rate coefficient for CIISC with an inert gas increases with T. It has been suggested that the fractional yield of CIISC will increase with temperature in reactive systems, thus reducing the rate coefficient for reac-tion at high temperature, with significant consequences for combustion systems. The present experiments demonstrate that this is not the case for reaction with H 2 and implies a different CIISC mechanism for reac-tive vs inert collision partners. Ó 2004 Published by Elsevier Inc. on behalf of The Combustion Institute.
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ABSTRACT: Quantum yields for acyl (RCO) radical production from ketone photolysis as a function of temperature, pressure and the atmospherically relevant wavelengths (308 and 320 nm) have been determined for methylethyl ketone (MEK), methylvinyl ketone (MVK) and diethyl ketone (DEK) via direct observation of the OH product from the RCO + O2 reaction. The methodology has been applied previously to acetone photolysis. The kinetics and OH yields of the RCO + O2 reactions have been investigated to demonstrate that this technique can be used to monitor the dissociation of higher ketones. These kinetic studies have been used to confirm CH3CO + R as the dominant radical dissociation mechanism in the unsymmetrical ketones MVK and MEK. At 308 nm MEK and DEK photolysis follows conventional Stern Volmer behaviour. MEK and DEK are quenched less efficiently than acetone; quenching efficiency increases with decreasing temperature (213-295 K). At 320 nm Stern Volmer plots of the RCO quantum yields show evidence for the involvement of multiple states in the dissociation. The wavelength dependence of this phenomenon is compared with that for acetone and the atmospheric implications for MEK and DEK lifetimes have been investigated by converting the measured quantum yields to photolysis rates. The calculated rates under typical atmospheric conditions are a factor 2-3 lower than if the quantum yields in the literature are used, influencing both the overall atmospheric lifetime of these ketones and their relative rates of removal by reaction with OH and by photolysis.
Faraday Discussions 02/2005; 130:73-88; discussion 125-51, 519-24. · 5.00 Impact Factor
