Vadim D. Knyazev

The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach To Isomer-resolved Chemical Kinetics

We have developed a multiplexed time- and photon-energy-resolved photoionization mass spectrometer for the study of the kinetics and isomeric product branching of gas phase, neutral chemical reactions. The instrument utilizes a side-sampled flow tube reactor, continuously tunable synchrotron radiation for photoionization, a multimass double-focusing mass spectrometer with 100% duty cycle, and a time- and position-sensitive detector for single ion counting. This approach enables multiplexed, universal detection of molecules with high sensitivity and selectivity. In addition to measurement of rate coefficients as a function of temperature and pressure, different structural isomers can be distinguished based on their photoionization efficiency curves, providing a more detailed probe of reaction mechanisms. The multiplexed three-dimensional data structure (intensity as a function of molecular mass, reaction time, and photoionization energy) provides insights that might not be available in serial acquisition, as well as additional constraints on data interpretation.

Inhibition of Premixed Methane Flames by Manganese and Tin Compounds

Abstract The first experimental measurements of the influence of manganese- and tin-containing compounds (MMT, TMT) on the burning velocity of methane/air flames are presented. Comparisons with Fe(CO) 5 and CF 3 Br demonstrate that manganese and tin-containing compounds are effective inhibitors. The inhibition efficiency of MMT is about a factor of two less than that of iron pentacarbonyl, and that of TMT is about 26 times less effective, although TMT is still about twice as effective as CF 3 Br. There exist conditions for which both MMT and TMT show a loss of effectiveness beyond that expected because of radical depletion, and the cause is believed to be particle formation. Kinetic models describing the inhibition mechanisms of manganese- and tin-containing compounds are suggested. Simulations of MMT- and TMT-inhibited flames show reasonable agreement with experimental data. The decomposition of the parent molecule for the tin and manganese species is found to have a small effect on the inhibition properties for the concentrations in this work. The inhibition effect of TMT is determined mostly by the rate of the association reaction H + SnO + M ↔ SnOH + M, and the catalytic recombination cycle is completed by the reactions SnOH + H ↔ SnO + H 2 and SnOH + OH ↔ SnO + H 2 O. The inhibition mechanism by manganese-containing compounds includes the reactions: MnO + H 2 O ↔ Mn(OH) 2 ; Mn(OH) 2 + H ↔ MnOH + H 2 O, and MnOH + OH (or H) ↔ MnO + H 2 O (or H 2 ), and the burning velocity is most sensitive to the rate of the reaction Mn(OH) 2 + H ↔ MnOH + H 2 O.

COMMENT ON : HINDERED ROTOR DENSITY-OF-STATES INTERPOLATION FUNCTION J. CHEM. PHYS. 106, 6675 (1997) AND THE HINDERED ROTOR DENSITY-OF-STATES J. CHEM. PHYS. 108, 1748 (1998)

It is demonstrated that an approximation to the partition function of a hindered rotor derived by McClurg, Flagan, and Goddard III is an equivalent of a formula published by Pitzer and Gwinn in 1942. Error in analytical expression for internal energy is pointed out. Classical density-of-states function derived by McClurg in a subsequent article has also been published before.

Classical Trajectories and RRKM Modeling of Collisional Excitation and Dissociation of Benzylammonium and tert-Butyl Benzylammonium Ions in a Quadrupole-Hexapole-Quadrupole Tandem Mass Spectrometer

Collision-induced dissociation of the benzylammonium and the 4-tert-butyl benzylammonium ions was studied experimentally in an electrospray ionization quadrupole-hexapole-quadrupole tandem mass spectrometer. Ion fragmentation efficiencies were determined as functions of the kinetic energy of ions and the collider gas (argon) pressure. A theoretical Monte Carlo model of ion collisional excitation, scattering, and decomposition was developed. The model includes simulation of the trajectories of the parent and the product ions flight through the hexapole collision cell, quasiclassical trajectory modeling of collisional activation and scattering of ions, and Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the parent ion decomposition. The results of modeling demonstrate a general agreement between calculations and experiment. Calculated values of ion fragmentation efficiency are sensitive to initial vibrational excitation of ions, scattering of product ions from the collision cell, and distribution of initial ion velocities orthogonal to the axis of the collision cell. Three critical parameters of the model were adjusted to reproduce the experimental data on the dissociation of the benzylammonium ion: reaction enthalpy and initial internal and translational temperatures of the ions. Subsequent application of the model to decomposition of the t-butyl benzylammonium ion required adjustment of the internal ion temperature only. Energy distribution functions obtained in modeling depend on the average numbers of collisions between the ion and the atoms of the collider gas and, in general, have non-Boltzmann shapes.

Kinetics of the Gas-Phase Reaction of OH with Chlorobenzene

The kinetics of the reaction of hydroxyl radicals with chlorobenzene was studied experimentally using a pulsed laser photolysis/pulsed laser induced fluorescence technique over a wide range of temperatures, 298-670 K, and at pressures between 13.33 and 39.92 kPa. The bimolecular rate constants demonstrate different behavior at low and high temperatures. At room temperature, T = 298.8 +/- 1.5 K, the rate constant is equal to (6.02 +/- 0.34) x 10(-13) cm3 molecule(-1) s(-1); at high temperatures (474-670 K), the rate constant values are significantly lower and have a positive temperature dependence that can be described by an Arrhenius expression k1(T) = (1.01 +/- 0.35) x 10(-11) exp[(-2490 +/- 170 K)/T] cm3 molecule(-1) s(-1). This behavior is consistent with the low-temperature reaction being dominated by reversible addition and the high-temperature reaction representing abstraction and addition-elimination channels. The potential energy surface of the reaction was studied using quantum chemical methods, and a transition state theory model was developed for all reaction channels. The temperature dependences of the high-temperature rate constants obtained in calculations using the method of isodesmic reactions for transition states (IRTS) and the CBS-QB3 method are in very good agreement with experiment, with deviations smaller than the estimated experimental uncertainties. The G3//B3LYP-based calculated rate constants are in disagreement with the experimental values. The IRTS-based model was used to provide modified Arrhenius expressions for the temperature dependences of the rate constant for the abstraction and addition-elimination (Cl replacement) channels of the reaction.

Molecular dynamics simulation of C-C bond scission in polyethylene and linear alkanes: effects of the condensed phase.

The reaction of C-C bond scission in polyethylene chains of various lengths was studied using molecular dynamics under the conditions of vacuum and condensed phase (polymer melt). A method of assigning meaningful rate constant values to condensed-phase bond scission reactions based on a kinetic mechanism accounting for dissociation, reverse recombination, and diffusional separation of fragments was developed. The developed method accounts for such condensed-phase phenomena as cage effects and diffusion of the decay products away from the reaction site. The results of C-C scission simulations indicate that per-bond rate constants decrease by an order of magnitude as the density of the system increases from vacuum to the normal density of a polyethylene melt. Additional calculations were performed to study the dependence of the rate constant on the length of the polymer chain under the conditions of the condensed phase. The calculations demonstrate that the rate constant is independent of the degree of polymerization if polyethylene samples of different lengths are kept at the same pressure. However, if instead molecular systems of different polyethylene chain lengths decompose under the conditions of the same density, shorter chains result in higher pressures and lower rate constants. The observed effect is attributed to a higher degree of molecular crowding (lower fraction of free intermolecular space available for molecular motion) in the case of shorter molecules.

Kinetics of the self reaction of cyclohexyl radicals.

The kinetics of the self-reaction of cyclohexyl radicals was studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 303-520 K and at bath gas (helium with up to 5% of radical precursors) densities (3.00-12.0) × 10(16) molecules cm(-3). Cyclohexyl radicals were produced by a combination of the 193 nm photolysis of oxalyl chloride ((CClO)(2)) with the subsequent fast reaction of Cl atoms with cyclohexane, and their initial concentrations were determined from real-time profiles of HCl. The observed overall c-C(6)H(11) + c-C(6)H(11) rate constants demonstrate negative temperature dependence, which can be described by the following expressions: k(1) = 4.8 × 10(-12) exp(+542 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainty of 16% over the 303-520 K temperature range. The fraction of disproportionation equal to 41 ± 7% was determined at 305 K; analysis of earlier experimental determinations of the disproportionation-to-recombination branching ratio leads to recommending this room-temperature value for other temperatures. The corresponding temperature dependences of the recombination (1a, bicyclohexyl product) and the disproportionation (1b, cyclohexene and cyclohexane products) channels are k(1a) = 2.8 × 10(-12) exp(+542 K/T) and k(1b) = 2.0 × 10(-12) exp(+542 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainties of 20% and 29%, respectively.

Thermal Decomposition of HN3

The two-channel thermal decomposition of hydrogen azide, HN(3), was studied computationally. The reaction produces triplet or singlet NH and N(2). A model of the reaction was created on the basis of the theoretical study of the reaction potential-energy surface and microscopic reaction rates by Besora and Harvey (Besora, M.; Harvey, J. N. J. Chem. Phys. 2008, 129, 044303) and the experimental data on the energy-dependent rate constants reported by Foy et al. (Foy, B. R.; Casassa, M. P.; Stephenson, J. C.; King, D. S. J. Chem. Phys. 1990, 92, 2782) The properties of the model were adjusted to fit the calculated k(E) dependence to the experimental one. The experiments on thermal decomposition of HN(3) described in the literature were analyzed via kinetic modeling; the results of the analysis demonstrate that all but one of the existing studies were affected by contributions from secondary kinetics. The model of the reaction was then used in master-equation calculations of the pressure effects and the value of the critical energy transfer parameter, DeltaE(down), was adjusted based on agreement with the experimental k(T,P) data. Finally, the model was used to determine pressure- and temperature-dependent rate constants for both channels of reaction 1, which do not conform to the traditional formalism of low-pressure-limit and falloff description. Uncertainties of the model and their influence on the calculated thermal rate constant values were analyzed. Finally, parametrized expression for rate coefficients were provided for a wide range of temperatures and pressures.

Monte Carlo/RRKM/Classical Trajectories Modeling of Collisional Excitation and Dissociation of n-Butylbenzene Ion in Multipole Collision Cells of Tandem Mass Spectrometers

The two-channel reaction of collision-induced dissociation (CID) of the n-butylbenzene cation under the conditions of multipole collision cells of tandem mass spectrometers was studied computationally. The results were compared with the experimental data from earlier CID studies. The Monte Carlo method used includes simulation of the trajectories of flight of the parent (n-C(4)H(9)C(6)H(5)(+)) and the product (C(7)H(7)(+) and C(7)H(8)(+)) ions in the electromagnetic field of multipole ion guides and collision cells, classical trajectory modeling of collisional activation and scattering of ions, and RRKM modeling of the parent ion decomposition. Experimental information on the energy dependences of the rates of the n-butylbenzene cation dissociation via two channels was used to create an RRKM model of the reaction. Effects of uncertainties in the critical parameters of the model of the reaction and the collision cells on the results of calculations were evaluated and shown to be minor. The results of modeling demonstrate a good agreement with experiment, providing support for the applied computational method in general and the use of classical trajectory modeling of collisional activation of ions in particular.

Kinetics of the reaction between methyl radical and acetylene

The reaction CH 3 +C 2 H 2 → C 3 H 4 +H (reaction 1) has been studied using laser photolysis/photoionization mass spectrometry. Rate constants were determined in time-resolved experiments as a function of temperature (750–1000 K). Rate constants of reaction 1 are independent of the bath gas density within the experimental range [M]=[He]+[C 2 H 2 ]=(6-24)×10 16 molecules cm −3 , C 3 H 4 was defected as a primary product of reaction 1. Within the 800–1000 K range of temperatures and bath gas densities, the rate constants of reaction 1 can be described by the Arrhenius expression k 1 =(6.3±2.9)×10 −13 exp(−(5011±422)K/ T ) cm 3 molecule −1 s −1 . The experimental results of the current study are compared with computational predictions based on models existing in the literature. New RRKM models based on the experimental data are created and used to extrapolate the results of the current study to higher temperatures.