Calculations on the competition between association and reaction for C3H(+) + H2

A potential energy surface has been calculated for the competing associative and reactive ion-molecule processes involving the reactants C3H(+) + H2. Our ab initio results show that the linear ion C3H+ and H2 can directly access the deep potential well of the propargyl ion H2CCCH+, which is calculated to lie 390 kJ mol-1 below the zero-point energy of the reactants. Isomerization between the propargyl ion and the lower energy, cyclic C3H3+ ion, calculated to lie 501 kJ mol-1 below the zero-point energy of reactants, can subsequently occur via two pathways. One of these pathways involves a transition state lying 22 kJ mol-1 below the energy of the reactants while the other, which occurs at much lower energies, involves two transition states and an intermediate. The dissociation of c-C3H3+ into c-C3H2(+) + H is calculated to occur directly, without any intermediate potential energy maximum, but the energy of the products lies 7.3 kJ mol-1 above the energy of the reactants. Using the minimum energy potential pathway and properties of the stationary point structures determined via ab initio methods, we have calculated both the association rate coefficient to produce C3H3+ as a function of density and the branching ratio between the propargyl and cyclic structures of the ion. Our results are in good agreement with some experimental results and in conflict with others. Specifically, we agree with the 1:1 branching ratio measured for the propargyl and cyclic isomers of C3H3+ at 80 and 300 K and we agree with the rate coefficient for radiative association measured at 80 K. We cannot reproduce reported measurements that the reactive channel (C3H2(+) + H) is the dominant channel at 80 K and at low gas densities, or that the association channel at high densities saturates at an effective rate coefficient well below the Langevin value -2x10(-11) cm3 s-1 at 300K and 1x10(-10) cm3 s-1 at 80K.     

Ab initio global potential-energy surface for H5(+) --> H3(+) + H2

An accurate global potential-energy surface (PES) is reported for H5(+) based on more than 100,000 CCSD(T)/aug-cc-pVTZ ab initio energies. This PES has full permutational symmetry with respect to interchange of H atoms and dissociates to H3(+) and H2. Ten known stationary points of H5(+) are characterized and compared to previous ab initio calculations. Quantum diffusion Monte Carlo calculations are performed on the PES to obtain the zero-point energy of H5(+) and the anharmonic dissociation energy (D0) of H5(+) --> H3(+) + H2. The rigorous zero-point state of H4D+ is also calculated and discussed within the context of a strictly classical approach to obtain the branching ratio of the reaction H4D+ --> H3(+) + HD and H2D+ + H2. Such an approach is taken using the PES and critiqued based on the properties of the quantum zero-point state. Finally, a simple procedure for adding the long range-interaction energy is described.     

Angle-energy distributions of Penning ions in crossed molecular beams. IV. He*(21 S,2 3S)+H2-->He+H2+ +e-

Relative doubly differential cross sections for the Penning ionization of H(2) by spin-state-selected metastable He (1s2s) are reported at center-of-mass collision energies E of 3.1 and 4.2 kcal/mol in a crossed supersonic beam experiment employing a rotatable mass spectrometer detector. The measurements are sufficiently dense in velocity space as to avoid having to functionalize the differential cross sections in order to transform the intensities into the c.m. The H(2) (+) product is scattered sharply forward, c.m. Deltatheta<10 degrees half-width at half-maximum, with respect to the incident direction of H(2) at both energies for both spin states. On the average the products have lost energy upon recoil, mean recoil energy E(')相似文献   

Theoretical study on the rate constants for the C2H5 + HBr --> C2H6 + Br reaction

The reaction C(2)H(5) + HBr --> C(2)H(6) + Br has been theoretically studied over the temperature range from 200 to 1400 K. The electronic structure information is calculated at the BHLYP/6-311+G(d,p) and QCISD/6-31+G(d) levels. With the aid of intrinsic reaction coordinate theory, the minimum energy paths (MEPs) are obtained at the both levels, and the energies along the MEP are further refined by performing the single-point calculations at the PMP4(SDTQ)/6-311+G(3df,2p)//BHLYP and QCISD(T)/6-311++G(2df,2pd)//QCISD levels. The calculated ICVT/SCT rate constants are in good agreement with available experimental values, and the calculate results further indicate that the C(2)H(5) + HBr reaction has negative temperature dependence at T < 850 K, but clearly shows positive temperature dependence at T > 850 K. The current work predicts that the kinetic isotope effect for the title reaction is inverse in the temperature range from 200 to 482 K, i.e., k(HBr)/k(DBr) < 1.     

Dynamics study of the reaction OH- + C2H2-->C2H- + H2O with crossed beams and density-functional theory calculations

The proton transfer reaction between OH- and C2H2, the sole reactive process observed over the collision energy range from 0.37 to 1.40 eV, has been studied using the crossed beam technique and density-functional theory (DFT) calculations. The center of mass flux distributions of the product C2H- ions at three different energies are highly asymmetric, characteristic of a direct process occurring on a time scale much less than a rotational period of any transient intermediate. The maxima in the flux distributions correspond to product velocities and directions close to those of the precursor acetylene reactants. The reaction quantitatively transforms the entire exothermicity into internal excitation of the products, consistent with an energy release motif in which the proton is transferred early, in a configuration in which the forming bond is extended. This picture is supported by DFT calculations showing that the first electrostatically bound intermediate on the reaction pathway is the productlike C2H- H2O species. Most of the incremental translational energy in the two higher collision energy experiments appears in product translational energy, and provides an example of induced repulsive energy release characteristic of the heavy+light-heavy mass combination.     

Theoretical study of HCN(+) + C2H2 reaction

A detailed theoretical investigation for the ion-molecule reaction of HCN (+) with C 2H 2 is performed at the B3LYP/6-311G(d,p) and CCSD(T)/6-311++G(3df,2pd) (single-point) levels. Possible energetically allowed reaction pathways leading to various low-lying dissociation products are probed. It is shown that eight dissociation products P 1 (H 2C 3N (+)+H), P 2 (CN+C 2H 3 (+)), P 3 (HC 3N (+)+H 2), P 4 (HCCCNH (+)+H), P 5 (H 2NCCC (+)+H), P 6 (HCNCCH (+)+H), P 7 (C 2H 2 (+)+HCN), and P 8 (C 2H 2 (+)+HNC) are both thermodynamically and kinetically accessible. Among the eight dissociation products, P 1 is the most abundant product. P 7 and P 3 are the second and third feasible products but much less competitive than P 1 , followed by the almost negligible product P 2 . Other products, P 4 (HCCCNH (+)+H), P 5 (HCNCCH (+)+H), P 6 (H 2NCCC (+)+H), and P 8 (C 2H 2 (+)+HNC) may become feasible at high temperatures. Because the intermediates and transition states involved in the reaction HCN (+) + C 2H 2 are all lower than the reactant in energy, the title reaction is expected to be rapid, as is consistent with the measured large rate constant at room temperature. The present calculation results may provide a useful guide for understanding the mechanism of HCN (+) toward other pi-bonded molecules.     

Prediction of product branching ratios in the C(3P)+C2H2-->l-C3H+H/c-C3H+H/C3+H2 reaction using ab initio coupled clusters calculations extrapolated to the complete basis set combined with Rice-Ramsperger-Kassel-Marcus and radiationless transition theories

Ab initio CCSD(T) calculations of intermediates and transition states on the singlet and triplet C3H2 potential energy surfaces extrapolated to the complete basis set limit are combined with statistical computations of energy-dependent rate constants of the C(3P)+C2H2 reaction under crossed molecular beam conditions. Rice-Ramsperger-Kassel-Marcus theory is applied for isomerization and dissociation steps within the same multiplicity and radiationless transition and nonadiabatic transition state theories are used for singlet-triplet intersystem crossing rates. The calculated rate constants are utilized to predict product branching ratios. The results demonstrate that, in qualitative agreement with available experimental data, c-C3H+H and C3+H2 are the most probable products at low collision energies, whereas l-C3H+H becomes dominant at higher Ec above approximately 25 kJ/mol.     

Quantum dynamics study on the product branching for the C(3P) + C2H2 reaction: cyclic-C3H versus linear-C3H

Reduced-dimensionality quantum reactive scattering calculations for the C(3P) + C2H2 reaction have been carried out in order to understand the product branching dynamics of cyclic-C3H + H and linear-C3H + H. Our model treats only two degrees of freedom but can explicitly describe both of the C3H isomer product channels. The lowest triplet potential energy surface has been obtained by the hybrid density-functional method at the B3LYP/6-31G(d,p) level of theory. The calculated reaction probabilities were found to be dominated by resonance consistent with the complex-formation potential, and the results show that cyclic-C3H is preferentially formed via the cyclic-C3H2 intermediate produced by insertion of C(3P) into the CC bond. We have found that the isomerization from the cyclic-C3H2 to linear-C3H2 intermediate is suppressed by a barrier separating potential wells corresponding to these two intermediates. It has also been found that the energy dependence of the calculated total reaction cross section is in good agreement with the result of crossed molecular beam experiments.     

Time-dependent quantum mechanical wave packet study of the He+H(2) (+)(v,j)-->HeH(+)+H reaction

A detailed three-dimensional time-dependent quantum dynamical study of the He+H(2) (+)(v=0-3,j=0)-->HeH(+)+H reaction is reported for different vibrational v states of H(2) (+) in its ground rotational (j=0) state over a range of translational E(trans) energies on an accurate ab initio potential energy surface published by Palmieri et al. Plots of reaction probability as a function of total energy E reveal a large number of oscillations indicating the presence of a number of reactive scattering resonances. When averaged over total angular momentum J, some of the oscillations survive, indicating that they may be amenable to experimental observation. A comparison of our present results with our earlier results on the McLaughlin-Thompson-Joseph-Sathyamurthy surface and the experimental results from different research groups reveal a good deal of agreement as well as some discrepancies between theory and experiment at the level of state-selected gas phase dynamics.     

Calculations on the rate of the ion-molecule reaction between NH3+ and H2

The rate coefficient for the ion-molecule reaction NH3(+) + H2 --> NH4(+) + H has been calculated as a function of temperature with the use of the statistical phase space approach. The potential surface and reaction complex and transition state parameters used in the calculation have been taken from ab initio quantum chemical calculations. The calculated rate coefficient has been found to mimic the unusual temperature dependence measured in the laboratory, in which the rate coefficient decreases with decreasing temperature until 50-100 K and then increases at still lower temperatures. Quantitative agreement between experimental and theoretical rate coefficients is satisfactory given the uncertainties in the ab initio results and in the dynamics calculations. The rate coefficient for the unusual three-body process NH3(+) + H2 + He --> NH4(+) + H + He has also been calculated as a function of temperature and the result found to agree well with a previous laboratory determination.     

Dynamics of the D+ + H2 and H+ + D2 reactions: a detailed comparison between theory and experiment

An extensive set of experimental measurements on the dynamics of the H(+) + D(2) and D(+) + H(2) ion-molecule reactions is compared with the results of quantum mechanical (QM), quasiclassical trajectory (QCT), and statistical quasiclassical trajectory (SQCT) calculations. The dynamical observables considered include specific rate coefficients as a function of the translational energy, E(T), thermal rate coefficients in the 100-500 K temperature range. In addition, kinetic energy spectra (KES) of the D(+) ions reactively scattered in H(+) + D(2) collisions are also presented for translational energies between 0.4 eV and 2.0 eV. For the two reactions, the best global agreement between experiment and theory over the whole energy range corresponds to the QCT calculations using a gaussian binning (GB) procedure, which gives more weight to trajectories whose product vibrational action is closer to the actual integer QM values. The QM calculations also perform well, although somewhat worse over the more limited range of translational energies where they are available (E(T) < 0.6 eV and E(T) < 0.2 eV for the H(+) + D(2) and D(+) + H(2) reactions, respectively). The worst agreement is obtained with the SQCT method, which is only adequate for low translational energies. The comparison between theory and experiment also suggests that the most reliable rate coefficient measurements are those obtained with the merged beams technique. It is worth noting that none of the theoretical approaches can account satisfactorily for the experimental specific rate coefficients of H(+) + D(2) for E(T)≤ 0.2 eV although there is a considerable scatter in the existing measurements. On the whole, the best agreement with the experimental laboratory KES is obtained with the simulations carried out using the state resolved differential cross sections (DCSs) calculated with the QCT-GB method, which seems to account for most of the observed features. In contrast, the simulations with the SQCT data predict kinetic energy spectra (KES) considerably cooler than those experimentally determined.     

Computational study on the kinetics and mechanism for the unimolecular decomposition of C6H5NO2 and the related C6H5 + NO2 and C6H5O + NO reactions

The kinetics and mechanisms for the unimolecular dissociation of nitrobenzene and related association reactions C(6)H(5) + NO(2) and C(6)H(5)O + NO have been studied computationally at the G2M(RCC, MP2) level of theory in conjunction with rate constant prediction with multichannel RRKM calculations. Formation of C(6)H(5) + NO(2) was found to be dominant above 850 K with its branching ratio > 0.78, whereas the formation of C(6)H(5)O + NO via the C(6)H(5)ONO intermediate was found to be competitive at lower temperatures, with its branching ratio increasing from 0.22 at 850 K to 0.97 at 500 K. The third energetically accessible channel producing C(6)H(4) + HONO was found to be uncompetitive throughout the temperature range investigated, 500-2000 K. The predicted rate constants for C(6)H(5)NO(2) --> C(6)H(5) + NO(2) and C(6)H(5)O + NO --> C(6)H(5)ONO under varying experimental conditions were found to be in good agreement with all existing experimental data. For C(6)H(5) + NO(2), the combination processes producing C(6)H(5)ONO and C(6)H(5)NO(2) are dominant at low temperature and high pressure, while the disproportionation process giving C(6)H(5)O + NO via C(6)H(5)ONO becomes competitive at low pressure and dominant at temperatures above 1000 K.     

Nonadiabatic time-dependent wave packet study of the D+ + H2 reaction system

A theoretical investigation on the nonadiabatic processes of the D(+) + H(2) reaction system has been carried out by means of exact three-dimensional nonadiabatic time-dependent wave packet calculations with an extended split operator scheme (XSOS). The diabatic potential energy surface newly constructed by Kamisaka et al. (J. Chem. Phys. 2002, 116, 654) was employed in the calculations. This study provided quantum cross sections for three competing channels of the reactive charge transfer, the nonreactive charge transfer, and the reactive noncharge transfer, which contrasted markedly to many previous quantum theoretical reports on the (DH(2))(+) system restricted to the total angular momentum J = 0. These quantum theoretical cross sections derived from the ground rovibrational state of H(2) show wiggling structures and an increasing trend for both the reactive charge transfer and the nonreactive charge transfer but a decreasing trend for the reactive noncharge transfer throughout the investigated collision energy range 1.7-2.5 eV. The results also show that the channel of the reactive noncharge transfer with the largest cross section is the dominant one. A further investigation of the v-dependent behavior of the probabilities for the three channels revealed an interesting dominant trend for the reactive charge transfer and the nonreactive charge transfer at vibrational excitation v = 4 of H(2). In addition, the comparison between the centrifugal sudden (CS) and exact calculations showed the importance of the Coriolis coupling for the reactive system. The computed quantum cross sections are also compared with the experimental measurement results.     

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.     

Quantum mechanical calculations for the H2O + hnu --> O(1D) + H2 photodissociation process

Quantum mechanical wavepacket calculations for the photodissociation of water in the second absorption band are presented. Using O + H2 Jacobi coordinates, partial cross sections for the O(1D) + H2 channel are calculated for different initial rotational states. Conical intersection and Renner-Teller effects are included. The branching ratios for the four accessible dissociation channels at 121.6 nm are in good agreement with experiment (J. Chem. Phys. 1982, 77, 2432). The calculations predict significant rotational and vibrational excitation of the H2 fragments. Photodissociation of ortho and para water produces predominantly, but not exclusively, ortho and para H2 fragments, respectively.     

Dissociation of benzene dication [C6H6]2+: exploring the potential energy surface

The singlet potential energy surface for the dissociation of benzene dication has been explored, and its three major dissociation channels have been studied: C6H6(2+) --> C3H3(+) + C3H3(+), C4H3(+) + C2H3(+), and C5H3(+) + CH3(+). The calculated energetics suggest that the products will be formed with considerable translational energy because of the Coulomb repulsion between the charged fragments. The calculated energy release in the three channels shows a qualitative agreement with the experimentally observed kinetic energy release. The formation of certain intermediates is found to be common to the three dissociation channels.     

High-temperature rate constants for CH3OH + Kr --> products, OH + CH3OH --> products, OH + (CH3)(2)CO --> CH2COCH3 + H2O, and OH + CH3 --> CH) + H2O

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm (corresponding to a total path length of approximately 4.9 m) has been used to study the dissociation of methanol between 1591 and 2865 K. Rate constants for two product channels [CH3OH + Kr --> CH3 + OH + Kr (1) and CH3OH + Kr --> 1CH2 + H2O + Kr (2)] were determined. During the course of the study, it was necessary to determine several other rate constants that contributed to the profile fits. These include OH + CH3OH --> products, OH + (CH3)2CO --> CH2COCH3 + H2O, and OH + CH3 --> 1,3CH2 + H2O. The derived expressions, in units of cm(3) molecule(-1) s(-1), are k(1) = 9.33 x 10(-9) exp(-30857 K/T) for 1591-2287 K, k(2) = 3.27 x 10(-10) exp(-25946 K/T) for 1734-2287 K, kOH+CH3OH = 2.96 x 10-16T1.4434 exp(-57 K/T) for 210-1710 K, k(OH+(CH3)(2)CO) = (7.3 +/- 0.7) x 10(-12) for 1178-1299 K and k(OH+CH3) = (1.3 +/- 0.2) x 10(-11) for 1000-1200 K. With these values along with other well-established rate constants, a mechanism was used to obtain profile fits that agreed with experiment to within <+/-10%. The values obtained for reactions 1 and 2 are compared with earlier determinations and also with new theoretical calculations that are presented in the preceding article in this issue. These new calculations are in good agreement with the present data for both (1) and (2) and also for OH + CH3 --> products.     

The effect of the torsional and stretching vibrations of C2H6 on the H + C2H6 --> H2 + C2H5 reaction

We present a three-dimensional quantum scattering model to treat reactions of the type H + C2H6 --> H2 + C2H5. The model allows the torsional and the stretching degrees of freedom to be treated explicitly. Zero-point energies of the remaining modes are taken into account in electronic structure calculations. An analytical potential-energy surface was developed from a minimal number of ab initio geometry evaluations using the CCSD(T,full)/cc-pVTZ//MP2(full)/cc-pVTZ level of theory. The reaction is endothermic by 1.5 kcal mol(-1) and exhibits a vibrationally adiabatic barrier of 12.0 kcal mol(-1). The results show that the torsional mode influences reactivity when coupled with the vibrational C-H stretching mode. We also found that ethyl radical products are formed internally excited in the torsional mode.     

Structural isomers of C2N+: a selected-ion flow tube study

Reactivities of the structural isomers CCN+ and CNC+ were examined in a selected-ion flow tube at 300 +/- 5 K. The less reactive CNC+ isomer was identified as the product of the reactions of C(+) + HCN and C(+) + C2N2; in these reactions only CNC+ can be produced because of energy constraints. Rate coefficients and branching ratios are reported for the reactions of each isomer with H2, CH4, NH3, H2O, C2H2, HCN, N2, O2, N2O, and CO2. Ab initio calculations are presented for CCN+ and CNC+; a saddle point for the reaction CCN+ --> CNC+ is calculated to be 195 kJ mol-1 above the CNC+. The results provide evidence that the more reactive CCN+ isomer is unlikely to be present in measurable densities in interstellar clouds.