Vibrational mode and collision energy effects on reaction of H2CO+ with C2D4

We report the effects of collision energy (Ecol) and five different H2CO+ vibrational modes on the reaction of H2CO+ with C2D4 over the center-of-mass E(col) range from 0.1 to 2.1 eV. Properties of various complexes and transition states were also examined computationally. Seven product channels are observed. Charge transfer (CT) has the largest cross section over the entire energy range, substantially exceeding the hard sphere cross section at high energies. Competing with CT are six channels involving transfer of one or more hydrogen atoms or protons and one involving formation of propanal, followed by hydrogen elimination. Despite the existence of multiple deep wells on the potential surface, all reactions go by direct mechanisms, except at the lowest collision energies, where short-lived complexes appear to be important. Statistical complex decay appears adequate to account for the product branching at low collision energies, however, even at the lowest energies, the vibrational effects are counter to statistical expectations. The pattern of Ecol and vibrational mode effects provide insight into factors that control reaction and interchannel competition.     

Vibrational mode and collision energy effects on reaction of H2CO+ with C2H2: charge state competition and the role of Franck-Condon factors in endoergic charge transfer

The effects of collision energy (E(col)) and six different H(2)CO(+) vibrational states on the title reaction have been studied over the center-of-mass E(col) range from 0.1 to 2.6 eV, including measurements of product ion recoil velocity distributions. Ab initio and Rice-Ramsperger-Kassel-Marcus calculations were used to examine the properties of complexes and transition states that might be important in mediating the reaction. Reaction is largely direct, despite the presence of multiple deep wells on the potential surface. Five product channels are observed, with a total reaction cross section at the collision limit. The competition among the major H(2) (+) transfer, hydrogen transfer, and proton transfer channels is strongly affected by E(col) and H(2)CO(+) vibrational excitation, providing insight into the factors that control competition and charge state "unmixing" during product separation. One of the more interesting results is that endoergic charge transfer appears to be controlled by Franck-Condon factors, implying that it occurs at large inter-reactant separations, contrary to the expectation that endoergic reactions should require intimate collisions to drive the necessary energy conversion.     

Reaction of formaldehyde cation with molecular hydrogen: effects of collision energy and H2CO+ vibrations

The effects on the title reaction of collision energy (E(col)) and five H(2)CO(+) vibrational modes have been studied over a center-of-mass E(col) range from 0.1 to 2.3 eV. Electronic structure and Rice-Ramsperger-Kassel-Marcus calculations were used to examine properties of various complexes and transition states that might be important. Only the hydrogen abstraction (HA) product channel is observed, and despite being exoergic, HA has an appearance energy of approximately 0.4 eV, consistent with a transition state found in the electronic structure calculations. A precursor complex-mediated mechanism might possibly be involved at very low E(col), but the dominant mechanism is direct over the entire E(col) range. The magnitude of the HA cross section is strongly, and mode specifically affected by H(2)CO(+) vibrational excitation, however, vibrational energy has no effect on the appearance energy.     

Product translational energy distributions and collision mechanics of the N + + CO reaction

Using a tandem mass spectrometer, kinetic energies of the five products CO ⁺, C ⁺, O ⁺, NO ⁺, CN ⁺ of reactive N ⁺ + CO collisions have been measured in the forward direction with respect to the N ⁺ beam. While CO ⁺ is observed mainly close to zero energy in the lab system, corresponding to formation by glancing collisions, there is evidence for formation of C ⁺ and O ⁺ via an intermediate NCO ⁺ complex at low impact energies. The productions of NO ⁺ and CN ⁺ show a very clear transition from complex to stripping reaction mechanism between 5 and 20 eV _lab. Highly excited NO ⁺ and CN ⁺ ions are formed up to impact energies of 60–70 eV _lab in the c.m. forward direction. In addition, these ions are formed in the backward c.m. direction up to very high collision energies (at least 200 eV _lab). This is explained by a collinear knock-on mechanism.     

Ab initio study of the potential energy surface for the OH+CO-->H+CO2 reaction

Potential energy surface for the reaction OH+CO-->H+CO2 has been calculated using the complete active space self-consistent-field and multireference configuration interaction methods with the correlation consistent triple-, quadruple-, and quintuple-zeta basis sets. A specific- reaction-parameters density functional theory has been suggested, in which the B3LYP functional is reoptimized to give the highly accurate potential energy surface with less computational efforts.     

Vibrational excitation of CO in the reaction: O + CS → CO + S

The relative rates at which O + CS → CO + S populates individual vibrational levels of CO have been determined (a) from infrared chemiluminescence experiments, and (b) by using a cw CO lawer to measure CO vibrational distributions produced when mixtures of CS₂ + O₂ are flash photolysed.     

CH4+CO2H2+CO

将廉价的碳源(CO2)转化为化石燃料可缓解由于温室气体引起的气候问题.CH4/CO2重整(CRM)是CO2转化利用的有效途径之一,要实现这个过程的关键是研制高效的光响应催化剂.本文采用WO3负载的第VIII族金属催化剂、引入光照能量来活化CO2,利用光热协同催化CRM.研究结果表明,光学材料WO3负载的第VIII族金属催化剂在可见光辅助下的催化活性是热驱动条件下的1.4～2.4倍,与等离子体金催化剂的活性增强率(1.7倍)相当.进一步以不同波段的可见光为光源,对WO3负载的第VIII族金属催化剂上催化活性提高的原因进行了研究.结果表明,活性增强率与WO3在可见光区域的吸光趋势并不吻合,说明并非WO3提高了其负载的第VIII族金属催化剂上CRM活性.除WO3外, WO3-x亦可作为光催化剂吸收可见光,因此,本文通过X射线光电子能谱、X射线衍射及紫外-可见分光光度法等进行表征.结果表明,在还原型CRM反应气氛下, WO3部分原位还原为WO3-x,并且活性增强率与WO3-x在可见光区域的吸光趋势相吻合,说明导致可见光辅助下活性增强的是WO3-x而不是WO3.热力学分析及原位电子顺磁共振波谱法结果表明, CO2的活化是CRM的速控步,该步骤吸热,在500 oC时不能自发进行.在可见光的辅助下, CO2可以被WO3-x通过Mars-vanKrevelen机理进行活化,提高速控步的反应速率,进而提高了催化活性.综上,本文为提高光催化活性提供了一条有效途径.     

Kinetic isotope effects for the H2 + C2H ↔ C2H2 + H reaction based on the ab initio calculations and a global potential energy surface

In the present paper, kinetic isotope effects of the title reaction are studied with canonical variational transition state theory on the modified Wang Bowman (MWB) potential energy surface (PES) (Chem Phys Lett 2005, 409, 249) and the ab initio calculations at the quadratic configuration interaction (QCISD (T, full))/aug‐cc‐pVTZ//QCISD (full)/cc‐pVTZ level. The calculated rate constants for the isotopic variants of this title reaction on the MWB PES have good agreement with those of the present ab initio calculations over the temperature range of 20–5000 K for the forward reactions and 800–5000 K for the reverse reactions, respectively. In particular, the forward rate constants for the title reaction and its isotopically substituted reactions have negative temperature dependences at about 40 K. Rate expressions are presented for all the studied reactions. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 289–298, 2010     

Nonadiabatic effects in the H+D2 reaction

The state-to-state dynamics of the H+D2 reaction is studied by the reactant-product decoupling method using the double many-body expansion potential energy surface. Two approaches are compared: one uses only the lowest adiabatic sheet while the other employs both coupled diabatic sheets. Rotational distributions for the reaction H+D2 (upsilon = 0, j = 0)-->HD(upsilon' = 3, j')+D are obtained at eight different collision energies between 1.49 and 1.85 eV; no significant difference are found between the two approaches. Initial state-selected total reaction probabilities and integral cross sections are also given for energies ranging from 0.25 up to 2.0 eV with extremely small differences being observed between the two sets of results, thus showing that the nonadiabatic effects in the title reaction are negligible at least for small energies below 2.0 eV.     

Mechanism and control of the F+H2 reaction at low and ultralow collision energies

This article uses theoretical methods to study the dependence on stereodynamical factors of the mechanism and reactivity of the F+H2 reaction at low and ultralow collision energies. The impact of polarization of the H2 reactant on total and state-to-state integral and differential cross sections is analyzed. This leads to detailed pictures of the reaction mechanism in the cold and ultracold regimes, accounting, in particular, for distinctions associated with the various product states and scattering angles. The extent to which selection of reactant polarization allows for external control of the reactivity and reaction mechanism is assessed. This reveals that even the simplest of reactant polarization schemes allows for fine, product state-selective control of differential and (for reactions involving more than a single, zero orbital angular momentum partial wave) integral cross sections.     

Vibrational population of H 2 + after electroionization of thermal H2

In an ion trap experiment we have determined the vibrational population of the lowest 9 vibrational levels of H ₂ ⁺ . We used photodissociation of the trapped molecules by 248 nm light from an excimer laser and the dependence of the photodissociation cross section from the vibrational state. Our results are in good agreement to calculations, which are based on the Franck-Condon principle, but include a variation of the internuclear distance in the transition matrix element.     

Exact quantum mechanical reaction probabilities for the collinear H + H2 reaction on a porter-karplus potential energy surface

Exact quantum mechanical calculation of the reaction probability for the collinear H + H₂ reaction on a Porter-Karplus potential energy surface are carried out by the finite-difference boundary value method at 6 energes in the threshold region and compared to close coupling, distorted wave, classical S matrix, transition state theory, and vibrational adiabatic calculations.     

Vibrational energy relaxation in liquid N2CO mixtures

The vibrational energy relaxation rates of the liquid nitrogenCO system have been measured by optically pumping the collision-induced fundamental vibrational absorption band of liquid N₂ with the output of an HBr TEA laser. A radiatively dominated value of 56 ± 10 s is found for the intrinsic nitrogen relaxation time. The CO contribution to the decay rate is explained on the basis of a simple kinetic model and found also to be radiatively dominated at low CO concentrations. The importance of radiative trapping and energy transport in evaluating the lifetimes is demonstrated.     

Vibrational mode analysis for the multichannel reaction of CH3Cl + OH

The recently presented ab initio calculations for the reaction system of CH₃Cl + OH (Dehestani and Shojaie, Int J Quantum Chem, in press) are applied to the vibrational mode analysis. Extending previous work, we use the vibrational mode analysis to elucidate the relationships of the reactants, the transition state, the intermediates (IM), and the products. The extensive investigation shows that the reaction mechanism is reliable. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Vibrational energy transfer and relaxation in O2 and H2O

Near-resonant vibrational energy exchange between oxygen and water molecules is an important process in the Earth's atmosphere, combustion chemistry, and the chemical oxygen iodine laser (COIL). The reactions in question are (1) O2(1) + O2(0) --> O2(0) + O2(0); (2) O2(1) + H2O(000) --> O2(0) + H2O(000); (3) O2(1) + H2O(000) <--> O2(0) + H2O(010); (4) H2O(010) + H2O(000) --> H2O(000) + H2O(000); and (5) H2O(010) + O2(0) --> H2O(000) + O2(0). Reanalysis of the data available in the chemical kinetics literature provides reliable values for rate coefficients for reactions 1 and 4 and strong evidence that reactions 2 and 5 are slow in comparison with reaction 3. Analytical solution of the chemical rate equations shows that previous attempts to measure the rate of reaction 3 are unreliable unless the water mole fraction is higher than 1%. Reanalysis of data from the only experiment satisfying this constraint provides a rate coefficient of (5.5 +/- 0.4) x 10(-13) cm3/s at room temperature, between the values favored by the atmospheric and laser modeling communities.     

·C2H3+O2→HC·O+H2CO 的密度泛函理论研究

应用密度泛函理论研究了@C2H3+O2→HC@O+H2CO的反应机理.在DFT(B3LYP/6-31G*)水平上对反应过程中所有反应物、中间体、过渡态和产物的几何构型进行优化,通过频率振动分析确认中间体和过渡态.计算IRC反应路径的能量,分析了中间体的异构化过程和各主要原子的自旋密度.     

Vibrational effects on the reaction of NO(2)(+) with C(2)H(2): effects of bending and bending angular momentum

NO(2)(+) in six different vibrational states was reacted with C(2)H(2) over the center-of-mass energy range from 0.03 to 3.3 eV. The reaction, forming NO(+)+C(2)H(2)O and NO+C(2)H(2)O(+), shows a bimodal dependence on collision energy (E(col)). At low E(col), the reaction is quite inefficient (<2%) despite this being a barrierless, exoergic reaction, and is strongly inhibited by E(col). For E(col)> approximately 0.5 eV, a second mechanism turns on, with an efficiency reaching approximately 27% for E(col)>3 eV. The two reaction channels have nearly identical dependence on E(col) and NO(2)(+) vibrational state, and identical recoil dynamics, leading to the conclusion that they represent a single reaction path throughout most of the collision. All modes of NO(2)(+) vibrational excitation enhance both channels at all E(col), however, the effects of bend (010) and bend overtone (02(0)0) excitation are particularly strong (factor of 4). In contrast, the asymmetric stretch (001), which intuition suggests should be coupled to the reaction coordinate, leads to only a factor of approximately 2 enhancement, as does the symmetric stretch (100). Perhaps the most surprising effect is that of the bending angular momentum, which strongly suppress reaction, even though both the energy and angular momentum involved are tiny compared to the collision energy and angular momentum. The results are interpreted in light of ab initio and Rice-Ramsperger-Kassel-Marcus calculations.     

The photoassociation and photodissociation in laser‐assisted collision reaction H + Cl+

The collision reaction H + Cl⁺ assisted by the ultra‐short laser pulse is investigated using the time‐dependent quantum wave packet method. The probability of dissociation depends on the yield ratio of association product HCl⁺. The greater the laser frequency is, the lower the vibrational level of HCl⁺ is. With lowering laser frequency, the probabilities of photoassociation and photodissociation increase, and the ratio of products H⁺ + Cl(²P⁰) to H(²S) + Cl⁺(¹D) also increases. The kinetic energy spectra of the dissociated fragments at low frequency are wider than those at high frequency. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Quantum wave packet study of the H+ + D2 reaction on diabatic potential energy surfaces

The exact three-dimensional nonadiabatic quantum dynamics calculations were carried out for the title reaction by a time-dependent wave packet approach based on a newly constructed diabatic potential energy surface (Kamisaka et al. J. Chem. Phys. 2002, 116, 654). Three processes including those of reactive charge transfer, nonreactive charge transfer, and reactive noncharge transfer were investigated to determine the initial state-resolved probabilities and reactive cross sections. The results show that a large number of resonances can be observed in the calculated probabilities due to the deep well on adiabatic ground surface and the dominant process is the reactive noncharge-transfer process. Some interesting dynamical features such as v-dependent and j-dependent behaviors of the probabilities are also revealed. In addition, a good agreement has been achieved in the comparison between the calculated quantum cross sections from the ground rovibrational initial state and the experimental measurement data.