Molecular dynamics study of the reaction C<Subscript>3</Subscript> + H <Subscript>3</Subscript><Superscript>+</Superscript>

Both a quantum molecular dynamic method and high level ab initio calculations (MP2, CCSD(T)) have been used to investigate the mechanism of the C₃ + H₃⁺ reaction, which is part of the ion chemistry in interstellar clouds. Furthermore statistic initial orientations in collision simulations have been set up in order to determinate reaction cross-sections and rate coefficients of all occurring reaction channels. Our analysis shows that the revealed mechanism is strongly determined by dynamic effects.     

Energy spectra and angular distribution of projectile-like fragments in 84 MeV <Superscript>12</Superscript>C + <Superscript>169</Superscript>Tm

Kinetic-energy spectra and angular distribution of projectile-like fragments have been measured in the reaction of 84 MeV ¹²C on ¹⁶⁹Tm, using the surface barrier silicon-based ΔE-E telescopes. The fragments close to the projectile show typical spectra of quasi-elastic transfer reactions, which were found to be in agreement with the calculations based on the direct surface transfer reaction model. A significant cross-section of fast alpha-particles was found at forward angles, reminiscent of incomplete fusion reactions, which could be explained in terms of the direct surface transfer reaction model after taking into account the level density of continuum states in the heavy reaction product. The results have been explained in terms of the continuous evolution of the reaction mechanism as a function of the mass transfer. Received: 13 March 2002 / Accepted: 3 May 2002     

Self-propagating high-temperature synthesis and magnetic features of Fe-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> granulated films

The classical solid-phase reaction between Fe₂O₃ and Al layers in thin films is initiated. It is shown that, in the reaction products, Fe granulated films are formed in the Al₂O₃ nonconducting matrix. Analysis of the reaction equation demonstrates that the volume fraction of iron in the granulated films is less than the percolation threshold. This determines the magnetic properties of iron clusters in a superparamagnetic state. It is assumed that the nanocrystalline microstructure exists in thin films after solid-phase reactions proceeding under conditions of self-propagating high-temperature synthesis.     

Near-barrier neutron transfer in reactions <Superscript>6</Superscript>He + <Superscript>45</Superscript>Sc, <Superscript>64</Superscript>Zn,and <Superscript>197</Superscript>Au

Experimental cross sections of formation of isotopes ⁴⁶Sc (in reaction ⁶He + ⁴⁵Sc), ^196,198Au (in reaction ⁶He + ¹⁹⁷Au), and ⁶⁵Zn (in reaction ⁶He + ⁶⁴Zn) are analyzed. The time-dependent Schrödinger equation for the outer neutrons of ⁶He and ¹⁹⁷Au nuclei is solved numerically to calculate the probability of neutron transfer and transfer cross sections. In reaction ⁶He + ¹⁹⁷Au, the contribution of fusion and subsequent evaporation to experimental data can be neglected, while the corresponding contributions to reactions ⁶He + ⁴⁵Sc and ⁶He + ⁶⁴Zn are considerable. Fusion–evaporation is taken into account using the computational code of the NRV knowledge base. The results of calculations are in satisfactory agreement with the experimental data.     

Potential Energy Surface for Oxidation of Indenyl C<Subscript>9</Subscript>H<Subscript>7</Subscript>

Ab initio calculations were performed to obtain local energy extrema, including an effect of reagents, intermediates, and reaction products on the potential energy surface for the C₉H₇+O₂ reaction, playing a significant role in oxidation of polycyclic aromatic hydrocarbons at combustion conditions. The final products, determined as a result of the calculations are styrenyl radical C₈H₇+CO₂, ortho-vinyl phenyl radical C₈H₇+CO₂ and 1-H-inden-1-one C₉H₆O+OH, which is predicted to be the prevailing reaction product.     

A comparative study on the gas‐phase and liquid‐phase thermal isomerization reaction of α‐pinene

In this paper, a method of preparation of ocimene is investigated, which is obtained from isomerization reaction of α‐pinene. Two kinds of experimental apparatus are established for the investigation of the thermal isomerization reaction of α‐pinene. The behavior of thermal isomerization reaction of α‐pinene is respectively discussed in the gas phase and in the liquid phase. Under gas phase conditions, the conversion of α‐pinene is 80% and the selectivity of ocimene is 30%–33%. Under liquid phase conditions, the conversion of α‐pinene is 60% and the selectivity of ocimene is 50%–54%. According to the kinetic‐molecular theory of ideal gases, two kinds of reaction models are proposed to visualize the reaction process. In addition, the mechanism and kinetics of thermal isomerization reaction of α‐pinene are respectively discussed. The conclusion is that the gas phase reaction temperature is calculated to be 390–450 °C and the liquid phase reaction temperature is calculated to be 450–550 °C. From a bond dissociation energy point of view, results support the hypothesis that the reaction involves biradical intermediates. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermal reaction characterization of micron-sized aluminum powders in CO<Subscript>2</Subscript>

The thermal reaction characterization of micron-sized aluminium powder in carbon dioxide were investigated by simultaneous thermal analysis technology (TG/DSC), using a series of heating rates (5, 10, 15, 20°C/min). The results showed that the reaction process of micron-sized aluminium powder in carbon dioxide was divided into three stages: the initial slow oxidation stage, the sharp oxidation stage and the last oxidation stage. The thermal performance was increased with the increase in the heating rates. Evolution of the samples was determined by collecting the products at the initial, sharp, and last oxidation stages of the process. The reaction products morphology was examined using scanning electron microscopy (SEM). The corresponding chemical changes were analysed by X-ray diffraction spectrometry (XRD). The effects of heating rate on the thermal reaction characteristics were discussed. A new reaction mechanism of micron-sized Al particle in CO₂ with gradually increased temperature was proposed.     

Evaluated Integral Cross Sections of the <Superscript>3</Superscript>H(<Emphasis Type="Italic">t</Emphasis>,2<Emphasis Type="Italic">n</Emphasis>)<Superscript>4</Superscript>He Reaction in the Low-Energy Region Obtained with Regard to Electron Screening

procedure is considered for analyzing ³H(t,2n)⁴He reaction proceeding in a gas environment with regard to electron screening [1–4]. Results from such an analysis are presented. An electron screening potential of 121 eV is obtained. The magnitude of this potential is three times higher than the one given in [5]. Starting with a 100 eV energy of particle interaction the cross sections of ³H(t,2n)⁴He reaction are calculated using the above potential. The reaction rates are calculated using the evaluated cross sections in the lowenergy region. Enhancement factors for cross sections and reaction rates are defined.     

Near-barrier neutron transfer in reactions with <Superscript>3</Superscript>He nucleus

Experimental cross sections for the formation of ^196,198Au isotopes in the ³He + ¹⁹⁷Au reaction and ^44,46Sc isotopes in the ³He + ⁴⁵Sc reaction are analyzed. To calculate transfer probabilities and cross sections, the time-dependent Schrödinger equation is numerically solved for the external neutrons of the ³He, ⁴⁵Sc, and ¹⁹⁷Au nuclei. It is shown that the contribution from the fusion channel with subsequent evaporation is important for the ³He + ⁴⁵Sc reaction and negligibly small for the ³He + ¹⁹⁷Au reaction. Fusion–evaporation is taken into account using the NRV and PACE codes. Calculation results demonstrate overall satisfactory agreement with experimental data.     

Olefin metathesis reaction on GaN (0 0 0 1) surfaces

Proof-of-concept reactions were performed on GaN (0 0 0 1) surfaces to demonstrate surface termination with desired chemical groups using an olefin cross-metathesis reaction. To prepare the GaN surfaces for olefin metathesis, the surfaces were hydrogen terminated with hydrogen plasma, chlorine terminated with phosphorous pentachloride, and then terminated with an alkene group via a Grignard reaction. The olefin metathesis reaction then bound 7-bromo-1-heptene. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements following each step in the reaction scheme. The XPS data was used to qualitatively identify surface chemical species and to quantitatively determine molecular surface coverage. The bromine atom in 7-bromo-1-heptene served as a heteroatom for identification with XPS. The reaction scheme resulted in GaN substrates with a surface coverage of 0.10 monolayers and excellent stability towards oxidation when exposed to oxygen plasma.     

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

The Diels–Alder (DA) reaction is one of the most important reactions in organic chemistry. The controversy surrounding this reaction as to whether it follows a concerted or stepwise mechanism has existed for a long time. The reaction of 1,3‐butadiene and ethylene is the paradigmatic example of the DA reaction. We have reinvestigated the mechanism of this reaction using density functional theory. The theoretical study considered all types of possible pathways for the reaction of 1,3‐butadiene and ethylene using six functionals at different rungs of Jacob's ladder. Therefore, a complete picture is given for a thorough understanding of the iconic DA reaction, and a new stationary point during the reaction processes has been reported for the first time. The calculated results indicated that three functionals, ωB97X‐D, M06‐2X, and B2‐PLYP, of the fourth and fifth rungs of Jacob's ladder performed well in the investigation of the mechanism of this reaction and that the reliable basis set should be larger than 6‐311+G(2d,p). The cis‐1,3‐butadiene more easily reacted with ethylene compared with 1,3‐butadiene in the trans conformation. The concerted mechanism was found to be energetically favorable, whose energy barrier is around 10 kcal/mol lower than that of the stepwise mechanism. Two investigated solvents, toluene and CH₃CN, had little impact on this simple DA reaction. Copyright © 2014 John Wiley & Sons, Ltd.     

The effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer of 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone in methanol: A TD‐DFT study

Excited‐state intermolecular or intramolecular proton transfer (ESIPT) reaction has important potential applications in biological probes. In this paper, the effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer reaction of the 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone (MQ) dye in methanol solvent is investigated by the density functional theory and time‐dependent density functional theory approaches. Both the primary structure parameters and infrared vibrational spectra analysis of MQ and its benzo‐analogue 2‐methyl‐3‐hydroxy‐4(1H)‐benzo‐quinolone (MBQ) show that the intermolecular hydrogen bond O₁―H₂?O₃ significantly strengthens in the excited state, whereas another intermolecular hydrogen bond O₃―H₄?O₅ weakens slightly. Simulated electron absorption and fluorescence spectra are agreement with the experimental data. The noncovalent interaction analysis displays that the intermolecular hydrogen bonds of MQ are obviously stronger than that of MBQ. Additionally, the energy profile analysis via the proton transfer reaction pathway illustrates that the ESIPT reaction of MBQ is relatively harder than that of MQ. Therefore, the effect of benzo‐annelation of the MQ dye weakens the intermolecular hydrogen bond and relatively inhibits the proton transfer reaction.     

Study of <Superscript>179</Superscript>Hf<Superscript><Emphasis Type="Italic">m</Emphasis>2</Superscript> excitation

Isomeric ratios of ¹⁷⁹Hf ^m2,g yields in the (γ, n) reaction and the cross section for the ¹⁷⁹Hf ^m2 population in the (α, p) reaction are measured for the first time at the end-point energies of 15.1 and 17.5 MeV for bremsstrahlung photons and 26 MeV for alpha particles. The results are σ = (1.1 ± 0.11) × 10^?27 cm² for the ¹⁷⁶Lu(α, p)¹⁷⁹Hf ^m2 reaction and Y _m2/Y _g = (6.1 ± 0.3) × 10^?6 and (3.7 ± 0.2) × 10^?6 for the ¹⁸⁰Hf(γ, n)¹⁷⁹Hf ^m22 reaction at Е _ep =15.1 and 17.5 MeV, respectively. The experimental data on the relative ¹⁷⁹Hf ^m2 yield indicate a single-humped shape of the excitation function for the ¹⁸⁰Hf(γ, n)¹⁷⁹Hf ^m2 reaction. Simulation is performed using the TALYS-1.4 and EMPIRE-3.2 codes.     

<Emphasis Type="Italic">Ab initio</Emphasis> simulation of interface reactions as a foundation of understanding polymorphism

Chemical reactions at solid/liquid or solid/gas hybrid interfaces govern the morphogenesis of growing solid state phases. In order to understand the polymorphism of solids, the understanding of the mechanisms and kinetics of these reactions is of crucial importance, as is an insight into the morphology of said surfaces on an atomistic scale. Ab initio simulations are a valuable tool to obtain these data, especially in materials design, where many possible materials for an application may have to be examined. In such cases the fabrication of all these materials for examination and characterization can be extremely time consuming and expensive. We present methods to determine surface properties and reaction energetics from ab initio simulations and demonstrate their potential using three examples: reaction energetics for the adsorption of adhesive component molecules on alumina surfaces, the functionalization of a silica surface with a fluorocarbon layer and the investigation of the wetting behavior of the functionalized surface, and the calculation of reaction energetics for a proton transfer process in the bacterial reaction centre of photosynthesis, including quantum mechanical effects as well as solvent and continuum electrostatic influences from the surrounding medium.     

Homo‐Diels–Alder reaction of a very inactive diene,bicyclo[2,2,1]hepta‐2,5‐diene,with the most active dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione. Solvent,temperature, and high pressure influence on the reaction rate

Solvent, temperature, and high pressure influence on the rate constant of homo‐Diels–Alder cycloaddition reactions of the very active hetero‐dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione (1), with the very inactive unconjugated diene, bicyclo[2,2,1]hepta‐2,5‐diene (2), and of 1 with some substituted anthracenes have been studied. The rate constants change amounts to about seven orders of magnitude: from 3.95^.10^?3 for reaction (1+2) to 12200 L mol^?1 s^?1 for reaction of 1 with 9,10‐dimethylanthracene (4e) in toluene solution at 298 K. A comparison of the reactivity (ln k₂) and the heat of reactions (?_r‐nH) of maleic anhydride, tetracyanoethylene and of 1 with several dienes has been performed. The heat of reaction (1+2) is ?218 ± 2 kJ mol^?1, of 1 with 9,10‐dimethylanthracene ?117.8 ± 0.7 kJ mol^?1, and of 1 with 9,10‐dimethoxyanthracene ?91.6 ±0.2 kJ mol^?1. From these data, it follows that the exothermicity of reaction (1+2) is higher than that with 1,3‐butadiene. However, the heat of reaction of 9,10‐dimethylanthracene with 1 (?117.8 kJ mol^?1) is nearly the same as that found for the reaction with the structural C=C counterpart, N‐phenylmaleimide (?117.0 kJ mol^?1). Since the energy of the N=N bond is considerably lower (418 kJ/bond) than that of the C=C bond (611 kJ/bond), it was proposed that this difference in the bond energy can generate a lower barrier of activation in the Diels–Alder cycloaddition reaction with 1. Linear correlation (R = 0.94) of the solvent effect on the rate constants of reaction (1+2) and on the heat of solution of 1 has been observed. The ratio of the volume of activation (?V^≠) and the volume of reaction (?V_r‐n) of the homo‐Diels–Alder reaction (1+2) is considered as “normal”: ?V^≠/?V_r‐n = ?25.1/?30.95 = 0.81. Copyright © 2012 John Wiley & Sons, Ltd.     

Understanding halogen‐substituent assistance in H‐atom abstraction‐based reactions of CHCl•− with CH4 − nXn (X = H,F, Cl; n = 0–3)

The effect of halogen‐substituent on hydrogen abstraction mechanisms was studied by applying density functional theory functional calculations to the gas‐phase reactions between CHCl^?? and CH_{4 ? n}X_n (X = H, F, Cl; n = 0–3), and it is found that a heavier X substituent in the substrate results in a greater stabilization of corresponding complex, a lower activation energy, a faster H‐abstraction reaction, and greater exothermicity. However, CH₄– reaction is more reactive than CH₃F– reaction under the same condition because of dominant π‐donation from the electronegative F atom. We also explored the reactivity difference for the seven reactions in terms of factors derived from bond order, second‐order perturbative energy, and activation strain model analysis. The rate constants are evaluated over a wide temperature range of 298–1000 K by the conventional transition state theory. Copyright © 2014 John Wiley & Sons, Ltd.     

Mechanistic insights into N‐heterocyclic carbene (NHC)‐catalyzed N‐acylation of N‐sulfonylcarboxamides with aldehydes

In the current work, density functional theory calculations were performed to elucidate the detailed reaction mechanism for N‐heterocyclic carbene (NHC)‐catalyzed oxidative N‐acylation reaction of amides with aldehydes affording imide products. According to the calculated results, the reaction is initiated by the nucleophilic attack of NHC to aldehydes forming zwitterionic intermediate, which can then form Breslow intermediate via proton transfer. The Breslow intermediate can then be oxidized affording the oxidative intermediate, which can then go through 1,2‐addition with the deprotonated N‐sulfonylcarboxamides. Subsequently, elimination of NHC catalyst produces the final imide product. Our results reveal that the proton in N‐sulfonylcarboxamides is probably abstracted by base t‐BuOK or DPQH, and the deprotonation process is barrier‐less. Moreover, for the second step, ie, the formation of Breslow intermediate, direct proton transfer is impossible to occur. On the contrary, the results reveal that t‐BuOH can mediate the proton transfer in this step and significantly lower the energy barrier to 24.1 kcal/mol, which is also the highest energy barrier for the whole reaction. The work provides not only valuable clues for elucidating the detailed reaction mechanism for the invaluable NHC‐catalyzed oxidative reactions but also mechanistic insights for the rational design of novel NHC‐catalyzed oxidative reactions in the future.     

Reactions of molybdenum atoms with NO,O<Subscript>2</Subscript>, N<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript> molecules behind shock waves

Experimental results on the interaction of Mo atoms with various oxygen-containing molecules (NO, O₂, N₂O, and CO₂) at high temperatures (>1200 K) are presented, which are in close agreement with measurements at moderate and low temperatures. It is demonstrated that the height of the activation barrier is additionally increased for spin-forbidden reactions and that an increase in the heat of reaction causes an increase in the rate constant for a given type of reaction. For the reactions of Mo atoms with O₂ and N₂O, interpolated temperature dependences of the rate constants, based on the high-temperature measurements conducted in the present work and the published low-temperature data, are proposed.     

Use of N‐chloro‐N‐methyl‐p‐toluenesulfonamide in N‐chlorination reactions

Second‐order rate constants (k₂) were determined for the addition of ten nitrogenous organic compounds (benzylamine, 2,2,2‐trifluoethylamine chlorhidrate, methylamine chlorhidrate, glycine ethyl ester chlorhidrate, glycine, glycylglycine chlorhidrate, morpholine, pyperidine, pyperazine and dimethylamine) to the N‐chloro‐N‐methyl‐p‐toluenesulfonamide (NCNMPT) in the formation reaction of N‐chloramines in aqueous solution at 25 °C and ionic strength 0.5 M. The series of nucleophiles considered is structurally very varied and covers five pK_a units. The kinetic behaviour is similar for all compounds, being the elementary step the transfer of chlorine from the NCNMPT molecule to the nitrogen of the free amino group. These reactions were found first order in both reagents. The values of the rate constants indicate that the more basic amines produce N‐chloramines more readily. Rate constants for the nucleophilic attack are shown to correlate with literature data for some of these nitrogenous organic compounds in their reaction with N‐methyl‐N‐nitroso‐p‐toluenesulfonamide. Both reactions involve that the rate determining step is the attack of nitrogenous compounds upon electrophilic centre (Cl or else NO group). NCNMPT is a particularly interesting substrate, for which has not hitherto been published kinetic information, that allows us to assess the efficiency and the competitiveness of this reaction and compare it with other agents with a Cl⁺ atom. Copyright © 2013 John Wiley & Sons, Ltd.     

Astrophysical Rates for ¹²N(p,)¹³O Direct Capture Reaction

The proton capture on the unstable nuclei plays a very important role in nucleonsynthesis. The ¹²N(p,)¹³O reaction rates at the energies of astrophysical interest are estimated with the spectroscopic factor and asymptotic normalization coefficient methods. The present results show that the ¹²N(p,)¹³O reaction may play an important role in x-ray bursts.