Mechanisms of inelastic scattering of low-energy protons by C6H6, C60, C6F12, and C60F48 molecules

The mechanisms of inelastic scattering of low-energy protons with a kinetic energy of 2–7 eV by C₆H₆, C₆F₁₂, C₆₀, and C₆₀F₄₈ molecules are studied using the methods of quantum chemistry and nonempirical molecular dynamics. It is shown that, for the C₆H₆ + proton and C₆₀ + proton systems, starting from a distance of 6 Å from the carbon skeleton, the electronic charge transfer from the aromatic molecule to H⁺ occurs with a probability close to unity and transforms the H⁺ ion into a hydrogen atom and the neutral C₆H₆ and C₆₀ molecules into cation radicals. The mechanism of interaction of low-energy protons with C₆F₁₂ and C₆₀F₄₈ molecules has a substantially different character and can be considered qualitatively as the interaction between a neutral molecule and a point charge. The Coulomb perturbation of the system arising from the interaction of the noncompensated proton charge with the Mulliken charges of fluorine atoms results in an inversion of the energies of the electronic states localized, on the one hand, on the positively charged hydrogen ion and, on the other hand, on the C₆F₁₂ and C₆₀F₄₈ molecules. As a result, the neutral molecule + proton state becomes the ground state. In turn, this inversion makes the electronic charge transfer energetically unfavorable. Quantum-chemical and molecular-dynamics calculations on different levels of theory showed that, for fluorine derivatives of some aromatic structures (C₆F₁₂, C₆₀F₄₈), the barriers to proton penetration through carbon hexagons are two to four times lower than for the corresponding parent systems (C₆H₆, C₆₀). This effect is explained by the absence of active π-electrons in the case of fluorinated molecules.     

Computational studies of the halooxyhalocarbenes XOCX (X = F,Cl)

Ab initio calculations at the B3LYP, MP2, MP4 and CCSD(T) levels of theory were performed to predict the stability of the halooxyhalocarbenes, XOCX (X = F, Cl). The calculations indicate that the nonlinear FOCF molecule is stable with an energy 16 kJ mol^?1 below the energy of possible reacting fragments F₂ and CO. However, a nonlinear equilibrium structure for ClOCCl was located, but it was found to be about 192 kJ mol^?1 higher in energy than the energy of Cl₂ and CO. The charge distribution in these molecules was analysed using the atoms in molecules (AIM) method.     

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.     

Reactive scattering of a supersonic deuterium atom beam : D+Br2, CF3I,C2F5I,C3F7I

Reactive scattering of D atoms with Br₂, CF₃I, C₂F₅I and C₃F₇I molecules has been studied at an initial translational energy E = 5·3 kJ mol^-1 using a supersonic beam of D atoms seeded in He. Deuterium halide product is scattered in the backward direction with respect to the incident D atoms, with substantial energy disposed into product translation in all cases. The fraction of the total available energy which is disposed into product translation, is greater for the fluoralkyl iodides than for Br₂ and decreases slightly along the series CF₃I, C₂F₅I, C₃F₇I. These results demonstrate that the reaction of D atoms with fluoroalkyl iodides occurs only in collisions at small impact parameters with strong repulsion between the reaction products. The potential energy surfaces for the reactions of the fluoroalkyl iodides are similar to that for the D + Br₂ reaction but involve the release of a still greater proportion of the reaction exoergicity in the exit valley of the surface. Only a small fraction, if any, of the product repulsion is transferred to internal excitation of the product fluoroalkyl radical.     

Enthalpies of formation and isomerization of cis‐ and trans‐decalin,and their oxa‐analogs by G3(MP2)//B3LYP calculations

G3(MP2)//B3LYP calculations have been carried out on trans‐ and cis‐decalin, and their mono‐, di‐, tri‐, and tetraoxa‐analogs. The main purpose of the work was to obtain enthalpies of formation for these compounds, and to study the relative stabilities of the cis–trans and positional isomers of the various (poly)oxadecalins. Comparison of the computational enthalpies of formation with the respective experimental ones, known only for the decalins and 1,3,5,7‐tetraoxadecalins, shows that in both cases the computational values are more negative than the experimental ones, the deviations being ?5 to ?7 kJ mol^?1 for the decalins and ?12 to ?17 kJ mol^?1 for the 1,3,5,7‐tetraoxadecalins. The respective computational enthalpies of cis–trans isomerization, however, are in excellent to satisfactory agreement with the experimental data. The cis–trans enthalpy differences vary from +11.0 kJ mol^?1 for decalin to ?15.4 kJ mol^?1 for 1,4,5,8‐tetraoxadecalin. Low relative enthalpy values were also calculated for the cis isomers of 1,8‐dioxadecalin (?3.7 kJ mol^?1), 1,3,6‐trioxadecalin (?4.6 kJ mol^?1), 1,3,8‐trioxadecalin (?9.7 kJ mol^?1), 1,4,5‐ trioxadecalin (?5.6 kJ mol^?1), 1,3,5,8‐tetraoxadecalin (?7.3 kJ mol^?1), and 1,3,6,8‐tetraoxadecalin (?14.5 kJ mol^?1). Copyright © 2009 John Wiley & Sons, Ltd.     

Pressure-induced dimerization kinetics of fullerene C60

Dimerization kinetics was studied for fullerene C₆₀ by IR spectroscopy at a pressure of 1.5 GPa in the temperature range 373–473 K. The kinetic curves for the formation of a dimer (C₆₀)₂ were obtained using its analytical IR band at 796 cm^?1. Under the assumption that pressure-induced C₆₀ dimerization is a second-order irreversible reaction, the reaction rate constants were determined at different temperatures. The corresponding activation energy and preexponential factor were found to be 134±6 kJ/mol and (1.74± 0.24)×10¹⁴ s^?1, respectively. The specific features of the solid-phase C₆₀ dimerization in simple cubic and face-centered cubic fullerite phases are discussed.     

Diffusion of chromium and manganese in γ-TiAl

The γ-TiAl intermetallic compound with suitable alloying additions has shown considerable promise as a material for high-temperature applications. Diffusion studies in this alloy system are useful in assessment of their creep behaviour and structural stability in service conditions. Tracer diffusion coefficients of ⁵¹Cr and ⁵⁴Mn in a γ-TiAl intermetallic compound containing 54.1 at. % aluminium were determined in the temperature range from 1095 to 1470?K. The temperature dependence of both the diffusing species follows a linear Arrhenius behaviour and can be expressed as D _Cr?=?4.4?×?10^?3exp(?350?kJ?mol^?1/RT)?m^2?s^?1 and D _Mn?=?1.2?×?10^?3?×exp(?326?kJ?mol^?1/RT)?m^2?s^?1. The data are analysed on the basis of empirical correlations between the diffusion and melting parameters applicable for conventional mono-vacancy diffusion mechanism in metals. It is concluded that impurity diffusion in γ-TiAl occurs through the migration of thermal vacancies via nearest-neighbour or next-nearest neighbour jumps.     

Accurate ground-state potential energy surfaces of the C2H2–Kr and C2H2–Xe van der Waals complexes

Accurate ab initio intermolecular potential energy surfaces (IPES) have been obtained for the first time for the ground electronic state of the C₂H₂–Kr and C₂H₂–Xe van der Waals complexes. Extensive tests, including complete basis set and all-electron scalar relativistic results, support their calculation at the CCSD(T) level of theory, using small-core relativistic pseudopotentials for the rare-gas atoms and aug-cc-pVQZ basis sets extended with a set of 3s3p2d1f1g mid-bond functions. All results are corrected for the basis set superposition error. The importance of the scalar relativistic and rare-gas outer-core (n–1)d correlation effects is investigated. The calculated IPES, adjusted to analytical functions, are characterized by global minima corresponding to skew T-shaped geometries, in which the Jacobi vector positioning the rare-gas atom with respect to the center of mass of the C₂H₂ moiety corresponds to distances of 4.064 and 4.229?Å, and angles of 65.22° and 68.67° for C₂H₂–Kr and C₂H₂–Xe, respectively. The interaction energy of both complexes is estimated to be ?151.88 (1.817?kJ?mol^?1) and ?182.76?cm^?1 (2.186?kJ?mol^?1), respectively. The evolution of the topology of the IPES as a function of the rare-gas atom, from He to Xe, is also discussed.     

4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione in the ene reactions with cyclohexene, 1‐hexene and 2,3‐dimethyl‐2‐butene. The heat of reaction and the influence of temperature and pressure on the reaction rate

The values of the enthalpy (53.3; 51.3; 20.0 kJ mol^?1), entropy (?106; ?122; ?144 J mol^?1K^?1), and volume of activation (?29.1; ?31.0; ?cm³ mol^?1), the reaction volume (?25.0; ?26.6; ?cm³ mol^?1) and reaction enthalpy (?155.9; ?158.2; ?150.2 kJ mol^?1) have been obtained for the first time for the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione 1 , with cyclohexene 4 , 1‐hexene 6 , and with 2,3‐dimethyl‐2‐butene 8 , respectively. The ratio of the values of the activation volume to the reaction volume (?V^≠_corr/ΔV_{r ? n}) in the ene reactions under study, 1 + 4 → 5 and 1 + 6 → 7 , appeared to be the same, namely 1.16. The large negative values of the entropy and the volume of activation of studied reactions 1 + 4 → 5 and 1 + 6 → 7 better correspond to the cyclic structure of the activated complex at the stage determining the reaction rate. The equilibrium constants of these ene reactions can be estimated as exceeding 10¹⁸ L mol^?1, and these reactions can be considered irreversible. Copyright © 2014 John Wiley & Sons, Ltd.     

Anomeric effect plays a major role in the conformational isomerism of fluorinated pnictogen compounds

According to our theoretical studies, the anomeric effect, an stereoelectronic interaction between lone pair and a vicinal antibonding orbital, has shown to contribute decisively for the conformational isomerism of 1‐fluoro‐N,N‐dimethylmethanamine ( 1 ) and of its corresponding P, As and Sb analogues ( 2 – 4 ). C? X bonds in 2 – 4 are larger than in the parent compound 1 , thus providing a LP_X/C? F^* interaction progressively weaker on going from 1 to 4 . However, such hyperconjugation contributed by more than 1.3 kcal mol^?1 for the stabilization of anti conformer in 4 (θ_{LP? X? C? F} = 180°), increasing to 24.1 kcal mol^?1 in 1 . An isodesmic reaction model supported these findings. Copyright © 2008 John Wiley & Sons, Ltd.     

Kinetics of the gas‐phase homogeneous unimolecular elimination of selected ethyl esters of 2‐oxo‐carboxylic acids

The gas‐phase elimination kinetics of selected ethyl esters of 2‐oxo‐carboxylic acid have been studied over the temperature range of 270–415 °C and pressures of 37–114 Torr. The reactions are homogeneous, unimolecular, and follow a first‐order rate law in a seasoned static reaction vessel, with an added free radical suppressor toluene. The observed overall and partial rate coefficients are expressed by the following Arrhenius equations:

• Ethyl oxalyl chloride
• log k_overall (s^?1) = (13.22 ± 0.45) ? (179.4 ± 4.9) kJ mol^?1 (2.303 RT)^?1
• Ethyl piperidineglyoxylate
• log k_(CO2) (s^?1) = (12.00 ± 0.30) ? (191.2 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (12.60 ± 0.09) ? (210.7 ± 1.2) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (12.22 ± 0.26) ? (193.4 ± 3.4) kJ mol^?1 (2.303 RT)^?1
• Ethyl benzoyl formate
• log k_(CO2) (s^?1) = (12.89 ± 0.72) ? (203.8 ± 9.0) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (13.39 ± 0.31) ? (213.3 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (13.24 ± 0.60) ? (205.8 ± 7.6) kJ mol^?1 (2.303 RT)^?1

The kinetic and thermodynamic parameters of these reactions, together with those reported in the literature, lead to consider three different mechanistic pathways of elimination. Copyright © 2010 John Wiley & Sons, Ltd.     

A computational characterization of N2@C60

Recent observations of N₂@C₆₀ are supported computationally. The geometry is optimized at the B3LYP/3-21G and PW91/3-21G levels. The lowest-energy structure has the N₂ unit oriented towards a pair of parallel pentagons so that the complex exhibits D_5d symmetry. Single-point energy calculations are further carried out at the B3LYP/6-31G*, PW91/6-31G* and MP2?=?FC/6-31G* levels and corrected for the basis set superposition error (BSSE). The MP2?=?FC/6-31G* treatment with the BSSE correction gives a stabilization energy of -9.3?kcal?mol^?1, whereas DFT approaches mostly fail to produce a stabilization. The entropy term for the encapsulation is also evaluated and leads to a standard Gibbs energy change upon encapsulation at room temperature of -3.3?kcal?mol^?1. The computed structural and vibrational characteristics are also reported.     

Solution‐Based Phototransformation of C60 Nanorods: Towards Improved Electronic Devices

A modified liquid–liquid interface precipitation synthesis of C₆₀ nanorods, effects and opportunities following an in situ photochemical transformation in the liquid state, and an electronic characterization using a field‐effect transistor (FET) geometry are reported. The nanorods feature a high aspect ratio of ≈10³ and a notably small average diameter of 172 nm. Interestingly, it is found that a decreased nanorod diameter appears to correlate with distinctly improved electronic properties, and an average electron mobility of 0.30 cm² V^?1 s^?1, as measured in a FET geometry, is reported for as‐grown nanorods, with the peak value being an impressive 1.0 cm² V^?1 s^?1. A photoexposure using green laser light (λ = 532 nm) is demonstrated to result in the formation of a polymer‐C₆₀ shell encapsulating a monomer‐C₆₀ bulk; such photo‐transformed nanorods exhibit an electron mobility of 4.7 × 10^?3 cm² V^?1 s^?1. It is notable that the utilized FET geometry only probes the polymer‐C₆₀ nanorod surface shell, and that the monomer‐C₆₀ bulk is anticipated to exhibit a higher mobility. Importantly, photoexposed nanorods can be conveniently processed as a stabile dispersion in common hydrophobic solvents, and this finding is attributed to the insoluble character of the polymer‐C₆₀ shell.     

Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.     

Adsorption of helium on isolated C60 and C70 anions

Adsorption of helium on free, negatively charged fullerenes is studied in this work. Helium nanodroplets have been doped with fullerenes and ionised by electron attachment. For suitable experimental conditions, C^?₆₀ and C^?₇₀ anions are found to be complexed with a large number of helium atoms. Prominent anomalies in the ion abundances indicate the high stability of the commensurate 1×1 phase in which all hollow adsorption sites are occupied by one atom each. The adsorption energy for an additional helium atom is about 40% less than for atoms in the commensurate layer, similar to our previous findings for fullerene cations and in agreement with theoretical dissociation energies. Similarly, an anomaly in the adsorption energy occurs when 60 helium atoms are attached to C^?₆₀ or 65 to C^?₇₀. For C₆₀, the anomaly coincides with the one observed for cationic complexes but for C₇₀ it does not. Implications of these features are discussed in light of several theoretical studies of neutral and positively charged helium–fullerene complexes.     

Determination of the reaction rate constant and activation energy for pressure-induced 2+2 cycloaddition of the C60 fullerene

The kinetics of fullerene solid-phase dimerization proceeding through the 2+2 cycloaddition of C₆₀ at a pressure of 1.5 GPa is investigated by vibrational spectroscopy in the temperature range 373–473 K. Kinetic curves for the formation of (C₆₀)₂ dimers are obtained using the analytical band at 796 cm^?1 in the IR spectra of the (C₆₀)₂ dimer molecule. Under the assumption that the pressure-induced dimerization of C₆₀ is an irreversible second-order reaction, the reaction rate constants are determined at different temperatures. The activation energy and the preexponential factor are found to be equal to 134±6 kJ/mol and (1.74±0.24)×10¹⁴ s^?1, respectively.     

The energetics of naphthalene derivatives. II. The isomeric 1— and 2—naphthyl acetates

The isomeric 1- and 2-naphthyl acetates (acetoxynaphthalenes) are at the confluence of diverse concepts, techniques and classes of organic compounds. Summing the results of literature measurements of the enthalpy of formation of their solids and of our new sublimation enthalpies reported herein, we derive gas phase enthalpies of formation of ?209.9 ± 1.4 and ?213.3 ± 1.3 kJ mol^?1 respectively. This corresponds to 2-naphthyl acetate being more stable than its 1-isomer by 3.4 ± 1.9 kJ mol^?1. We also performed MP2(full)/6-31G(d) calculations on these species, resulting in enthalpies of formation of ?212.9 ± 3.9 and ?212.2 ± 3.9 kJ mol^?1 for 1- and 2-naphthyl acetate and a difference of ?0.7 kJ mol^?1 respectively in satisfactory agreement with the above experimental results.     

NQR, NMR and Crystal Structure Studies of [C(NH2)3]2HgX4 (X = Br, I)

The crystal structure of [C(NH₂)₃]₂HgBr₄ has been determined at room temperature: monoclinic, space group C2/c, with a = 10.035(2), b = 11.164(2), c = 13.358(3) Å, β = 111.67(3)°, and Z = 4. The crystal consists of planar [C(NH₂)₃]⁺ and distorted tetrahedral [HgBr₄]^2? ions. The Hg atom is located on a two-fold axis such that two sets of inequivalent Br atoms exist in an [HgBr₄]^2? ion. In accordance with the crystal structure, two ⁸¹Br NQR lines widely separated in frequency were observed between 77 and ca. 380 K. [C(NH₂)₃]₂HgI₄ yielded four ¹²⁷I NQR lines ascribable to m = ±1/2 ? ±3/2 transitions, indicating that its crystal structure is different from the bromide complex. The ¹H NMR T ₁ measurements showed a single minimum for the bromide but two minima for the iodide. The analyses based on the C₃ reorientations of the planar [C(NH₂)₃]⁺ ions gave the activation energies of 29.8 kJ mol^?1 for the bromide, and 30.2 and 40.0 kJ mol^?1 for the iodide.     

Investigation of the kinetics of OH∗ and CH∗ chemiluminescence in hydrocarbon oxidation behind reflected shock waves

The temporal variation of chemiluminescence emission from OH^?(A² Σ ⁺) and CH^?(A² Δ) in reacting Ar-diluted H₂/O₂/CH₄, C₂H₂/O₂ and C₂H₂/N₂O mixtures was studied in a shock tube for a wide temperature range at atmospheric pressures and various equivalence ratios. Time-resolved emission measurements were used to evaluate the relative importance of different reaction pathways. The main formation channel for OH^? in hydrocarbon combustion was studied with CH₄ as benchmark fuel. Three reaction pathways leading to CH^? were studied with C₂H₂ as fuel. Based on well-validated ground-state chemistry models from literature, sub-mechanisms for OH^? and CH^? were developed. For the main OH^?-forming reaction CH+O₂=OH^?+CO, a rate coefficient of k ₂=(8.0±2.6)×10¹⁰ cm³?mol^?1?s^?1 was determined. For CH^? formation, best agreement was achieved when incorporating reactions C₂+OH=CH^?+CO (k ₅=2.0×10¹⁴ cm³?mol^?1?s^?1) and C₂H+O=CH^?+CO (k ₆=3.6×10¹²exp(?10.9 kJ?mol^?1/RT) cm³?mol^?1?s^?1) and neglecting the C₂H+O₂=CH^?+CO₂ reaction.