Analysis of the long range potentials of the X 1Σ+ and a 3Σ+ states of NaK

The difference in energy between the singlet and triplet states of NaK dissociating to Na(3s) and K(4s) is found from experimental data and from pseudopotential calculations. The contributions of various one- and two-electron integrals are evaluated, illustrating the present ambiguity over the exchange integral and the exchange interaction terms.     

Ab initio study of the reaction path of the reaction HNCO+CN

HNCO is a convenient photolytic source of NCO and NH radicals for laboratory kinetics studies of elementary reaction[1] and plays an important role in the combustion and atmosphere chemistry. It can re- move deleterious compounds rapidly from exhausted ga…     

Quasi-classical trajectory study of the dynamics of the Cl + CH4→ HCl + CH3 reaction

We present an on-the-fly classical trajectory study of the Cl + CH(4)→ HCl + CH(3) reaction using a specific reaction parameter (SRP) AM1 Hamiltonian that was previously optimized for the Cl + ethane reaction [S. J. Greaves et al., J. Phys Chem A, 2008, 112, 9387]. The SRP-AM1 Hamiltonian is shown to be a good model for the potential energy surface of the title reaction. Calculated differential cross sections, obtained from trajectories propagated with the SRP-AM1 Hamiltonian compare favourably with experimental results for this system. Analysis of the vibrational modes of the methyl radical shows different scattering distributions for ground and vibrationally excited products.     

The influence of the temperature on the liquid–liquid equlibria of the mixture limonene + ethanol + H2O

In this work, experimental liquid–liquid equilibria (LLE) of the limonene + ethanol + water system are presented. The LLE of this system has been measured at 293.15, 303.15, 313.15 and 323.15 K. The equilibrium data presented are correlated using NRTL and UNIQUAC equations. Finally, the reliability of these models is tested by comparison with experimental results.     

Adiabatic calculations of the 2Σ+g excited states of He+2

The first six ²Σ⁺_g adiabatic potential energy curves of He⁺₂ are calculated with the MRD CI method employing configuration selection (T = 10 μ hartree) and perturbative energy corrections and using two basis sets differing in the number of diffuse functions. The non-adiabatic matrix elements at the numerous avoided crossings are also calculated and approximate diabatic curves are constructed. Various aspects of the results are discussed.     

Determination of the Rate Constants of the Reactions Cr + O2 + M → CrO2 + M and Cr + O2 → CrO + O

Kinetics and Catalysis - The rate constants of the interactions of chromium atoms with molecular oxygen through recombination Cr + O2 + M → CrO2 + M (I) and exchange Cr + O2 → CrO + O...     

Affinity of Cu+ for the copper-binding domain of the amyloid-β peptide of Alzheimer's disease

The role of metal ions in Alzheimer's disease etiology is unresolved. For the redox-active metal ions iron and copper, the formation of reactive oxygen species by metal amyloid complexes has been proposed to contribute to Alzheimer's disease neurodegeneration. For copper, reactive oxygen species are generated by copper redox cycling between its 1+ and 2+ oxidation states. Thus, the AβCu(I) complex is potentially a critical reactant associated with Alzheimer's disease etiology. Through competitive chelation, we have measured the affinity of the soluble copper-binding domain of the amyloid-β peptide for Cu(I). The dissociation constants are in the femtomolar range for both wild-type and histidine-to-alanine mutants. These results indicate that Cu(I) binds more tightly to monomeric amyloid-β than Cu(II) does, which leads us to propose that Cu(I) is a relevant in vivo oxidation state.     

Quantum dynamics of the S+OH→SO+H reaction

First accurate quantum mechanical scattering calculations have been carried out for the S((3)P)+OH(X?(2)Π)→SO(X?(3)Σ(-))+H((2)S) reaction using a recent ab initio potential energy surface for the ground electronic state, X?(2)A("), of HSO. Total and state-to-state reaction probabilities for a total angular momentum J=0 have been determined for collision energies up to 0.5 eV. A rate constant has been calculated by means of the J-shifting approach in the 10-400 K temperature range. Vibrational and rotational product distributions show no specific behavior and are consistent with a mixture of direct and indirect reaction mechanisms.     

Quasi-classical trajectory approach to the stereo-dynamics of the reaction F+HO→HF+O

Quasi-classical trajectory (QCT) calculations are employed for the reaction F + HO(0,0)→HF + O based on the adiabatic potential energy surface (PES) of the ground 3A″triplet state. The average rotational alignment factor P2(j′·k) as a function of collision energy and the four polarization dependent generalized differential cross sections have been calculated in the center-of-mass (CM) frame, separately. The distribution P(θr) of the angle between k and j′, the distribution P(θr) of dihedral angle denoting k-k′-j′ correlation, and the angular distribution P(θr, Φr) of product rotational vectors in the form of polar plots are calculated as well. The effect of Heavy-Light-Heavy (HLH) mass combination and atom F's relatively strong absorbability to charges on the alignment and the orientation of product molecule HF rotational angular momentum vectors j′ is revealed.     

Mean potential statistical theory of the H+ + D2 → HD + D+ reaction

The reactive collision process H(+) + D(2)(ν = 0, j = 0) → HD + D(+) is theoretically analyzed for collision energies ranging from threshold up to 1.3 eV. It is assumed that the reaction takes place via formation of a collision complex. In calculations, a statistical theory is used, based on a mean isotropic potential deduced from a full potential energy surface. Calculated integral cross sections, opacity functions, and rotational distributions of the HD products are compared with recent statistical and quantum mechanical calculations performed using a full potential energy surface. Satisfactory agreement between the results obtained using the two statistical methods is found, both of which however overestimate the existing quantum mechanical predictions. The effects due to the presence of identical particles are also discussed.     

Nodal surfaces of the wave functions of the hydrogen molecule in the triplet state 3Σu +

For molecular hydrogen in the triplet state ³Σ_u ⁺, the nodal surfaces of the wave function corresponding to the minimum basis set of Slater orbitals in the Hartree—Fock approximation and those of the wave function used in calculations by the diffusion quantum Monte Carlo method were plotted and analyzed. Taking account of the condition for antisymmetrical wave function of the triplet state ³ S of He atom, the Hartree-Fock approximation in the minimum basis set of one-electron orbitals is inappropriate for a priori determination of the nodal surfaces of many-electron wave functions (MWF). An MWF quantum chemical method developed by the authors is outlined. The alternative nodal surfaces for H₂ (³Σ_u ⁺) a priori specified in this method are presented.     

Study of the ν2 + ν3 infrared band of ONCl

Two hundred and sixty A type rovibrational lines of the ν₂ + ν₃ vibrational band of ¹⁶O¹⁴N³⁵Cl, around 925 cm⁻¹, have been assigned; a least-squares calculation with a r.m.s. deviation of 0.0006 cm⁻¹ has made it possible to measure several constants of the (011) vibrational level.     

Point group symmetries of the molecular orbitals of HD+ beyond the Born–Oppenheimer approximation

The isotope shifts of the electronic states of HD⁺ are calculated, for the first time, within an adiabatic MO-LCAO theory. A typical heteronuclear C_∞v correlation diagram comes out, obeying conservation of point group orbital symmetries and noncrossing rule.     

Fitting of the voltage–Li+ insertion curve of LiFePO4

Fitting of the voltage vs. insertion curves of the LiFePO₄ electrode was based on theoretical expressions describing the Li⁺ diffusive process in a solid medium. The noninteracting gas model for the chemical potential of ions distributed in a solid matrix was taken into account, and the diffusion coefficient and the energy activation for the diffusion process were accordingly calculated. The polarization curves at various discharge stages were theoretically obtained, and a good agreement was found with the experimental data at all discharge rates. A mathematical relation describing the trend of the diffusion resistance vs. insertion degree was also developed.     

Acceleration of the reaction OH + CO → H + CO2 by vibrational excitation of OH

The collision complex formed from a vibrationally excited reactant undergoes redissociation to the reactant, intramolecular vibrational relaxation (randomization of vibrational energy), or chemical reaction to the products. If attractive interaction between the reactants is large, efficient vibrational relaxation in the complex prevents redissociation to the reactants with the initial vibrational energy, and the complex decomposes to the reactants with low vibrational energy or converts to the products. In this paper, we have studied the branching ratios between the intramolecular vibrational relaxation and chemical reaction of an adduct HO(v)-CO formed from OH(X(2)Π(i)) in different vibrational levels v = 0-4 and CO. OH(v = 0-4) generated in a gaseous mixture of O(3)/H(2)/CO/He irradiated at 266 nm was detected with laser-induced fluorescence (LIF) via the A(2)Σ(+)-X(2)Π(i) transition, and H atoms were probed by the two-photon excited LIF technique. From the kinetic analysis of the time-resolved LIF intensities of OH(v) and H, we have found that the intramolecular vibrational relaxation is mainly governed by a single quantum change, HO(v)-CO → HO(v-1)-CO, followed by redissociation to OH(v-1) and CO. With the vibrational quantum number v, chemical process from the adduct to H + CO(2) is accelerated, and vibrational relaxation is decelerated. The countertrend is elucidated by the competition between chemical reaction and vibrational relaxation in the adduct HOCO.     

Comment on the possible role of the reaction H+H2O→H2+OH in the radiolysis of water at high temperatures

In a recent paper (Radiation Physics and Chemistry, 2005, vol. 74, pp. 210) it was suggested that the anomalous increase of molecular hydrogen radiolysis yields observed in high-temperature water is explained by a high activation energy for the reaction H+H₂O→H₂+OH. In this comment we present thermodynamic arguments to demonstrate that this reaction cannot be as fast as suggested. A best estimate for the rate constant is 2.2×10³ M⁻¹ s⁻¹ at 300 °C. Central to this argument is an estimate of the OH radical hydration free energy vs. temperature, ΔG_hyd(OH)=0.0278t−18.4 kJ/mole (t in °C, equidensity standard states), which is based on analogy with the hydration free energy of water and of hydrogen peroxide.     

What are the Implications of Nonequilibrium in the O+OH and O+HO2 Reactions?

Vibrationally excited O2, OH, and HO2 species have been suggested (J. Phys. Chem. A 2004, 108, 758) to provide clues for explaining the "ozone deficit problem" and "HOx dilemma" in the middle atmosphere under conditions of local thermodynamic disequilibrium (LTD), but the question arises of how much LTD will affect the title ozone sink reactions. Besides providing novel kinetic results, it is shown that LTD tends to disfavor ozone depletion relative to traditional atmospheric modeling under Boltzmann equilibration, which is partly due to competition between the various reactive channels. The calculations also suggest that the title LTD processes can be important sources of highly vibrationally excited O2 in the middle atmosphere. Moreover, LTD is shown to offer an explanation for the fact that some down revision of the O + HO2 rate constant, or the ratio of the O + HO2 to O + OH rate constants, is required to improve agreement between the predictions of traditional modeling and observation. This, in turn, provides significant evidence supporting LTD at such altitudes.     

Lack of salt effect on the kinetics of the reaction SO2−4 + H3O+ → HSO−4 + H2O

It is found that the broadening of the 1100-cm⁻¹ line of SO⁻²₄, caused by increasing [H₃O⁺], is unaffected by addition of 4 M LiCl, NaBr, KCl and NH₄Cl. This finding is in line with the lack of influence of NaCl reported earlier. The significance of these findings, in terms of the reaction mechanism, is discussed.