Theoretical determination of the rate coefficient for the HO2 + HO2 → H2O2+O2 reaction: adiabatic treatment of anharmonic torsional effects

The HO(2) + HO(2) → H(2)O(2) + O(2) chemical reaction is studied using statistical rate theory in conjunction with high level ab initio electronic structure calculations. A new theoretical rate coefficient is generated that is appropriate for both high and low temperature regimes. The transition state region for the ground triplet potential energy surface is characterized using the CASPT2/CBS/aug-cc-pVTZ method with 14 active electrons and 10 active orbitals. The reaction is found to proceed through an intermediate complex bound by approximately 9.79 kcal/mol. There is no potential barrier in the entrance channel, although the free energy barrier was determined using a large Monte Carlo sampling of the HO(2) orientations. The inner (tight) transition state lies below the entrance threshold. It is found that this inner transition state exhibits two saddle points corresponding to torsional conformations of the complex. A unified treatment based on vibrational adiabatic theory is presented that permits the reaction to occur on an equal footing for any value of the torsional angle. The quantum tunneling is also reformulated based on this new approach. The rate coefficient obtained is in good agreement with low temperature experimental results but is significantly lower than the results of shock tube experiments for high temperatures.     

Microwave spectroscopic and theoretical studies on the phenylacetylene···H2O complex: C-H···O and O-H···π hydrogen bonds as equal partners

Rotational spectra of five isotopologues of the title complex, C(6)H(5)CCH···H(2)O, C(6)H(5)CCH···HOD, C(6)H(5)CCH···D(2)O, C(6)H(5)CCH···H(2)(18)O and C(6)H(5)CCD···H(2)O, were measured and analyzed. The parent isotopologue is an asymmetric top with κ = -0.73. The complex is effectively planar (ab inertial plane) and both 'a' and 'b' dipole transitions have been observed but no c dipole transition could be seen. All the transitions of the parent complex are split into two resulting from an internal motion interchanging the two H atoms in H(2)O. This is confirmed by the absence of such doubling for the C(6)H(5)CCH···HOD complex and a significant reduction in the splitting for the D(2)O analog. The rotational spectra, unambiguously, reveal a structure in which H(2)O has both O-H···π (π cloud of acetylene moiety) and C-H···O (ortho C-H group of phenylacetylene) interactions. This is in agreement with the structure deduced by IR-UV double resonance studies (Singh et al., J. Phys. Chem. A, 2008, 112, 3360) and also with the global minimum predicted by advanced electronic structure theory calculations (Sedlack et al., J. Phys. Chem. A, 2009, 113, 6620). Atoms in Molecule (AIM) theoretical analysis of the complex reveals the presence of both O-H···π and C-H···O hydrogen bonds. More interestingly, based on the electron densities at the bond critical points, this analysis suggests that both these interactions are equally strong. Moreover, the presence of both these interactions leads to significant deviation from linearity of both hydrogen bonds.     

Theoretical studies on the electron capture properties of the H2SO4...HOO˙ complex and its implications as an alternative source of HOOH

To better understand the potential role of sulfuric acid aerosols in the atmosphere, the electron capture properties of the H(2)SO(4)...HOO˙ complex have been systematically investigated by employing the MP2 and B3LYP methods in combination with the atoms in molecules (AIM) theory, energy decomposition analysis (EDA), and ab initio molecular dynamics. It was found that the electron capture process is a favorable reaction thermodynamically and kinetically. The excess electron can be captured by the HOO˙ fragment initially, and then the proton of the H(2)SO(4) fragment associated with the intermolecular H-bonds is transferred to the HOO˙ fragment without any activation barriers, resulting in the formation of the HOOH species directly. Therefore, the electron capture process of the H(2)SO(4)...HOO˙ complex provides an alternative source of HOOH in the atmosphere. The nature of the coupling interactions in the electron capture products are clarified, and the most stable anionic complex is also determined. Additionally, the influences of the adjacent water molecules on the electron capture properties are investigated, as well as the distinct IR features of the most stable electron capture product.     

Theoretical studies of the radical reaction H2CSiH2 + H

Ab initio molecular orbital calculations on the transition states and barrier heights for the addition of atomic hydrogen to silaethylene are carried out. The activation energy for the addition to the silicon site is lower than that to the carbon site, while the exothermicity is smaller.     

Spectral studies on Ag8+ ions irradiated LAHCl·H2O and LAHBr·H2O single crystals

L-arginine hydrochloride monohydrate and L-arginine hydrobromide monohydrate single crystals are irradiated by 100 MeV Ag8+ swift heavy ions. The residual gases liberated from the irradiated samples are monitored as a function of ion fluence using quadrupole mass analyzer. The C2H3+, C2H2, N2, CO, HCl and CO2 are the dominant gases liberated. Fourier transform infrared spectra of irradiated crystals explain the breaking of bonds in a localized region of the crystals. The crystallinity of irradiated crystals is analyzed by powder X-ray diffractions.     

Theoretical Study on Mechanism of C5H7·+O2 Reaction

The potential energy surface (PES) for the reaction of E,E-pentadienyl with molecular oxygen was theoretically studied at the G3B3//B3LYP/6-311G(d,p) level of theory. The first step of the reaction was found to be the direct adduction of molecular O2 on either the C1 or the C3 atoms of E,E-pentadienyl, forming two C5H7O2· isomers. These two C5H7O2· isomers undergo a series of isomerization processes through either the hydrogen-transfer or cyclization pathway. In the final step, the hydrogen-transferred and cyclized isomers decompose into unsaturated aldehydes, unsaturated ketones, and hydroxyl radicals. Involves 20 stable species and 14 transition states, and the energies and structures of all reactants, products and transition states were calculated. Based on the calculated barriers and heats of formation, the authors suggest that the C2H3O·+C3H4O formation channel is the dominant channel for the C5H7·+O2 reaction. The possible existence of C5H7O2· radicals as long lifetime intermediates is also proposed, which is consistent with the recent photoionization mass spectrometric experiments by Zils et al.     

Theoretical studies on the substitution effect of fluorine on ethylene

The substitution effect of fluorine on ethylene is investigated by means of studyingthe properties of the charge distribution at the bond critical points with the theory of atomsin molecules.It is found that fluorine atom acts not only as a σ electron acceptor,but also asa π electron donor,and these double effects are reflected in the quantity of ellipticity,Lap-lacian and the charge density of charge distribution at the bond critical points.For C—C,C—Fbonds,the major axis of elliptical contours is perpendicular to the molecular plane,but forC—H bond,it is parallel to the molecular plane.Other effects originating from the substi-tution have also been discussed.     

Theoretical Studies on the Stabilities and Hydrogen Bond Actions of （H2O）n Clusters

1 INTRODUCTION In the latest ten years, the structure and function of water clusters have captured the interest of chemists. One of the most important study objects in water cluster is to describe the behavior of water so- lution quantitatively at molecule level, which will pave the way for the solving of some environmental and other scientific problems, such as the formation of acid rain and nucleation mechanism of little water drop. Besides, weak interaction in water clusters could be al…     

Thermogravimetric studies of the synthesis of cas from gypsum, CaSo4·2H2O and phosphogypsum

Using a heating rate of 2°C min^–1, CaS reacts with oxygen in air from 700°C to form CaSO₄, with a complete conversion at 1100°C. Synthesis of CaS from the reaction between CaSO₄ containing compounds and carbon compounds in air would not be possible, as the carbon reacts from 600°C with oxygen in the air to give CO₂. Heating stoichiometric amounts of carbon and pure CaSO₄, synthetic gypsum or phosphogypsum in a nitrogen atmosphere, results in the formation of CaS from 850°C. Using a heating rate of 10°C min^–1, the formation of CaS is completed at 1080°C. Addition of 5% Fe₂O₃ as a catalyst lowers the starting temperature of the reaction to 750°C. Activation energy values at different fraction reaction values () differ between 340 and 400 kJ mol^–1. The relationship between the activation energy values and conversion () indicates that the reaction proceeds via multiple steps.     

Theoretical studies on structures and UV-Vis spectra of C_(70)O

Systematic studies on eight isomers of C70O were performed by means of INDO methods It has been indicated that the O atom is mainly added to the C1-C2 or C3-C3 bond and an epoxide feature with C1 symmetry is formed.Based on the optimized geometries,the UV-Vis spectra were calculated.It has been found that the main peaks of C70O resemble those of C70 and the characteristic absorptions beyond 460 nm are produced,which is m agree ment with the experimental results.Theoretical assignments about the absorptions were carried out and the reason for the red-shift of the absorptions was discussed.C70O is probably composed of four isomers according to the calculated results.     

Theoretical studies of the g factors and local structures of the Ni3+ centers in Na2Zn(SO4)2·4H2O and K2Zn(SO4)2·6H2O crystals

The local structures and the g factors g_i (i = x, y, z) for Ni³⁺ centers in Na₂Zn(SO₄)₂·4H₂O (DPPH) and K₂Zn(SO₄)₂·6H₂O (PHZS) crystals are theoretically studied by using the perturbation formulas of the g factors for a 3d⁷ ion with low spin (S = 1/2) in orthorhombically compressed octahedra. In these formulas, the contributions to g factors from both the spin-orbit coupling interactions of the central ion and ligands are taken into account, and the required crystal-field parameters are estimated from the superposition model and the local geometry of the systems. Based on the calculations, the Ni-O bonds are found to suffer the axial compression δz (or Δz) of about 0.111 Å (or 0.036 Å) along the z-axis for Ni³⁺ centers in DPPH (or PHZS) crystals. Meanwhile, the Ni-O bonds may experience additional planar bond length variation δx (≈0.015 Å) along x- and y-axes for the orthorhombic Ni³⁺ center in DPPH. The theoretical g factors agree well with the experimental data. The obtained local structural parameters for both Ni³⁺ centers are discussed.     

Theoretical studies of the reactions of M+ (M = Ta,W, Re) with CS2

Gas-phase CS₂ activation by M⁺ (M = Ta, W, Re) was studied by the B3LYP density functional method.The geometries for reactants, transition states, and products were completely optimized. CS₂ activation mediated by M⁺ (M = Ta, W, Re) were found to be a spin-forbidden process as a result of the crossing among the multistate energetic profiles. On the basis of the Hammond postulate, this was a typical two-state reactivity reaction. Among the different potential energy surfaces, the crossing points had been explored. The spin–orbit coupling (SOC) was also calculated between the electronic states of different multiplicities at the crossing point to estimate the intersystem crossing probability. For CP1, CP2, and CP4, the computed SOC constants were 80.28, 128.65, and 526.77 cm^?1, which obtained by using one-electron spin–orbit Hamiltonian in Gaussian 09.     

Quantum chemical studies on addition reactions of carbene with carbon monoxide and formaldehyde

MNDO method has been employed to study the reaction paths and to optimize the structures of the reactants, products and transition states of the addition reactions of carbene with carbon monoxide and formaldehyde available. Mechanisms have been obtained.     

Theoretical Studies on the Abstraction Reaction of Atomic O（^3p） with Si2H6

The hydrogen abstraction reaction of O(^3P) with Si2H6 has been studied theoretially. Two transition states of ^3A″ and ^3A′ symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 leve with 6-311G (d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200-3000K using canonical variational transition-state sheory (CVT) with small curvature tunneling effect(SCT). The calculated CVT/SCT rate constants match well with the experimental value.     

Theoretical and computational studies of organometallic reactions: successful or not?

Theoretical and computational methods are powerful in studying transition metal complexes. Our theoretical studies of C–H σ‐bond activation of benzene by Pd(II)–formate complex and that of methane by Ti(IV)‐imido complex successfully disclosed that these reactions are understood to undergo heterolytic σ‐bond activation and the driving force is the formation of strong O–H and N–H bonds in the former and the latter, respectively. Orbital interactions are considerably different from those of σ‐bond activation by oxidative addition. The transmetallation, which is a key process in the cross‐coupling reaction, is understood to be heterolytic σ‐bond activation. Our theoretical study clarified how to accelerate this transmetallation. Also, we wish to discuss weak points in theoretical and computational studies of large systems including transition metal elements, such as the necessity to incorporate solvation effect and to present quantitatively correct numerical results. The importance of solvation effects is discussed in the oxidative addition of methyliodide to Pt(II) complex which occurs in a way similar to an S_N2 substitution. To apply the CCSD(T) (coupled cluster singles and doubles with perturbative triples correction) method, which is the gold standard of electronic structure theory, to large system, we need to reduce the size of the system by employing a small model. But, such modeling induces neglects of electronic and steric effects of substitutents which are replaced in the small model. Frontier‐orbital‐consistent quantum‐capping potential (FOC‐QCP) was recently proposed by our group to incorporate the electronic effects of the substituents neglected in the modeling. The CCSD(T) calculation with the FOC‐QCP was successfully applied to large systems including transition metal elements. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 10: 000–000; 2010: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900019     

Structure of the complex [trans-SnF4(H2O)2· (18-crown-6)· 2H2O]

The molecular and crystal structure of the title complex (I) obtained by addition of tin fluoride in a hydrofluoric acid solution to 18-crown-6 in methanol was investigated by X-ray structure analysis. The crystals are monoclinic, space group P2₁/n, a = 13.497(3), b = 7.806(2), c = 9.892(2) Å, β = 95.57(3)°, Z = 2 for C₁₂H₃₂F₄O₁₀Sn. In the polymer chain, the crown ether molecules alternate with the inorganic complexes [trans-SnF₄(H₂O)₂] and are linked to them by O-H...O type hydrogen bonds involving the intermediate water molecules. The weak C-H...F interactions bind the chains into the layers which are parallel to the xz plane.     

Theoretical study of the N—H···O red-shifted andblue-shifted hydrogen bonds

Theoretical calculations are performed to study the nature of the hydrogen bonds in complexes HCHO···HNO, HCOOH···HNO, HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F. The geomet- ric structures and vibrational frequencies of these six complexes at the MP2/6-31 G(d,p), MP2/6-311 G(d,p), B3LYP/6-31 G(d,p) and B3LYP/6-311 G(d,p) levels are calculated by standard and counterpoise-corrected methods, respectively. The results indicate that in complexes HCHO···HNO and HCOOH···HNO the N—H bond is strongly contracted and N—H···O blue-shifted hydrogen bonds are observed. While in complexes HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F, the N—H bond is elongated and N—H···O red-shifted hydrogen bonds are found. From the natural bond orbital analysis it can be seen that the X—H bond length in the X—H···Y hydrogen bond is controlled by a balance of four main factors in the opposite directions: hyperconjugation, electron density redistribu- tion, rehybridization and structural reorganization. Among them hyperconjugation has the effect of elongating the X—H bond, and the other three factors belong to the bond shortening effects. In complexes HCHO···HNO and HCOOH···HNO, the shortening effects dominate which lead to the blue shift of the N—H stretching frequencies. In complexes HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F where elongating effects are dominant, the N—H···O hydrogen bonds are red-shifted.