A computational study of interactions between acetic acid and water molecules

Density functional theory calculations were performed for the title reactions to elucidate the difference between the strong cyclic hydrogen bond of (Me-COOH)(2) and the electrolytic dissociation, MeCOOH <==> Me-COO(-) + H(+), as a weak acid. The association of water clusters with acetic acid dimers strengthens the cyclic hydrogen bond. A nucleophilic attack of the carboxylic carbon by a water cluster leads to a first zwitterionic intermediate, MeCOO(-) + H(3)O(+) + (HO)(3)C-Me. The intermediate is unstable and is isomerized to a neutral interacting system, MeCOOH...(HO)(3)C-Me + H(2)O. The ethanetriol, (HO)(3)-CMe is transformed to an acetic acid monomer. The monomer may be dissociated to give a second zwitterionic intermediate with reasonable proton-relay patterns and energy changes. In proton relay reaction channels, H in MeCOOH is not an acidic proton but is always a hydroxy proton.     

A theoretical deduction of the shape and size of nanocarbons suitable for hydrogen storage

We evaluated the adsorption energy of a hydrogen molecule in nanocarbons consisting of graphene sheets. The nanocarbon shapes were a pair of disks with separation 2d, a cylinder with radius d, and a truncated sphere with radius d. We obtained the adsorption energy in the form of a 10–4 Lennard–Jones function with respect to 1/d. The values of the potential depth (D) and equilibrium distance (d _e), respectively, were 94 meV and 2.89 Å for the disk pair, 158 meV and 3.14 Å for the cylinder, and 203 meV and 3.37 Å for the sphere. When d=d _e, the adsorption energy of the disk pair (cylinder) became deeper than ?0.9D, and it approached ?D when the radius (length) increased to more than twice its separation (radius). The adsorption energy of the sphere was increased from ?D to ?0.5D when the radius of the opening increased from 0 to d _e. These results suggest that porous carbon materials can increase the adsorption energy by up to ～200 meV if the carbon atoms are arranged on a spherical-like surface with ～7 Å separation. This may lead to practical hydrogen storage for fuel cells.     

Nitridation of Si(100)-( 2x1) surface by NH3: a quantum chemical cluster model study

Based on density functional cluster model calculations, we present the first detailed mechanisms for the complete decomposition of NH3 to NHx(a) (x = 0-2) on the Si(100)-(2x1) surface. Three kinds of elementary processes, namely, N-H bond cleavage, NHx(a) insertion into the Si-Si surface dimer bond or backbond, and H2 libration, are investigated. A plausible microscopic mechanism for the nitridation of Si(100)-(2x1) surface by NH3 is proposed.     

Role of hydrogen bonds in acid-catalyzed hydrolyses of esters

Acid-catalyzed ester hydrolyses were studied by means of DFT calculations. A model composed of ester and H₃O⁺(H₂O)₁₅ was adopted, and substrates esters are ethyl acetate, ethyl para-X-substituted benzoates (X?=?O₂N, Cl, H, iso-Bu, MeO, and Me₂N), and isobutyl benzoate. For the ethyl acetate, a stepwise path, precursor????TS1????Int1????Int2????TS2????product, was obtained. Here, TS is the transition state, and Int is the tetrahedral intermediate. The path is somewhat different from the established A_AC2 mechanism; the carbocation intermediate was calculated to be absent in the present model. The absence holds even for benzoates that may stabilize the cation except the X?=?Me₂N substituted one. At each local energy minimum, the cation character is retained in H₃O⁺. Proton relays along hydrogen bonds were found to prompt interchanges of covalent bonds. The rate-determining step is either TS1 for the electron-withdrawing X or TS2 for the electron-donating one.     

A significant role of alkaline cations on the Reimer-Tiemann reaction

The Reimer-Tiemann (R-T) reaction was investigated by DFT calculations. A model composed of CHCl(3), PhO(-)(Na(+))H(2)O and [NaOH(H(2)O)(2)](2) was employed for geometry optimizations. A K(+)-containing model was also investigated. The dichlorocarbene reagent, which has been thought of for a long time, was found to intervene only transiently in the carbenoid form. In this form, the Na(+) (or K(+)) coordination to CCl(2) enhances its electrophilicity toward C(6)H(5)O(-). The counter ion also works to stabilize the precursor phenoxide ion and intermediates of the substituted phenoxides in the hexagonal pyramidal coordination. The Na(+)-containing reaction consists of seven elementary processes, (K(+), six ones) with extremely high exothermicity and spontaneity.     

Development of New Strain Gage for High-Pressure Hydrogen Gas Use

The output changes of two conventional strain gages (Cu–Ni and Ni–Cr) and a newly-selected strain gage for high-pressure hydrogen gas use (Fe–Cr–Al) in 90 MPa hydrogen and nitrogen gases were measured under unloading conditions to find a high-performance strain gage for high-pressure hydrogen gas use. The changes in the outputs of the Cu–Ni and Ni–Cr gages in hydrogen gas were much larger than those in nitrogen gas, and the Fe–Cr–Al gage showed almost the same output changes in both gases. These results imply that the Fe–Cr–Al gage is superior to the others as a strain gage for high-pressure hydrogen gas use. A large amount of hydrogen entered the Cu–Ni and Ni–Cr foils, and the electrical resistances of these foils were significantly changed by hydrogen exposure, whereas almost no hydrogen entered the Fe–Cr–Al foil, and its electrical resistance was not changed. These resistance changes of the foils as a result of hydrogen entry were consistent with the gage output changes in hydrogen gas.     

A microscopic theory for solution chemical reactions: Introduction of reactant and medium structures into generalized langevin equation formalism

A microscopic formulation of solution chemical reactions, taking reactants and medium structures into consideration, is presented on the basis of microscopic understandings obtained by recent quantum chemical methods (i.e., ab initio molecular orbital theory, etc.). Assuming thermal equilibrium of the medium bath, an effective internal Hamiltonian is derived, and, further, its derivative with respect to internal normal coordinates is proved explicitly to give the same force field as is provided by the free-energy surface or potential of mean force. The free-energy surface can be expressed in the composite normal coordinate system (CNCS ) consisting of some normal coordinate systems of isolated reactants and surrounding solvent molecules (i.e., medium solvent molecules). In CNCS , in use of diagonal elements obtained in the Hessian matrix of the free-energy surface, effective normal-mode frequencies, which reflect the equilibrium solvent effect, are estimated. Furthermore, on the generalized Langevin equation (GLE ) treatment, a closed expression of the time-dependent frictional coefficient is derived on a microscopic basis, reflecting the reactant and solvent structures. The nonequilibrium effect is estimated by an analytical expression similar to that in the Grote–Hynes theory. The rate constant is evaluated for a typical model system and it is shown that the equilibrium rate constants should be reduced by a factor 0.997. Finally, it is concluded that the present microscopic theory is reasonably applicable to the estimation of chemical reaction rate constants in solution. © 1994 John Wiley & Sons, Inc.     

Statistical simulation based on right skewed distributions

Statistical simulations in medical and biological research are usually conducted with normal random numbers. However, in many cases, the distributions of real data in medical fields are usually right skewed. The conclusions led by simulations with the misspecified model might be misleading because of a gap between real data’s distribution and theoretical one. In this paper, we provide the simulation procedure for right skewed data based on reparameterized, easily interpretable parameters of the Box–Cox transformation model which includes multivariate distributions and regression models. We also show that the provided procedure is widely applicable to real world based on laboratory data, and then we provide parameter vector sets obtained by reparameterized parameter estimates that would cover almost all situations in which the distributions of data were right skewed and unimodal.