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1.
Katō T 《The Journal of chemical physics》2004,120(2):829-838
The dissociation and association dynamics of N2O4 [see text] 2NO2 in liquid state are studied by classical molecular dynamics simulations of reactive liquid NO2. An OSPP+LJ potential between NO2 molecules, which is a sum of an orientation-sensitive pairwise potential (OSPP) between N-N atoms proposed in Paper I [J. Chem. Phys. 115, 10852 (2001)] and Lennard-Jones potentials between N-O and O-O atoms, has been used in the simulation. The reaction dynamics is studied as a function of well depth De and anisotropy factors of the OSPP potential: Atheta (0< or =Atheta< or =1) for the rocking angle and Atau (0< or =Atau< or =0.5) for the torsional angle of relative NO2-NO2 orientation. The lifetime tauD of initially prepared NO2 dimers is found to increase as De increases, Atheta increases, and Atau decreases. Dissociation and association dynamics are studied in detail around the extreme limit of pure NO2-dimer liquid: De=0.12 x 10(-18) J, Atheta=0.5, and Atau=0.1, which has been found to reproduce both the observed liquid phase equilibrium properties and Raman band shapes of the dissociation mode very well. The dissociation dynamics from microscopic reaction trajectories is compared with the potential of the mean force (PMF) as a function of the N-N distance R. The PMF of reactive liquid NO2 shows a transition state barrier at R=2.3-2.5 A, and NO2-trimer structure is found to be formed at the barrier. Two types of dissociation of the NO2 dimer-the dissociation by collisional activation of the reactive mode to cross the dissociation limit and the NO2-mediated dissociation via bond transfer-are studied. The latter needs less free energy and is found to be much more probable. The dissociation trajectories and PMF in reactive liquid NO2 are compared with those of a reactive NO2 pair in inert solvent N2O4. 相似文献
2.
The refractive index of SiO2-P2O5 glass prepared by a modified chemical vapor deposition method is measured using an interference microscope. It is found that the refractive index in bulk form increases linearly at 9.5×10-4 (mol.%)-1 as the P2O5 concentration increases. It is also found that quenching at extremely high speed reduces the refractive index over 2 mol.% P2O5. The wavelength dispersion of the refractive index dn/dλ is constant up to 5 mol.% P2O5 producing a refractive index difference of 5×10-3 compared with fused silica. Consequently, this glass materials is thought to be suitable for wide band-width optical fiber applications. 相似文献
3.
Utaro Furukane Toshiatsu Oda 《Journal of Quantitative Spectroscopy & Radiative Transfer》1985,33(6):645-651
Lasing conditions for He have been evaluated numerically. We have used a collisional radiative model to calculate overpopulation densities Δnij, which are defined as differences between population densities per unit statistical weight of the upper and lower excited levels i and j, respectively. Laser oscillations for the level pairs 21P-31S, 21P-41S, 21P-31D, 21P-41D, 31D-41F, 31P-41S, 31P-41D, and 33P-43S are possible when the electron densities are within well defined limits at low electron temperature (Te = 0.1 eV). For level pairs of the singlet state, the inversion mechanism for He is the same as for H. Only collisional processes produce population inversion in the triplet level pair 33P-43S. 相似文献
4.
Chōkō Shibata 《Reports on Mathematical Physics》1978,13(1):117-128
The curvature tensors and other important tensors of a Finsler space with Kropina metric are studied. We find conditions for such a space to be affinely connected in Berwald's sense. 相似文献
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6.
Gikō Ikegami 《Inventiones Mathematicae》1989,95(2):215-246
Summary We define a constraint system
, [0,0), which is a kind of family of vector fields
on a manifold. This is a generalized version of the family of the equations
, [0,0),x
m
,y
n
. Finally, we prove a singular perturbation theorem for the system
, [0,0).Dedicated to Professor Kenichi Shiraiwa on his 60th birthday 相似文献
7.
Katō T 《The Journal of chemical physics》2004,120(21):10127-10132
Transition state dynamics of dissociation and association reactions N2O4 <==> 2NO2 in liquid state are studied by classical molecular dynamics simulations of reactive liquid NO(2) at 298 K. An OSPP+LJ potential between NO(2) molecules proposed in paper I [J. Chem. Phys. 115, 10852 (2001)], which takes into account the orientational sensitivity of the chemical bond, has been used in the simulation. The trajectory and energy evolution of various reactions are studied in the OSPP+LJ liquid, which reproduces both the observed liquid phase equilibrium constant and Raman band shape of the dissociation mode. It is found that a NO(2) pair in reactive liquid NO(2) is bound when E(T)<0 and dissociates when E(T)>0, and the dissociation of a reactant pair occurs when the transition state (TS) surface of E(T)=0 is crossed from negative to positive, where E(T) is the sum of the potential and kinetic energies of intermolecular motion of the pair. Two types of dissociation are found depending on the source of energy for dissociation; the first type D is the dissociation via collisional activation of the reactive mode by solvent molecules, and the second type T is the dissociation via bond transfer from a dimer to a monomer NO(2) through the TS of NO(2) trimer. It is concluded that the type T dissociation is found to be much more probable than the type D dissociation because of easy energy conservation. The reactant experiences the TS of NO(2) trimer for a long time (1-10 ps) in NO(2) mediated bond transfer reactions, and crossing and recrossing trajectories and dynamics in the TS neighborhood are studied. 相似文献
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9.
Tsunehisa Hirashita Shō Kuwahara Sota Okochi Makoto Tsuji Shuki Araki 《Tetrahedron letters》2010,51(14):1847-1851
In high-temperature water a series of benzyl and allylic alcohols reacted with 1,3-dicarbonyl compounds and activated aromatic compounds to give the alkylated products without added catalysts. 相似文献
10.
Tadashi Nakata Takaaki Kuwabara Yōichirō Tani Takeshi Oishi 《Tetrahedron letters》1982,23(9):1015-1016
()-Oudemansin has been synthesized starting from -cinnamaldehyde by a route involving the stereoselective Zn(BH4)2 reduction of β-keto ester. 相似文献