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1.
Aleinikov N. N. Vasil'ev G. K. Kashtanov S. A. Makarov E. F. Chernyshev Yu. A. 《Kinetics and Catalysis》2001,42(2):233-237
The dependence of the rate of a photochemical reaction of XeO4with H2on the concentrations of H2and the diluent gases He and CO2is studied at room temperature. The results are compared with the data for the dark reaction. A mechanism with the elementary energetic branched-chain reaction OH
(v) + XeO4OH
+ O
+ XeO3is proposed to explain the results of the study. 相似文献
2.
V. Ya. Kavun A. A. Udovenko N. F. Uvarov V. I. Sergienko L. A. Zemnukhova 《Journal of Structural Chemistry》2002,43(2):246-251
Fluoride and ammonium ion dynamics in (NH4)3Sb4F15 was studied by 1H and 19F NMR spectroscopy in the range 180-440 K. Types of ionic motion were determined, and their activation energies were estimated. The crystal structure of a single crystal of (NH4)3Sb4F15 (space group
) was solved. In the range
K, a reversible phase transition has been found. Based on the experimental values of conductivity
of (NH4)3Sb4F15 (
S/cm at T = 440 K), this antimony(III) fluoride is classified as a superionic conductor. 相似文献
3.
Group contributions to
in seven solvents and to
in three solvents have been tabulated. The variation of
group parameters is discussed in terms of the solvent compressibility coefficient, T. The scaled particle theory (SPT) is used to calculate cavity contributions to
and C
p2
o
. Interaction contributions are obtained from the cavity terms and
and
values estimated through the additivity schemes.
values are more sensitive to solute-solvent interactions than
in water and less sensitive in methanol. The SPT results for heat capacities support the concept of structural promotion by hydrophobic solutes in water. 相似文献
4.
In this brief work we express the cycle index of the molecular point groups as a function of a limited number of initial geometrical parameters. Such parameters are the number
of elements composing the domain D of sites of substitutions in the molecule belonging to the point group G, and the numbers
of sites of D lying on the symmetry elements
for G. 相似文献
5.
Summary A general definition of reaction graphs is presented. For a pair of isomeric molecular graphs
and
, related by a chemical transformation
, the reaction graph
is determined using a maximal common subgraph defined for vertex mapping
. A binary operation defined for graphs constructed over the same vertex set enables us to decompose the reaction graph
into the sum of prototype reaction graphs. A decomposition of an overall reaction graph can be advantageously used for the construction of a reaction network. An oriented path in this network beginning at
and ending at
corresponds to a breakdown of the transformation
into a sequence of intermediates. 相似文献
6.
We derive two expansions of the Randles–Sevcik function
: an asymptotic expansion of
for x and its Taylor expansion at any x
0
. These expansions are accompanied by error bounds for the remainder at any order of the approximation. 相似文献
7.
Retrodisproportionation reactions R"C=NR" + HY R"
NHR" +
, RCN + HY R
=NH +
, RN=NR + HY R
NHR +
, RNO + HY R
OH +
, and RNO2 + HY RN(
)OH +
(where HY represents hydrocarbons, alcohols, phenols, amines, thiophenols, etc.) are considered as sources of radical generation. The enthalpies of these reactions are calculated. The parabolic model is used to calculate the rate constants for 254 such reactions. Various HY compounds acting as hydrogen-atom donors are compared with nitrogen-containing compounds acting as hydrogen-atom acceptors. The PhN(O) and PhNO2 compounds exhibit the highest activity among the studied acceptors. 相似文献
8.
A. V. Luzanov 《Journal of Structural Chemistry》2002,43(2):189-194
A technique for calculating spin perturbation effects in the framework of the previously developed matrix version of the full configuration interaction method is presented. The method is adapted to calculations of
-electron atom–atomic spin polarizability defined as the
-contribution to the indirect spin–spin nuclear coupling constant. Particular calculations show that pronounced long-range spin–spin coupling is actually possible in some characteristic conjugated systems such as polymethine dye carbocations or some nonalternant hydrocarbons. At the same time, spin–spin correlators appearing in McKonnel's theory are inapplicable in describing such long-range effects. 相似文献
9.
A. A. Lavrentiev B. V. Gabrelyan V. A. Dubeiko I. Ya. Nikiforov 《Journal of Structural Chemistry》2002,43(1):69-79
The effect of pseudovacancies on the density of electronic states of valence electrons in AgGaS2, CdGa2S4, and InPS4 is studied both experimentally, by means of X-ray spectroscopy, and theoretically, by calculating the partial densities of electronic states using the local coherent potential. The compounds under study are the derivatives of the sphalerite structural type (doubled cell) with gradually increasing deficiency of metals from
to
and further to
, where
is a vacancy. The environment of the metal atoms remains tetrahedral, while that of the sulfur atoms changes with increasing number of vacancies from four (AgGaS2) to three (CdGa2S4) and two (InPS4). For the compounds under study, SK and PK X-ray emission and absorption spectra were recorded at a resolution of about 0.2 eV, and the local partial densities of states were calculated for all components of the compounds. The theoretical curves practically coincide in shape and energy position of fine structure elements with the corresponding experimental curves. This allowed reliable conclusions about the energy positions of electronic states at the top of the valence band and about the dependence of the SK emission and absorption spectra in the series of compounds under study on variation of the crystal structure and on the chemical composition of the nearest surroundings of sulfur atoms. 相似文献
10.
Debashis Banerjee Ashis Kumar Laha Prasanta Chatterjee Sanjib Bagchi 《Journal of solution chemistry》1995,24(3):301-310
The extent of local excess or deficiency of a component solvent near the solute
in a mixed binary solvent has been calculated using the Hall formalism for the Kirkwood-Buff equation. The possibility of calculation of the two solute-solvent Kirkwood-Buff parameters
using the
values is discussed. A model calculation using literature data for preferential solvation in mixed binary solvents is presented. The solute-solvent and solvent-solvent interactions and the relative size of the solvents are also shown to be relevant factors in determining the
values. 相似文献
11.
G. R. Okroyan D. F. Kushnarev G. A. Kalabin A. G. Proidakov 《Journal of Structural Chemistry》2002,43(2):242-245
Relaxation characteristics of Na+ and K+ water clusters were studied by 17O NMR spectroscopy. The influence of viscosity
and pH of solution was taken into account; for both electrolytes in the concentration range
-4 M, spin–spin relaxation times are greater than those for pure water. For K+ clusters, maxima of the concentration dependence of 17O spin–spin relaxation time have been found. 相似文献
12.
Because of their exceptional reactivity, fluorine and fluorinated gases are of primary importance for the modification of the surface properties of materials. This study is devoted to surface treatment of thin nitrile gloves, made of carboxylated nitrile butadiene rubber latex, using either direct fluorination (10% F2gas diluted in N2) or plasma-enhanced fluorination in radio-frequency cold plasmas using fluorinated gases (CF4, CHF3). Mechanisms of fluorination of these co-elastomers have been proposed on the basis of the assignment of the different components of the XPS spectra. Several mechanisms have been observed depending on the fluorination conditions. Although the modification of nitrile gloves is already effective for fluorination reactions at room temperature, an important activation is observed for experiments carried out at 90°C. When the treatments are carried out at room temperature, a gradual fluorination occurs: in the case of 10% diluted F2 gas, monofluorinated C—F groups are the species most found at the surface and perfluoro groups CF
n
are present in lower amount. An addition reaction takes place at the
CH=CH
double bonds of the polybutadiene entities, leading to
CHF=CHF
units. Whatever the fluorination method, thermal activation yields a more massive fluorination of the surface that finally leads to perfluorinated
CF2
groups and terminal —CF3 groups. 相似文献
13.
The dependencies of the relative permittivity of over 50 liquids on the pressure P, as
, and of some 40 liquids on the (square of the) electric field E at ambient conditions, as
were obtained from literature data. The function
was fitted to a simple expression in and the compressibility, T. These data were used to obtain the limiting slope for the partial molar volumes and the electrostriction of electrolytes in various solvents. 相似文献
14.
F.P. Temme 《Journal of mathematical chemistry》1997,21(4):373-384
On existence of limiting
‐module decompositional sets for weak
‐branching at high n; on Voronoi polyhedral dual as geometric analogues to Cayley’s SU2
embedding theorem; and on SU
dual group with retention of self‐associacy over subduced irrep set, as being the sufficient further condition to ensure
the determinacy of SU
embeddings.
In the context of structures arising from nuclear permutation (NP) or NMR dual‐group spin algebras, the first conjecture sets
out the high‐index n, and thus weak‐branching limit (WBL), aspects of
module decompositions as giving rise to a set of numerical values for the associated Kostka coefficients which are invariant
to further incrementation in the
index; the existence of such combinatorial limit properties, implicit in sst
tableaux enumerations, has not been addressed in the mathematics literature to date. Conjectures 2 and 3 are concerned with
the questions of geometric and sufficient algebraic realisations of the determinacy of natural finite group embeddings in
specific SU
permutation groups. In conjecture 2, the Voronoi dual‐structures to the regular polyhedra for NP/NMR automorphic SU2
embedded spin symmetries hold the key to physical insight. Specifically, they provide a novel combinatorial geometric view
of Cayley’s theorem; the mid‐face intersecting
‐axes of the initial NMR automorphic solids become (vertex) body‐diagonal axes of the specific‐dual Voronoi polyhedra, where
a distinctness condition from the spin‐sites gives raise to a geometric statement of Cayley’s theorem. Conjecture 3 is concerned
with SU
embeddings for which the simple Cayley criterion alone is an insufficient condition to guarantee determinacy. The
self‐associacy property and its retention over the subduced irrep‐subset(s) (i.e., comparable to studies of
system‐invariants via Yamanouchi–Gel’fand subduction chains) is now seen as indicative of retention of determinacy for such
SU
group embeddings through the above sufficiency condition.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
15.
The enthalpies and entropies of evaporation of Al(CH3)3–Sn(CH3)4and Ga(CH3)3–Sn(CH3)4solutions were determined. It was established that solvates are formed in these systems and that the dissociation energies of specific interactions in them change in the following order:
(10.3) >
>
>
(4.08 kJ mol–1),
(6.52) >
(5.14) >
>
(4.08 kJ mol–1). 相似文献
16.
Carbonate stability constants for yttrium and all rare earth elements have been determined at 25°C and 0.70 molal ionic strength by solvent exchange and inductively coupled plasma–mass spectrometry (ICP–MS). Measured stability constants for the formation of
and
from M3+ are in good agreement with previous direct measurements, which involved the use of radio-chemical techniques and trivalent ions of Y, Ce, Eu, Gd, Tb, and Yb. Direct ICP–MS measurements of
and
formation constants are also in general agreement with modeled stability constants for the metals La, Pr, Nd, Sm, Dy, Ho, Er, Tm, and Lu, based on linear-free energy relationship (LFER). The experimental procedures developed in this work can be used for assessing the complexation behavior of other geochemically important ligands such as phosphate, sulfate, and fluoride. 相似文献
17.
Perturbative solution of the RPA equation. An application to the calculation of rotational strengths
The RPA equation is solved by perturbation in Møller-Plesset (MP) and Epstein-Nesbet (EN) partitions, which are first compared on a specific example. To still accelerate the faster one (EN), a third scheme is proposed, which involves preliminary diagonalization within a limited subset
, followed by usual EN perturbation between
and the rest of the whole configuration space. Criteria for the choice of
are given. 相似文献
18.
We examine a few computational geometric problems concerning the structures of polymers. We use a standard model of a polymer, a polygonal chain (path of line segments) in three dimensions. The chain can be reconfigured in any manner as long as the edge lengths and the angles between consecutive edges remain fixed, and no two edges cross during the motion. We discuss preliminary results on the following problems.Given a chain, select some interior edge
, defining two subchains which are adjacent to
. We keep the two subchains individually rigid and rotate one around
while leaving the other fixed in space, while maintaining the vertex-angles at
. We call this motion an edge spin at
. An O(n
2) algorithm for this problem is given as well as an (nlogn) lower bound on the time complexity.In determining whether a chain can be reconfigured from one conformation to another, it is useful to consider reconfiguring through some canonical conformation. In our three-dimensional case, the most obvious choice is to flatten a chain into the plane. However, we demonstrate that determining if a given chain can be reconfigured into the plane without self-intersecting is NP-hard, even if the restriction that it must lie monotonically is added. We then provide an O(n) algorithm to decide if a chain has a non-crossing convex coil conformation (where all angles turn in the same direction), although we cannot yet decide if a sequence of motions to reconfigure a chain into a convex coil conformation exists. 相似文献
19.
István Szalkai 《Journal of mathematical chemistry》1999,25(1):31-46
The phases of multicomponent systems (mixtures, states, etc.) containing the compounds
are
, where
and
. For
(quaternary or higher dimensional systems), the displaying methods and visual investigations in the
dimensional Euclidean space
are tangentially or not at all described in the literature. In this paper we first develop the theoretical (both mathematical and computational) background in any dimension in
. We focus not only on the important points, lines, surfaces of these systems, and computing method of the states of some processes in such systems, but also on the approximating methods of the above mentioned lines and surfaces, and, finally, on the question which is the region where a state (a point) falls into. Using the above results a computer program for PC's was created for evaluating and displaying the approximated surfaces. This program is described in I. Szalkai, SALT3DIM.exe – A program for handling 4 component mixtures, Preprint No. 047, University of Veszprém (1996), and the computing results are planned to be published in a forthcoming paper (I. Szalkai, Handling multicomponent systems in
. II: Computational results, J. Chem. Inf. Comput. Sci., submitted). 相似文献
20.
A second-order method is developed for the numerical solution of the initial-value problems
,
,
and
,
,
, in which the functions
and
, where A and B are positive real constants, are the reaction terms arising from the mathematical modelling of chemical systems such as in
enzymatic reactions and plasma and laser physics in multiple coupling between modes. The method is based on three first-order
methods for solving u and v, respectively. In addition to being second-order accurate in space and time, the method is seen to converge to the correct
fixed point (
, V* = A/B) provided
. The approach adopted is extended to solve a class of non-linear reaction–diffusion equations in two-space dimensions known
as the “Brusselator” system. The algorithm is implemented in parallel using two processors, each solving a linear algebraic
system as opposed to solving non-linear systems, which is often required when integrating non-linear partial differential
equations (PDEs).
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献