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41.
An analytical potential energy surface (PES) representation of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+)) system was developed by fitting around 600 CCSD(T)/cc-pVQZ ab initio points. Rate constant calculations for this reaction and its isotopic variants (D(2) and HD) were performed using the quasiclassical trajectory (QCT) method, obtaining a good agreement with experimental data. Calculations conducted to determine the cross section of the title reaction, considering collision energies (E(T)) below 0.3 eV, also led to good accord with experiments. This PES appears to be suitable for kinetics and dynamics studies. Moreover, the QCT results show that, although the hypotheses of a widely used capture model are not satisfied, the resulting expression for the cross section can be applied within a suitable E(T) interval, due to errors cancellation. This could be a general situation regarding the application of this simple model to ion-molecule processes. 相似文献
42.
Freiría A Bastida R del Carmen Fernández-Fernández M Macías A Valencia L Vicente M 《Inorganic chemistry》2005,44(4):930-934
We report here the first pentanuclear Ba(II) complex of a new tri-aza, tri-oxa macrocycle with two carboxymethyl "arms" pending from two N atoms, H2L2. The crystal structure corresponds to the formula [Ba5(H0.375L2)4(ClO4)(CH3CH2OH)(H2O)2](ClO4)2.5 x 9.5H2O and reveals the presence of four molecules of the ligand surrounding five Ba(II) ions, giving rise to an unusual structure with the metal ions inside a spherical organic cavity. 相似文献
43.
A dynamics study [cross section and microscopic mechanism versus collision energy (E(T))] of the reaction O+ + H2 --> OH+ + H, which plays an important role in Earth's ionosphere and interstellar chemistry, was conducted using the quasiclassical trajectory method, employing an analytical potential energy surface (PES) recently derived by our group [R. Martinez et al., J. Chem. Phys. 120, 4705 (2004)]. Experimental excitation functions for the title reaction, as well as its isotopic variants with D2 and HD, were near-quantitatively reproduced in the calculations in the very broad collision energy range explored (E(T) = 0.01-6.0 eV). Intramolecular and intermolecular isotopic effects were also examined, yielding data in good agreement with experimental results. The reaction occurs via two microscopic mechanisms (direct and nondirect abstraction). The results were satisfactorily interpreted based on the reaction probability and the maximum impact parameter dependences with E(T), and considering the influence of the collinear [OHH]+ absolute minimum of the PES on the evolution from reactants to products. The agreement between theory and experiment suggests that the reaction mainly occurs through the lowest energy PES and nonadiabatic processes are not very important in the wide collision energy range analyzed. Hence, the PES used to describe this reaction is suitable for both kinetics and dynamics studies. 相似文献
44.
A. Lainez M. M. Rodrigo Emmerich Wilhelm J. -P. E. Grolier 《Journal of solution chemistry》1992,21(1):49-65
Excess molar volumes V
E
and excess molar heat capacities C
P
/E
at constant pressure have been obtained, as a function of mole fraction x1, for several binary liquid mixtures belonging either to series I: pyridine+n-alkane (ClH2l+2), with l=7, 10, 14, 16, or series II: piperidine+n-alkane, with l=7, 8, 10, 12, 14. The instruments used were a vibrating-tube densimeter and a Picker flow microcalorimeter, respectively. V
E
of pyridine+n-heptane shows a S-shaped composition dependence with a small negative part in the region rich in pyridine (x1>0.90). All the other systems show positive V
E
only. The excess volumes increase with increasing chain length l of the n-alkane. The excess molar heat capacities of the mixtures belonging to series II are all negative, except for a small positive part for piperidine+n-heptane in the region rich in piperidine (x1>0.87). The C
P
/E
at the respective minima, C
P
/E
(x1,min
), become more negative with increasing l, and the x1,min
values range from about 0.26 (l=7) to 0.39 (l=14). Most interestingly, mixtures of series I exhibit curves of C
P
/E
against x1 with two minima and one maximum, the so-called W-shape curves.Dedicated to Professor A. Néckel on the occasion of his 65th birthday. Communicated in part at the XVIIèmes Journées de Calorimétrie, d'Analyse Thermique et de Thermodynamique Chimique, Ferrara, Italy, 27–30 October, 1986. 相似文献
45.
Jenny?ZevallosEmail author Alejandro?Toro-Labbé Otilia?Mó Manuel?Yá?ez 《Structural chemistry》2005,16(3):295-303
High level ab initio and density functional theory calculations have been carried out to investigate the relative stability of the different conformers of hyponitrous acid and its mono- and dithio-derivatives. Geometries and vibrational frequencies were obtained at the B3LYP/6-311+G(d,p) level and final energies through B3LYP/6-311++G(3df,2pd) single point calculations. The reliability of this theoretical scheme has been assessed by comparing these DFT results with those obtained at the G3 level of theory, for some suitable cases. The cis conformers of hyponitrous acid and its mono- and dithio-derivatives are systematically more stable than the
trans ones because in the cis conformation a dative interaction between the nitrogen-lone pairs and the σNX^* antibonding orbital is significantly favored. Quite interestingly, in general, the conformers presenting an intramolecular hydrogen bond (IHB) are not the global minima of the corresponding potential energy surfaces and only for hyponitrous acid the conformer with a OH ⋅s O IHB is slightly more stable than the cis conformer without IHB. The low stability of the tautomers with IHB is closely related with another weak intramolecular interaction which involves the lone-pairs of the chalcogen atoms and the πNN* antibondig orbital, and which is significantly perturbed when the IHB is formed. 相似文献
46.
47.
M. A. Sanz N. Granizo M. Gradzielski M. M. Rodrigo M. Valiente 《Colloid and polymer science》2005,283(6):646-652
We have made a comparative study between the micellar regions of the octyl -d-glucoside (OG)–tetraethylene glycol monododecyl ether and the OG–poly(ethylene glycol) 20,000 systems by means of surface tension and viscosimetric measurements. The incorporation of the tetraethylene glycol monododecyl ether nonionic surfactant in the OG micelles decreases the critical micelle concentration, whereas the presence of polymer increases it. The nonionic surfactant mixture exhibits nonideal mixing behaviour. The data fit to Rubinghs treatment with a value of –5.1, which implies a modest attraction between both surfactants. The surfactant–poly(ethylene glycol) 20,000 system does not form mixed micelles. The incorporation of polymer increases the critical micelle concentration of the surfactant. The viscosity for the surfactant–polymer system is higher than that for the pure polymer, demonstrating a surfactant-induced structuring. 相似文献
48.
Voltammetric behavior of zaleplon and its differential pulse polarographic determination in capsules
Larenas G Bollo S Rodriguez M Lemus I Nuñez-Vergara LJ Squella JA Alvarez-Lueje A 《Journal of AOAC International》2005,88(4):1135-1141
In this work both the electrochemical behavior and the analysis of the hypnotic pyrazolopyrimidine derivative zaleplon were studied. Zaleplon in ethanol-0.1M Britton Robinson buffer solution (30-70) showed 2 irreversible, well-defined cathodic responses in the pH range of 2-12 using differential pulse polarography (DPP), tast polarography, and cyclic voltammetry. From chronocoulometric studies, it was possible to conclude that one electron was transferred in each reduction peak or wave. For analytical purposes, the DPP technique working at pH 4.5 for peak I was selected, which exhibited adequate repeatability, reproducibility, and selectivity. The recovery was 99.97 +/- 1.52%, and the detection and quantitation limits were 5.13 x 10(-7)M and 1.11 x 10(-6)M, respectively. The DPP method was applied successfully to the individual assay of capsules in order to verify the content uniformity of zaleplon. Treatment of the sample is not required because the excipients do not interfere, the method is not time consuming, and it is less expensive than column liquid chromatography. 相似文献
49.
Quantum chemical calculations were carried out to study the interaction of hydrogen sulfide with molecular oxygen in the gas phase. The basic mechanism, the rates of reaction, and the potential energy surface were calculated. Isomers and transition states that connect the reactants with intermediates and products of reaction were identified using the G2 method and B3LYP/6-311+G(3df,2p) functional. Hydrogen abstraction to form HO2 + SH is the dominant product channel and proceeds through a loose transition state well-described at the level of calculation employed. The temperature dependence of the rate coefficient in the range 300-3000 K has been determined on the basis of the ab initio potential energy surface and with variational transition-state theory. The reaction is 169.5 kJ mol(-1) endothermic at 0 K with a rate constant given by 2.77 x 10(5) T(2.76) exp(-19 222/T) cm3 mol(-1) s(-1) and should proceed slowly under atmospheric thermal conditions, but it offers a route to the initiation of H2S combustion at relatively low temperatures. 相似文献
50.
Gray M Cuello AO Cooke G Rotello VM 《Journal of the American Chemical Society》2003,125(26):7882-7888
Two receptors, a diaminotriazine derivative (DAT) and diamidopyridine (DAP), are complementary to the electroactive naphthalimide (N) through three-point hydrogen bonding. The association constants of the two receptors were evaluated for both the fully oxidized and the radical anion forms of N. In the oxidized state, the two receptors displayed identical binding constants. Diamidopyridine, however, lowers the reduction potential of naphthalimide to a far greater extent than does diaminotriazine, indicating a greater affinity for diamidopyridine by naphthalimide in the radical anion form. This behavior was mirrored by EPR experiments that showed small deviations from the hyperfine coupling pattern of N(red) in the presence of DAT, with greater effects seen for the N(red).DAP complex. Computational simulations using the UB3LYP/6-311+G(d,p)//UHF/6-31G(d) hybrid gave theoretical hyperfine constants in good quantitative agreement with the experimental results. Using this correlation, we determined that electrostatics and hydrogen bond polarizability play key roles in controlling redox-modulated molecular recognition. 相似文献