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71.
72.
Branko S. Jursic 《Theoretical chemistry accounts》1998,99(5):289-294
A computational study of perfluorinated methane derivatives was performed with complete basis set ab initio methods. The
total energies for their neutral, cation, and anionic states were computed. From these values, the energy gaps between different
electronic states, ionization potentials, electron affinities, and C-F bond dissociation energies were calculated. The computed
values are compared with experimental data and the reliability of complete basis set ab initio methods is discussed. New values
for C-F bond dissociation energies are suggested.
Received: 12 January 1998 / Accepted: 2 April 1998 / Published online: 29 July 1998 相似文献
73.
Summary The first-order polarized basis sets for the use in high-level-correlated investigations of molecular electric properties have been generated for Pb, Bi, Po, and At. The performance of the standard [10.17.14.5/13.11.8.2] and extended [20.17.14.9/13.11.8.4] basis sets has been examined in nonrelativistic and quasirelativistic calculations for atoms and simple closed-shell hydrides. The relativistic contributions to electric dipole properties of those systems have been evaluated by using the recently developed quasirelativistic scheme. The predicted dipole polarizability of At is in good agreement with the results of other relativistic calculations. The calculated quasirelativistic dipole moments of BiH3 (–0.499 a.u.), PoH2 (–0.207 a.u.), and AtH (+0.036 a.u.) involve a significant relativistic contribution which amounts to —0.230 a.u., –0.177 a.u., and –0.097 a.u., respectively. The basis set details append this paper. They are also available as a part of the basis set library of the MOLCAS system. 相似文献
74.
Hydrolyses of phosphorus halides, (RO)(2)POX where R = H or Me and X = F or Cl, in the gas phase and in the reaction field have been investigated theoretically with ab initio and the density functional theory (DFT). The free energy of activation in the reaction field was also estimated using the Onsager method with a correction of entropy change and basis set superposition error (BSSE). The reaction of (MeO)(2)POF proceeds through a path with bifunctional catalysis regardless of the medium, but the reaction of (MeO)(2)POCl proceeds through bifunctional and general base catalysis in the gas phase and in water, respectively. The estimated free energy barrier of 23 kcal/mol for the hydrolysis of (MeO)(2)POF is in good agreement with the experimental values of 24 kcal/mol, and relative barrier of 3 kcal/mol to the (MeO)(2)POCl is also in good agreement with the experimental values of 5 kcal/mol of diisopropyl phosphorus halides ((Pr(i)O)(2)POX, X = F and Cl). 相似文献
75.
磺化丁基橡胶离聚体在混合溶剂中的聚集行为 总被引:1,自引:0,他引:1
用顺磁共振(ESR)谱和粘度法考察了磺化丁基橡胶离聚体在二甲苯/正己醇混合溶剂中的聚集行为.ESR谱表明离聚体的离子基团发生聚集,其聚集程度受极性共溶剂(正己醇)的影响.粘度考察表明,在不同的浓度时离子基团有不同的聚集形式,低浓度时以分子内聚集为主,高浓度时以分子间聚集为主.离聚体的聚集度(DA)与浓度(c)的关系可用经验式DA=Aexp(kc2)表示,其中A、k为常数.k值反映聚集度受浓度影响的程度,醇含量增大时k值减小,这是因为醇对离子的溶剂化作用导致离子聚集的倾向减小. 相似文献
76.
使用了不同密度泛函方法计算X-H (X = C, N, O, Si, P, S) 键离解能,并分析不同密度泛函方法的计算精度。研究发现大多数密度泛函方法包括B3LYP, B3P86, B3PW91, G96LYP, PBE1PBE,和BH&HLYP都明显低估键离解能13-25 kJ/mol。该现象与是否使用无限基组无关,因为即使使用无限基组键离解能仍然被低估。因此密度泛函方法不适合用于键离解能的估算。其中B3P86方法的偏差最小。进一步分析表明,使用限制性开壳层计算并无任何优势,在大多数情况下非限制性开壳层计算实际上比限制性开壳层计算要好。最后,我们发现了密度泛函方法对键离解能的低估是系统的,因此建议利用校准后的UDFT/6-311++G(d, p)方法计算化学键离解能。 相似文献
77.
K. J. Hyver 《Journal of separation science》1988,11(1):69-72
For clinical and environmental analyses utilizing capillary gas chromatography/mass spectrometry (GC/MS), increased sensitivity and speed of analysis are highly desirable. These performance advantages are realized using a WCOT column of 100 μm i.d. as compared to the more conventional 200 μm i.d. capillary columns. The improved sensitivity of capillary direct GC/MS with the 100 μm i.d. column for the confirmation of drugs of abuse will be demonstrated. For environmental analysis, the superior efficiency and resolution of the 100 μm i.d. column can be employed for the separation of priority pollutants. This approach is more amenable to capillary direct GC/MS providing a more effective interface to the mass spectrometer. As a result improved sensitivity and a considerable decrease in analysis time is achieved over that obtained with the larger diameter environmental specialty phase columns. 相似文献
78.
T. A. Isaev N. S. Mosyagin A. V. Titov A. B. Alekseyev R. J. Buenker 《International journal of quantum chemistry》2002,88(5):687-690
The correlation calculation of the electronic structure of PbH is carried out with the generalized relativistic effective core potential (GRECP) and multireference single‐ and double‐excitation configuration interaction (MRD‐CI) methods. The 22‐electron GRECP for Pb is used and the outer core 5s, 5p, and 5d pseudospinors are frozen using the level‐shift technique, so only five external electrons of PbH are correlated. A new configuration selection scheme with respect to the relativistic multireference states is employed in the framework of the MRD‐CI method. The [6, 4, 3, 2] correlation spin–orbit basis set is optimized in the coupled cluster calculations on the Pb atom using a recently proposed procedure, in which functions in the spin–orbital basis set are generated from calculations of different ionic states of the Pb atom and those functions are considered optimal that provide the stationary point for some energy functional. Spectroscopic constants for the two lowest‐lying electronic states of PbH (2Π1/2, 2Π3/2) are found to be in good agreement with the experimental data. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
79.
This paper presents a method for the construction of a graphene paste electrode (GPE) from reduced graphene oxide (RGO). The GPE was successfully used for the determination of medetomidine. The influence of some experimental variables such as pH, supporting electrolyte, scan rate, and possible interferences were studied. Differential pulse voltammetric (DPV) peak currents of medetomidine increased linearly with its concentration in the range from 0.009 to 2.5 µM. The limit of detection (LOD) and limit of quantitation (LOQ) values for the determination of medetomidine were 2.8 and 9.2 nM, respectively. Also, for the first time, the electroreduction behavior of medetomidine was investigated. 相似文献
80.
Yury Yu. Rusakov Irina L. Rusakova Leonid B. Krivdin 《Magnetic resonance in chemistry : MRC》2014,52(5):214-221
Four‐component relativistic calculations of 77Se–13C spin–spin coupling constants have been performed in the series of selenium heterocycles and their parent open‐chain selenides. It has been found that relativistic effects play an essential role in the selenium–carbon coupling mechanism and could result in a contribution of as much as 15–25% of the total values of the one‐bond selenium–carbon spin‐spin coupling constants. In the overall contribution of the relativistic effects to the total values of 1J(Se,C), the scalar relativistic corrections (negative in sign) by far dominate over the spin‐orbit ones (positive in sign), the latter being of less than 5%, as compared to the former (ca 20%). A combination of nonrelativistic second‐order polarization propagator approach (CC2) with the four‐component relativistic density functional theory scheme is recommended as a versatile tool for the calculation of 1J(Se,C). Solvent effects in the values of 1J(Se,C) calculated within the polarizable continuum model for the solvents with different dielectric constants (ε 2.2–78.4) are next to negligible decreasing negative 1J(Se,C) in absolute value by only about 1 Hz. The use of the locally dense basis set approach applied herewith for the calculation of 77Se–13C spin‐spin coupling constants is fully justified resulting in a dramatic decrease in computational cost with only 0.1–0.2‐Hz loss of accuracy. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献