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51.
52.
Even systems in which strong electron correlation effects are present, such as the large near-degeneracy correlation in a
dissociating electron pair bond exemplified by stretched H2, are represented in the Kohn–Sham (KS) model of non-interacting electrons by a determinantal wavefunction built from the
KS molecular orbitals. As a contribution to the discussion on the status and meaning of the KS orbitals we investigate, for
the prototype system of H2 at large bond distance, and also for a one-dimensional molecular model, how the electron correlation effects show up in the
shape of the KS σ
g
orbital. KS orbitals φHL and φFCI obtained from the correlated Heitler-London and full configuration interaction wavefunctions are compared to the orbital
φLCAO, the traditional linear combination of atomic orbitals (LCAO) form of the (approximate) Hartree-Fock orbital. Electron correlation
manifests itself in an essentially non-LCAO structure of the KS orbitals φHL and φFCI around the bond midpoint, which shows up particularly clearly in the Laplacian of the KS orbital. There are corresponding
features in the kinetic energy density t
s
of the KS system (a well around the bond midpoint) and in the one-electron KS potential v
s
(a peak). The KS features are lacking in the Hartree-Fock orbital, in a minimal LCAO approximation as well as in the exact
one.
Received: 11 December 1996 / Accepted: 10 January 1997 相似文献
53.
54.
Electrochemical impedance spectroscopy is used to characterize thin p-doped polypyrrole (PPy) films in propylene carbonate (PC) solutions and poly(trifluorophenyl)thiophene (PTFPT), in solutions based on sulfolane (SF). It appears that the latter film is much less swelled compared to the former one. One consequence of this difference is that the PTFPT film shows a much higher bulk resistance compared to that for the PPy film. Another important consequence is that the swelling of the PTFPT film is essentially physically non-homogeneous. Two parallel, uncoupled paths, with different chemical diffusion coefficients, model the experimental results adequately. In order to quantify the impedance spectra for both polymer films, we use a model proposed by Rubinstein et al. explaining the difference in the diffusion coefficients of Ru(bpy)3+/2+
3 within a thin Nafion film. The model can also predict the impedance spectra for composite powdery electrodes containing different particle sizes, such as composite cathodes and graphite anodes used in lithium batteries. 相似文献
55.
56.
Mathematical apparatus, which makes it possible to perform calculations of the current-voltage characteristics of cathodes of fuel cells with a solid polymer electrolyte in conditions where there are present extraneous diffusion restrictions is proposed. In so doing, the partial pressure of oxygen and the absolute pressure of gas in the gas chamber may assume any values. First of all presented are the results of calculations of the current-voltage characteristics intrinsic to active layers of the air and oxygen cathodes, which are performed under the assumption that the extraneous diffusion restrictions are absent altogether. Thereafter, in the same conditions (at the same parameters that characterize the active layer of a cathode), obtained are results of a calculation of the current-voltage characteristics inherent in the air and oxygen cathodes in the presence of extraneous diffusion restrictions. Afterward there is performed an analysis of the way a gas-diffusion layer restricts the process of generation of current in a cathode and of what measures should be taken in order for the extraneous diffusion restrictions to become less significant. 相似文献
57.
Garavelli M Ruggeri F Ogliaro F Bearpark MJ Bernardi F Olivucci M Robb MA 《Journal of computational chemistry》2003,24(11):1357-1363
MMVB is a QM/MM hybrid method, consisting of a molecular mechanics force field coupled to a valence bond Heisenberg Hamiltonian parametrized from ab initio CASSCF calculations on several prototype molecules. The Heisenberg Hamiltonian matrix elements Q(ij) and K(ij), whose expressions are partitioned here into a primary contribution and second-order correction terms, are calculated analytically in MMVB. When the original MMVB force field fails to produce potential energy surfaces accurate enough for dynamics calculations, we show that significant improvements can be made by refitting the second-order correction terms for the particular molecule(s) being studied. This "local" reparametrization is based on values of K(ij) extracted (using effective Hamiltonian techniques) from CASSCF calculations on the same molecule(s). The method is demonstrated for the photoisomerization of s-cis butadiene, and we explain how the correction terms that enabled a successful MMVB dynamics study [Garavelli, M.; Bernardi, F.; Olivucci, M.; Bearpark, M. J.; Klein, S.; Robb, M. A. J Phys Chem A 2001, 105, 11496] were refitted. 相似文献
58.
《Arabian Journal of Chemistry》2020,13(10):7289-7301
Black pepper oils have been investigated frequently in the recent years. However, there is a significant variation in physicochemical properties and bioactivity of oils depended on extraction techniques. In this study, the systemic investigation of four various extraction methods was performed to evaluate the physicochemical characterizations, antioxidant and antibacterial activity. The investigation of 1H NMR, FTIR and UV–Vis spectra confirmed presence of non-volatile components in oils extracted through supercritical CO2 and hexane-soaking extractions which induced their typical thermal properties. The isothermal behaviour of extracted oils related to evaporation was within range of 3.2–7.3% (w/w) at 27 °C. The SEM images of the black pepper confirmed different operation manners of mechanism between extractions using the solvents and heating process. The lowest MIC for both essential oils from conventional hidrodistillation and microwave-assisted hidrodistillation against two bacteria including E. coli and B. subtilis were found to be 137 µg mL−1. The non-isothermal decomposition kinetics were investigated on the essential oil of microwave-assisted hydrodistillation extraction. The activation energies and pre-exponent factors of non-isothermal decomposition were found to be in range of 36.5–73.7 KJ mol−1 and 4.98 × 103–1.97 × 108 s−1, respectively, dependent on conversional fractions of the oil. The results revealed that chemical components, physicochemical properties and bioactivity of black pepper essential oils depended on the extraction techniques. 相似文献
59.
金属/氮/碳催化剂(M/N/C,M=Fe、Co等)是最有发展前景的非贵金属电催化剂之一,其性能依赖于催化剂表面的活性物种密度.通过常规的热解含氮前驱物与金属盐的方法制得的催化剂往往存在金属活性物种被包埋而不能有效利用的缺点.考虑到石墨相氮化碳(g-C3N4)富含类吡啶氮和亚纳米孔腔结构,将g-C3N4包覆在高导电性碳纳米笼(hCNC)表面,进而利用表层g-C3N4的配位和限域作用锚定大量Co2+离子,获得的Co/g-C3N4/hCNC复合物经热解后形成了活性位高度暴露、导电性好、孔结构丰富的Co/N/C催化剂.800℃热解得到的最优化催化剂在碱性介质中展现出优异氧还原活性,其起始电位(0.97 V)与商业Pt/C催化剂相当,且抗甲醇干扰性能和稳定性优异.此项研究提供了一种构建具有高度暴露活性位的M/N/C催化剂的有效策略. 相似文献
60.
《Arabian Journal of Chemistry》2022,15(4):103712
Although recent decades have witnessed the synthesis of 1,3,4-thiadiazoles via phosphorus POCl3-promoted cyclization reaction, simultaneous access to 2-amino-1,3,4-thiadiazole and 2-amino-1,3,4-oxadiazole analogs remains unexpected and elusive. Herein, a detailed regiocontrolled synthesis of 2-amino-1,3,4-thiadiazoles in good to high yields with good regioselectivities from readily available thiosemicarbazides using POCl3 was disclosed. Meantime, to establish a comprehensive structure–activity relationship, 2-amino-1,3,4-oxadiazole derivatives as single regioisomers were prepared via EDCI·HCl-triggered cyclization of the thiosemicarbazide intermediates. The in vitro anti-influenza assays proved that the selected compounds with the pyrazine/pyridine ring exhibited certain inhibitory activities against influenza A virus strains A/HK/68 (H3N2) and A/PR/8/34 (H1N1) in MDCK cells. Among them, N-(adamantan-1-yl)-5-(5-(azepan-1-yl)pyrazin-2-yl)-1,3,4-thiadiazol-2-amine (4j) was the most active compound, and exhibited favorable activity with EC50 values of 3.5 μM and 7.5 μM, respectively. In addition, the molecular docking results explained the reason why compound 4j had dual inhibitory activity and revealed the reasonable binding mode of this compound with the M2-S31N and M2-WT ion channels. This compound had the potential to be further developed as an anti-influenza drug. 相似文献