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911.
The electronic spectrum of VCr has been studied using the complete-active-space self-consistent field complete-active-space second-order perturbation theory approach. Potential-energy curves for 12 electronic states have been computed. Transition energies, with respect to the X2 ground state, for some of the calculated electronic states are (with possible experimental values within parentheses) 0.53 eV (0.56) for A2+, 1.03 eV (1.14) for A4, 1.20 eV (1.14) for B2, 1.45 eV (1.51) for B4, 1.60 eV (1.51, 1.78) for C2, and 1.61 eV (1.63) for A4–.
AcknowledgementsThe research reported in this communication was supported by a grant from the Swedish Natural Science Research Council (NFR). S. Alex and D.G. Leopold are acknowledged for providing results from their negative ion photoelectron spectroscopy on VCr.Contribution to Björn Roos Honorary Issue 相似文献
912.
Ivan Gutman 《Monatshefte für Chemie / Chemical Monthly》1989,120(12):1043-1047
Summary The recently proposed statistical method for the calculation of resonance energies in the conjugated circuit theory is tested on the example of polyacenes. It is found that for the estimation of the resonance energy with a 10% average error, the method requires a sample consisting of about 20 (randomly chosen) Kekulé structures. Further increase of the sample size gives no significant gain in the accuracy of the method.
Überprüfung der statistischen Methode in der Konjugierten-Ring-Theorie
Zusammenfassung Die unlängst vorgeschlagene statistische Methode in der Konjugierten-Ring-Theorie (conjugated circuit theory) wird am Beispiel der Polyacene getestet. Es wurde festgestellt, daß für die Abschätzung der Resonanzenergien bei einem mittleren Fehler von 10% für diese Methode ungefähr 20 (willkürlich gewählte) Kekulé-Strukturen nötig sind. Weitere Erhöhung dieser Anzahl bringt keine signifikante Verbesserung der Genauigkeit der Methode.相似文献
913.
HCN(HNC)与NH3, H2O和HF分子间相互作用的理论研究 总被引:1,自引:0,他引:1
在MP2/aug-cc-pVTZ水平上, 对HCN(HNC)与NH3, H2O和HF分子间可能存在的氢键型复合物进行了全自由度能量梯度优化, 通过在相同水平上的频率验证分析发现了稳定的分子间相互作用形式是HCN(HNC)作为质子供体或作为质子受体形成的复合物. 基组重叠误差对总相互作用能的影响均小于3.34 kJ/mol. 通过自然键轨道(NBO)分析, 研究了单体和复合物中的原子电荷和电荷转移对分子间相互作用的影响. 对称性匹配微扰理论(SAPT, Symmetry Adapted Perturbation Theory)能量分解结果表明, 在分子间相互作用中, 静电作用与诱导作用占主导地位, 而诱导作用与复合物的电荷转移之间具有良好的正相关性. 相似文献
914.
A mathematical representation based on a linear elastic theory is proposed by which one may investigate the dependences of molecular orientation and crystallinity on the crystal lattice moduli and linear thermal expansion coefficients in the direction perpendicular to the chain axis as commonly measured by x-ray diffraction. In the theoretical calculation, a previously introduced model was employed in which oriented crystalline phase is surrounded by oriented amorphous phase and the strains of the two phases at the boundary are identical. The mathematical analysis indicated that the lateral crystal lattice moduli and linear thermal coefficients as measured by x-ray diffraction may be different from the intrinsic crystal moduli and linear thermal coefficients of a crystal unit cell, depending on the structure of the polymer solid. The numerical calculation was applied to nylon 6. As a result, it may be confirmed that the lateral crystal lattice moduli measured by x-ray diffraction are sensitive to the morphology of the bulk speciments and close to the intrinsic crystal moduli if the morphology of the test specimen can be represented by a parallel model with respect to the original stretching longitudinal direction. 相似文献
915.
A general partial summation method for including arbitrary classes of diagrams to all orders in the coupled cluster based size consistent energy functional for closed shell states is developed. Since the various reduced density matrices which appear in the energy functional are essentially the time-independent analogues of the corresponding many body Green functions, it is possible to derive Dyson-like equations for these quantities. By expanding the associated proper self energy parts in terms of the T-amplitudes, one can carry out partial summations in the reduced density matrices and thus in energy. At a higher level, higher order terms in a proper self energy can also be generated by renormalizing the internal propagators in it, and considering only the irreducible self-energy terms. 相似文献
916.
917.
The optimized structures and proton transfer reactions of 3-methyl-5-hydroxyisoxazole and its water complexes (3-M-5-HIO · (H2O)n · (n = 0–3)) were computed at B3LYP and MP2 theoretical level. The results indicates that 3-M-5-HIO has four isomers (Ecis, Etrans, K1 and K2), and the keto tautomer, and K2 is the most stable isomer in the gas phase. Hydrogen bonding between 3-M-5-HIO and the water molecules can dramatically lower the barrier by the concerted transfer mechanism. Ecis · (H2O)3 → K1 · (H2O)3 and Ecis · (H2O)2 → K2 · (H2O)2 is found to be very efficient. Comparing with the proton transfer mechanism of 5-HIO shows that the methyl substitution prevents the intramolecular proton transfer. 相似文献
918.
Influence
of heating rate on kinetic quantities of solid phase thermal decomposition 总被引:1,自引:0,他引:1
Thermogravimetric
analyses of thermal decomposition (pyrolysis, thermal dissociation and combustion)
of 9 different samples were carried out in dynamic conditions at different
heating rates. The kinetic parameters (E, A and km)
of thermal decomposition were determined and interrelations between the parameters
and heating rate q were analyzed. There
were also relations between Arrhenius and Eyring equations analyzed for thermal
decomposition of solid phase. It was concluded that Eyring theory is an element,
which interconnects used thermokinetic equations containing Arrhenius law
and suggests considering kinetic quantities in way relative to 3 kinetic constants
(E, A
and km). Analysis
of quantities other than km (i.e. E, A, Δ+H, Δ+S) in relation to heating rate is an incomplete method
and does not lead to unambiguous conclusions. It was ascertained that in ideal
case, assuming constant values of kinetic parameters (E
and A) towards heating rate and satisfying
both Kissinger equations, reaction rate constant km
should take on values intermediate between constants (km)1
and (km)2
determined from these equations. Whereas behavior of parameters E and A towards q were not subjected to any rule, then plotting relation km vs. q in the background of (km)1
and (km)2
made possible classification of differences between thermal decomposition
processes taking place in oxidizing and oxygen-free atmosphere. 相似文献
919.
B3LYP/6-31G* density functional theory calculations have been carried out on the structure and stability of ten B20N20 clusters. It was found that two new proposed isomers with two octagons, twelve hexagons, eight squares in Cab and C2 symmetry were more stable than the isomer with sixteen hexagons and six squares in C2 symmetry which was previously deemed to the most stable by 79.5 and 13.8 kJ/mol respectively. The isomer with two decagons in S10 symmetry is much higher in energy than the most stable structure in C4h symmetry by 637.2 kJ/mol. 相似文献
920.
S. F. Ruzankin V. F. Anufrienko S. A. Yashnik Z. R. Ismagilov 《Journal of Structural Chemistry》2006,47(3):404-412
This paper reports on quantum-chemical analysis of the linear structure of CuCl2 by Hartree-Fock (HF) and density functional theory (DFT) methods and also by time-dependent HF (TD HF) and DFT (TD DFT) techniques. Using pure DFT exchange correlation functional (B3LYP) yields the best agreement with the experimental electronic spectra of CuCl2. In this case, the odd electron is delocalized over the molecule, spin density on copper being 0.27. The ground state of the CuCl2 molecule is 2Πg with linear geometry. 相似文献