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261.
The molecular structure of trichloronitromethane has been studied in the gas phase using electron diffraction data. The molecules are found to undergo low barrier rotation about the CN bond with a planar CNO2 moiety in agreement with HF/MP2/B3LYP/6-311G(d,p) calculations. The experimental data are consistent with a dynamic model using a potential function for the torsion of V = (V6/2)(1 − cos 6τ). The major geometrical parameters (rg and ) for the eclipsed form, obtained from least squares analysis of the data are as follows: r(NO3) = r(NO4) = 1.213(2) Å, r(CN) = 1.592(6) Å, r(CCl)av = 1.749(1) Å, Cl5CN/Cl6CN = 109. 6°/106.3°(2), O3NC/O4NC = 117. 6°/114.1°(4), τCl5C1N2O3 = 0.0°, and V6 = 0.20(25) kcal/mol. 相似文献
262.
Ye Xu Dr. Huifeng Yao Lijiao Ma Ling Hong Jiayao Li Qing Liao Yunfei Zu Jingwen Wang Mengyuan Gao Prof. Long Ye Prof. Jianhui Hou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9089-9095
Decreasing the energy loss is one of the most feasible ways to improve the efficiencies of organic photovoltaic (OPV) cells. Recent studies have suggested that non-radiative energy loss ( ) is the dominant factor that hinders further improvements in state-of-the-art OPV cells. However, there is no rational molecular design strategy for OPV materials with suppressed . Herein, taking molecular surface electrostatic potential (ESP) as a quantitative parameter, we establish a general relationship between chemical structure and intermolecular interactions. The results reveal that increasing the ESP difference between donor and acceptor will enhance the intermolecular interaction. In the OPV cells, the enhanced intermolecular interaction will increase the charge-transfer (CT) state ratio in its hybridization with the local exciton state to facilitate charge generation, but simultaneously result in a larger . These results suggest that finely tuning the ESP of OPV materials is a feasible method to further improve the efficiencies of OPV cells. 相似文献
263.
With the introduction of the concept of the iso‐spectrum‐level series, a linear relationship is found between the first differences of the ionization potential of excited states and nuclear charge Z along an iso‐spectrum‐level series, and the ionization potential of excited states of Be‐like sequence are studied systematically on the basis of the weakest bound electron potential model theory. The expression of nonrelativistic ionization potential is derived from the weakest bound electron potential model theory, and relativistic effects are included by using a fourth‐order polynomial in Z. As a demonstration, the ionization potentials of [He]2s2p 3P, [He]2s3s 1S0, [He]2s3p 1P, [He]2s3d 1D2, and [He]2s4d 1D2 series for a range of Be‐like sequence from Z = 4–23 are calculated. The results are compared with the experimental data and the recent sophisticated ab initio results. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 344–350, 2003 相似文献
264.
The computational results for curcumin at the B3LYP/6-31G(d,p) level show that the enol form of curcumin is more stable than the diketo form because of an intramolecular hydrogen bond, which extends the conjugation effect in the enol chain, formed in the enol structure. Cis-diketone form can not be obtained, presumably due to the strong repulsion between the carbonyl dipoles aligned in parallel. According to the phenolic O-H bond dissociation enthalpy, curcumin in its most stable form can be suggested to be a relatively good antioxidant. In order to avoid overcoming H-bond interaction and to improve the antioxidant activity of curcumin, a catechol moiety was incorporated into curcumin for designing a novel antioxidant. It is found that the designed molecule is much more efficient to scavenge radical than curcumin, comparable to vitamin E. Moreover, the ionization potential of the designed molecule is similar to that of curcumin, indicating that the designed molecule can not display the prooxidant effect. 相似文献
265.
IR spectra of 24 structural isomers of (HF)
n
(n=4–8) clusters were calculated in the framework of semiempirical theory of polyatomic molecule vibrations. Based on the results
obtained and available experimental data it is proposed that (HF)
n
associates comprising 3–5-membered cycles with attached monomeric HF units are present in molecular beams and gas phase.Ab initio calculations performed by the SCF method show the existence of local minima corresponding to such structures on the potential
energy surface of (HF)
n
clusters (n=4–6).
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 435–443, March, 1997. 相似文献
266.
Summary The solution of the Schrödinger equation for diatomic molecules when the finite element method is used gives the possibility to evaluate highly accurate basis-independent potential energy curves. In this work such types of numerically accurate potential energy curves on the HF level have been evaluated for Li2, Na2 and K2 and could be used as benchmarks in the optimization of basis sets. A comparison between recent LCAO HF calculations in which extended basis sets are used and the accurate values determined in this work show that there is a difference in total energy of 4×10–5 and 10–3 a.u. for Li, Li2, and Na, Na2, respectively. Evaluated dissociation energies are, however, due to the cancellation of numerical errors in much better agreement. Further, it is found that different exchange correlation potentials for the heavier molecules such as those given by von Barth-Hedin and Vosko, Wilk and Nusair reproduce experimental properties such as dissociation energies, vibrational frequencies almost as well as those achieved with advanced CI methods. TheX potential gives accurate bond lengths for Na2 and K2, whereas the dissociation energies are too small. 相似文献
267.
《Surface and interface analysis : SIA》2005,37(9):737-742
A novel method that allows the determination of the electrical potential of a polymer surface has been applied for polypropylene film treated by N2 + H2 cold plasma. The plasma treatment results in formation on the film surface of NH2 groups, which then gets transformed to NH3+ in contact with an electrolyte and leads to the formation of an electrical double layer. The method consists of theoretical calculation of electrical model potential, using the measurement of the electrical capacitance of the film in contact with an electrolyte by dielectric spectroscopy. Comparison with the results obtained by theoretical model shows similar dependencies of the electrical potential as a function of amino‐groups density and electrolyte concentration, but systematic differences of absolute values are observed. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
268.
Paul G. Mezey 《Theoretical chemistry accounts》1985,67(1):43-61
The family of all possible reaction mechanisms on a potential surface has an algebraic structure with potential applications in quantum chemical molecular design and synthesis planning.Transformation properties and equivalence relations of reaction paths on potential energy hypersurfaces lead to a topological definition of reaction mechanisms. The family of all fundamental reaction mechanisms on the hypersurface has a group structure,the fundamental group of an appropriately defined topological space. Isomorphism and homomorphism relations between fundamental groups of reaction mechanisms are used to characterize the chemically important topological properties of various subsets of a hypersurface, or those of different excited state hypersurfaces. 相似文献
269.
CHANG Kai-Guo LU Xiang-Ping DU Fu-Ying ZHAO Min-ShouChangchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun Jilin China 《中国化学》1994,(6)
The apparent standard potential of Dy/Dy(III) system in the LiCl-KCl eutectic has been determined by the logarithmic analysis of the semi-integrals of voltammograms, logarithmic analysis of chronopotentiograms and the open circuit potentiometry. The dysprosium equilibrium potentiab for various concentration of dysprosium chloride in the LiCl-KCl eutectic melt between 400-500℃ were first determined experimentally, and the apparent standard potential of this system and its temperature dependance have been calculated. 相似文献
270.
Maksymilian Ignaczak Andrzej Grzejdziak Barbara Olejniczak 《Monatshefte für Chemie / Chemical Monthly》1989,120(6-7):515-527
Summary The conditional protonation constants (=0.1) for 2,2:6,2-terpyridine, logK
1=4.93, logK
2=3.69, were determined by thepH-metric method. The compositions of complexes of Ag2+ and Ag+ ions with 2,2:6,2-terpyridine (tp) were studied and equilibria of the complex formation process were described. The values of conditional complex formation constants are as follows: for Ag(tp)
2
+
:log01=5.79, log02=9.68, for Ag(tp)
2
2+
:log02=25.31, while the conditional constant of the Ag(tp)NO3 precipitate formation is:K
SO=2.45·104. Using coulometric and chronovoltamperometric measurements, the redox systems being formed in the complex solutions of Ag(II) and Ag(I) were determined and described including their formal potentials.
Komplexibildungsgleichgewichte und Redoxpotentiale des Systems Ag(II)/Ag(I) in Gegenwart von 2,2:6,2-Terpyridin in Wasser
Zusammenfassung Mit Hilfe derpH-metrischen Methode wurden die konditionalen Protonationskonstanten (=0.1) von 2,2:6,2-Terpyridin bestimmt: logK 1=4.93, logK 2=3.69. Es wurde auch die Zusammensetzung der Komplexe von Ag(II) und Ag(I) mit 2,2:6,2-Terpyridin(tp) bestimmt sowie die Gleichgewichte der komplexbildung beschrieben. Die Werte der Konditionalkomplexbildungskonstanten sind: für Ag(tp) 2 + :log01=5.79, log02=9.68, für Ag(tp) 2 2+ :log02=25.31 und für das Löslichkeitsprodukt Ag(tp)NO3:K SO –1 =4.08·10–5. Die in Komplexlösungen von Ag(II) und Ag(I) vorliegenden Redoxsysteme wurden mittels cyclischer Voltametrie und Coulometrie untersucht und die Formalpotentialwerte dieser Systeme in Wasser bestimmt.相似文献