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301.
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
302.
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
303.
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
304.
Egorochkin A. N. Voronkov M. G. Skobeleva S. E. Zderenova O. V. 《Russian Chemical Bulletin》2001,50(1):35-42
The first vertical ionization potentials (I) of phosphorus compounds P(Xi)3, OP(Xi)3, SP(Xi)3, (4-XC6H4)3P, and PCX are related to the inductive, resonance, and polarizability parameters of inorganic, organic, and organometallic substituents X by dependences of the type I = I
H + aI + bR
+ + c, where I
H is the I value for X = H. The I values are also affected by hyperconjugation. The ratio of the contributions of the resonance (bR
+) and polarizability (c) effects to the I value is determined by the degree of delocalization of the unpaired electron and the positive charge in the radical cations formed upon ionization of neutral molecules. The R
+ resonance parameters of organosilicon, organogermanium, and organotin substituents bound to the P
·+ radical cation center were calculated for the first time. 相似文献
305.
Geometrical parameters associated with N-H ... N types of hydrogen bonds have been analysed using crystal structure data on
nucleic acids, amino acids and related compounds. Histograms depicting the frequency distribution of N-H ... N length (l) and H-N ... N angle (θ) have been drawn and conclusions on the favoured geometry of such bonds have been arrived at. The
distribution ofl shows a pronounced maximum in the range between 2.9? and 3.0? with an overall average of 2.98 ?. The θ distribution shows
a pronounced maximum for the hydrogen bond angle in the range 0°-10°, with a rapid fall-off in frequency for nonlinear hydrogen
bonds. The frequency shows a cos6θ dependence as compared to cos2θ dependence term used earlier to predict the angular dependence of hydrogen bond potential energy in proteins and polypeptides. 相似文献
306.
G. I. Berezin G. A. Petukhova N. S. Polyakov M. L. Gubkina 《Russian Chemical Bulletin》1997,46(3):443-447
The state of water adsorbed on active carbons and canal soot was studied using the “chemical potential—entropy—temperature”
diagram. In the range of the relative pressures from 0.174 to 1, the state of adsorbed water is similar to the state of a
stretched liquid. The molar volume, heat of evaporation, and surface tension of stretched water were calculated at different
relative pressures. Near the spinodal, the molar volume of stretched water is 25% higher, and the surface tension is considerably
lower compared to water.
Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 464–468, March, 1997. 相似文献
307.
Dr. Aaron R. Finney Dr. Sébastien Lectez Dr. Colin L. Freeman Prof. John H. Harding Dr. Stephen Stackhouse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8725-8740
A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and many more fields. This is particularly true for minerals processing, given governmental concerns about lanthanide security of supply and the drive to identify environmentally sustainable processing routes. Despite much effort, even in simple systems, the mechanisms and thermodynamics of LnIII association with small anions remain unclear. In the present study, molecular dynamics (MD), using a newly developed force field, provide new insights into LnCl3(aq) solutions. The force field accurately reproduces the structure and dynamics of Nd3+, Gd3+ and Er3+ in water when compared to calculations using density functional theory (DFT). Adaptive-bias MD simulations show that the mechanisms for ion pairing change from dissociative to associative exchange depending upon cation size. Thermodynamics of association reveal that whereas ion pairing is favourable, the equilibrium distribution of species at low concentration is dominated by weakly bound solvent-shared and solvent-separated ion pairs, rather than contact ion pairs, reconciling a number of contrasting observations of LnIII–Cl association in the literature. In addition, we show that the thermodynamic stabilities of a range of inner sphere and outer sphere coordination complexes are comparable and that the kinetics of anion binding to cations may control solution speciation distributions beyond ion pairs. The techniques adopted in this work provide a framework with which to investigate more complex solution chemistries of cations in water. 相似文献
308.
The ground state of the van der Waals-type lanthanide dimer Yb2 has been studied by means of relativistic energy-consistent ab initio pseudopotentials using three different core definitions.
Electron correlation was treated by coupled-cluster theory, whereby core-valence correlation effects have been accounted for
either explicitly by correlating the energetically highest coreorbitals or implicitly by means of an effective core-polarization
potential. Results for the first and second atomic ionization potentials, the atomic dipole polarizability, and the spectroscopic
constants of the molecular ground state are reported. Low-lying excited states have been investigated with spin-orbit configuration
interaction calculations. It is also demonstrated for the whole lanthanide series that correlation effects due to the atomic-like,
possibly open 4f-shell in lanthanides can be modeled effectively by adding a core-polarization potential to pseudopotentials attributing the
4f-shell to the core.
Received: 3 April 1998 / Accepted: 27 July 1998 / Published online: 9 October 1998 相似文献
309.
Dr. E. L. Mehler 《Theoretical chemistry accounts》1974,35(1):17-32
A new method is proposed for calculating correlation effects in atomic and molecular systems. The basis of the method is the
formulation of a set of partial configuration expansions which yield directly variational orbital correlation corrections
which are appropriately summed in order to obtain an estimate of the total correlation energy. This method is applied to the
ground state of boron hydride and its cation at the equilibrium distance of BH. The results of the method are compared in
detail with independent electron pair results and second order CI results. It is further shown that multiple substitutions
are approximately accounted for in this method and the extent to which they are included is compared with other approximations.
Finally, three methods of increasing accuracy, aimed at reducing the necessary computational effort, are given for determining
the vertical ionization potential. The most economical method yields an IP of 9.70 eV or 0.03 eV less than the experimental
IP. Completion of the basis is estimated to improve this value to 9.77 eV. 相似文献
310.
The recently proposed electron-hole potential (EHP) method for excited states is extended to the multi-configurational case. The variation equation is solved using the quadratic convergence method. The EHP methods are shown to be approximations to the complete singly excited configuration interaction (CSECI) in the variational sense. Extended Brillouin theorems are proved for the EHP methods. The excitation energies and wave functions obtained by one and two configurational EHP methods agree well with those of the CSECI method. The EHP methods have clear advantage in the computer time requirement over the CI method and are especially suited for a calculation of approximate excited states of large molecules. The EHP methods are applicable to excited states which belong to the same irreducible representation as the ground state. 相似文献