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991.
M.?Prasad S.?P.?MoulikEmail author A. Al.?Wardian S.?Moore A.?van?Bommel R.?PalepuEmail author 《Colloid and polymer science》2005,283(8):887-897
The clouding points (CP) of the nonionic surfactants p-tert-octyl phenyl polyoxyethylene ether (Triton X 100), Brij-56 and Brij-97, and the water soluble polymer polyvinylmethylether (PVME) have been measured in the presence of the ionic surfactants alkyl (C10, C12, C14 and C16) triphenyl phosphonium bromides (ATPBs). The threshold additive concentrations required for efficient CP enhancement of the systems that were studied have been determined. Considering CP as the threshold state of phase separation, the energetics of the process at different additive concentrations has been evaluated. The spontaneity of free energy of the clouding process (G
c
0
) at the transition concentrations followed the order PVME > TX 100 Bj 56 > Bj 97. The clouding process has been found to be energetically endothermic with fairly large enthalpy and entropy changes that nicely compensate each other. The compensation temperature has been evaluated and compared with different types of the clouding agents.This revised version was published online in January 2005 with corrections to the names of the authors. 相似文献
992.
Addition–elimination reactions involving a nucleophile and a remote leaving group [SH
N(AE)tele] are well-known under basic conditions, especially amongst electron-poor six-membered heterocycles, but are less commonly
encountered for five-membered heterocycles and are rare under acidic conditions. Concentrated HCl converts 1-hydroxy-1H-pyrazolo[3,4-c] isoquinoline and 1-hydroxy-1H-pyrazolo[3,4-c]quinoline into 3-chloro-1H-pyrazolo[3,4-c]isoquinoline and 3-chloro-1H-pyrazolo[3,4-c]quinoline, respectively. However, apparently neither the isomeric 1-hydroxy-1H-pyrazolo[4,3-c](iso)-quinolines nor the parent 1-hydroxypyrazole undergo this reaction. Additionally, all these systems are refractory under
basic conditions. We present a plausible mechanism for the reaction, involving the 3-addition of Cl- to the diprotonated heterocycle, followed by the elimination of water. Calculations of the initial transition states and
intermediates, using optimisation at B3LYP/6-311+G(d,p), including thermochemistry [HF/6-31+G(d)], and single-point Poisson–Boltzmann
self-consistent reaction field determination of the free energy of solvation (Jaguar Poisson–Boltzmann self-consistent reaction
field), support this mechanism and reproduce the observed order of reactivity, the addition step being 2–4 kcal less favourable
for the isomeric 1-hydroxy-1H-pyrazolo[4,3-c](iso)quinolines and provide a rationalisation for the role of strong acid.
Received: 27 June 2002 / Accepted: 6 September 2002 /
Published online: 14 February 2003 相似文献
993.
An overview is given on recent advances of density functional theory (DFT) as applied to the calculation of nuclear magnetic
resonance (NMR) chemical shifts and electron spin resonance (ESR) g-tensors. This is a new research area that has seen tremendous progress and success recently; we try to present some of these
developments. DFT accounts for correlation effects efficiently. Therefore, it is the only first-principle method that can
handle NMR calculations on large systems like transition-metal complexes. Relativistic effects become important for heavier
element compounds; here we show how they can be accounted for. The ESR g-tensor is related conceptually to the NMR shielding, and results of g-tensor calculations are presented. DFT has been very successful in its application to magnetic properties, for metal complexes
in particular. However, there are still certain shortcomings and limitations, e.g., in the exchange-correlation functional,
that are discussed as well.
Received: 24 October 1997 / Accepted: 19 December 1997 相似文献
994.
995.
The potential energy surface (PES) for the CF3CFHO2+HO2 reaction has been theoretically investigated using the DFT [B3LYP/6‐311G(d,p)] and B3LYP/6‐311++G(3df,3pd)//B3LYP/6‐311G(d,p) levels of theory. Both singlet and triplet PESs are investigated. The reaction mechanism on the triplet surface is simple. It is revealed that the formation of CF3CFHOOH+3O2 is the dominant channel on the triplet surface. On the basis of the ab initio data, the total rate constants for the reaction CF3CFHO2+HO2 in the T = 210–500 K range have been computed using conventional transition state theory with Wigner's tunneling correction and have been fitted by a rate constant expression as k = 1.04 ×10?12(cm3 molecule?1 s?1) exp (700.33/T). Calculated transition state rate constants with Wigner's tunneling correction for the reaction CF3CFHO2+HO2 are in good agreement with the available experimental values. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
996.
Stefan Motiu Daniela Dogaru Valentin Gogonea 《International journal of quantum chemistry》2007,107(5):1248-1252
This work puts forth a reaction pathway for the reactivation of exogenous ligand inhibited H‐cluster, the active site of Fe‐only hydrogenases. The H‐cluster is a dimetal complex, Fe–Fe, with the metal centers bridged by di(thiomethyl)amine. Exogenous ligands, H2O, and OH?, are bound to the distal iron (Fed). Density functional theory (DFT) calculations on the native and ruthenium‐modified H‐cluster have been performed using the B3LYP functional with 6‐31+G** and 6‐311+G** basis sets. We have ascertained that there is a thermodynamically favorable pathway for the reactivation of the OH? inhibited H‐cluster, which proceeds by an initial protonation of the Fed–OH? complex. The proposed reaction pathway has all its intermediate reactions ensue exothermically. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
997.
LIU Peng-jun ZHANG Lian-hua SUN Hao CHANG Ying-fei WANG Rong-shun 《高等学校化学研究》2006,22(5):635-638
The reaction mechanisms of HNCS with NH(X^3∑ ) were theoretically investigated. The minimum energy paths (MEP) of the reaction were calculated by using the density functional theory(DFT) at the B3LYP/6-311 + + G^** level. The equilibrium structural parameters, the harmonic vibrational frequencies, the total energies, and the zeropoint energies(ZPE) of all the species were calculated. The single-point energies along the MEP were further refined at the QCISD(T)/6-311 + + G^* * level. It was found that the mechanisms of the HNCS + NH(X^3∑) reaction involve two channels producing the HNC + HNS and the N2H2 + CS products. Channel 1 plays a dominant role and the HNC + HNS are the main preduets. The reaction is exothermie. 相似文献
998.
The mechanism of a cycloaddition reaction between singlet dichloromethylene germylene and ethylene has been investigated with B3LYP/6-31G* method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies for the involved conformations were calculated by CCSD(T)//B3LYP/6-31G* method. On the basis of the surface energy profile obtained with CCSD(T)// B3LYP/6-31G* method for the cycloaddition reaction between singlet dichloromethylene germylene and ethylene, it can be predicted that the dominant reaction pathway is that an intermediate INT1 is firstly formed between the two reactants through a barrier-free exothermic reaction of 61.7 kJ/mol, and the intermediate INT1 then isomerizes to an active four-membered ring product P2.1 via a transition state TS2, an intermediate INT2 and a transition state TS2.1, in which energy barriers are 57.7 and 42.2 kJ/mol, respectively. 相似文献
999.
N. M. Avram Gh. E. Drgnescu M. R. Kibler 《International journal of quantum chemistry》2002,88(3):303-309
The coupling between doubly degenerate electronic states and doubly degenerate vibrations is analyzed for an octahedral system on the basis of the introduction of an anharmonic Morse potential for the vibronic part. The vibrations are described by anharmonic coherent states and their linear coupling with the electronic states is considered. The matrix elements of the vibronic interaction are built and the energy levels corresponding to the interaction Hamiltonian derived. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
1000.
A homologous series of 2,4-dichlorobenzyl alkyl ethers (DCBEs) have been synthesized and purified for use as retention index calibrants and internal standards. They are stable, sensitive to ECD and FID and ideal for GC-MS, with base peaks at m/z 159/161. The retention index calibration against the n-alkanes for a linear temperature program (LTP) series is given and recommendations made for the most suitable members of the DCBE series for use as internal standards in organochlorine (OC) residue analysis. 相似文献