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161.
G A Olah T Mathew E R Marinez P M Esteves M Etzkorn G Rasul G K Prakash 《Journal of the American Chemical Society》2001,123(47):11556-11561
Quantitative rearrangement of pivalaldehyde to methyl isopropyl ketone is observed in acids such as trifluoromethanesulfonic acid, anhydrous HF, and trifluoroethyl alcohol-BF3 but not in trifluoroacetic acid. Studies in a mixture of trifluoroacetic acid and trifluoromethanesulfonic acid show that acids with H(o) < or = -11 are able to carry out complete isomerization. These results and density functional theory calculations at the B3LYP/6-31G level suggest that protonated pivalaldehyde undergoes further protosolvation at higher acidities to a reactive superelectrophilic species resulting in rearrangement. A mechanism for the pivalaldehyde rearrangement to methyl isopropyl ketone in strong protic acids involving a reactive protosolvated superelectrophilic intermediate is suggested. Aspects of the related mechanism of the reaction with isobutane with CO in HF/BF3 medium leading to methyl isopropyl ketone are also discussed. 相似文献
162.
163.
Adaptive tensor product wavelet methods are applied for solving Poisson’s equation, as well as anisotropic generalizations, in high space dimensions. It will be demonstrated that the resulting approximations converge in energy norm with the same rate as the best approximations from the span of the best N tensor product wavelets, where moreover the constant factor that we may lose is independent of the space dimension n. The cost of producing these approximations will be proportional to their length with a constant factor that may grow with n, but only linearly. 相似文献
164.
William R Cullen Mathew Dodd Basil U Nwata Deborah A Reimer Kenneth J Reimer 《应用有机金属化学》1989,3(4):351-353
Inorganic arsenic(III) and arsenic(V), methyl-arsenicals, antimony(III), and antimony(V), and butyltin derivatives are present in the shells of molluscs found in the coastal waters of British Columbia. 相似文献
165.
I.M. KrishnakumarBeena Mathew 《European Polymer Journal》2002,38(9):1745-1752
To correlate the coupling difficulty and nature of the support in solid-phase peptide synthesis, a set of difficult peptides were built under identical conditions on rigid and hydrophobic divinyl benzene-crosslinked polystyrene (DVB-PS) and flexible and polar 1,4-butanediol dimethacrylate-crosslinked polystyrene (BDDMA-PS) resins of same functional capacity (∼2 mmol/g). The difficult coupling stages observed on each support were identified by monitoring the acylation time, coupling yield and deprotection efficiency. The yield and purity of the peptides prepared on BDDMA-PS were higher than when DVB-PS support was used. 相似文献
166.
Wolfgang Oppolzer Robert J. Mills Werner Pachinger Thomas Stevenson 《Helvetica chimica acta》1986,69(7):1542-1545
EtAlCl2-promoted additions of organocopper reagents to camphor-derived, conjugated N-enoyl-sultams gave saturated and olefinic β-silylcarboxyl derivatives with high diastereodifferentiation. Nondestructive removal of the chiral auxiliary followed by oxidative Si-C bond cleavage furnished enantiomerically pure acetate-derived aldols and propionate-derived ‘anti’ -aldols (via silyl-directed α-methylation). 相似文献
167.
Mortar methods with dual Lagrange multiplier bases provide a flexible, efficient and optimal way to couple different discretization
schemes or nonmatching triangulations. Here, we generalize the concept of dual Lagrange multiplier bases by relaxing the condition
that the trace space of the approximation space at the slave side with zero boundary condition on the interface and the Lagrange
multiplier space have the same dimension. We provide a new theoretical framework within this relaxed setting, which opens
a new and simpler way to construct dual Lagrange multiplier bases for higher order finite element spaces. As examples, we
consider quadratic and cubic tetrahedral elements and quadratic serendipity hexahedral elements. Numerical results illustrate
the performance of our approach.
This work was supported in part by the Deutsche Forschungsgemeinschaft, SFB 404, C12, the Netherlands Organization for Scientific
Research and by the European Community's Human Potential Programme under contract HPRN-CT-2002-00286. 相似文献
168.
169.
Mathew D. Penrose 《Communications in Mathematical Physics》2001,218(1):153-176
Identical cars are dropped sequentially from above into a large parking lot. Each car is positioned uniformly at random,
subject to non-overlap with its predecessors, until jamming occurs. There have been many studies of the limiting mean coverage
as the parking lot becomes large, but no complete proof that such a limit exists, until now.
We prove spatial laws of large numbers demonstrating that for various multidimensional random and cooperative sequential adsorption
schemes such as the one above, the jamming limit coverage is well-defined.
Received: 18 August 2000 / Accepted: 13 November 2000 相似文献
170.
Mathew D. Halls Julia Velkovski H. Bernhard Schlegel 《Theoretical chemistry accounts》2001,105(6):413-421
Scaling factors for obtaining fundamental vibrational frequencies from harmonic frequencies calculated at six of the most
commonly used levels of theory have been determined from regression analysis for the polarized-valence triple-zeta (pVTZ)
Sadlej electric property basis set. The Sadlej harmonic frequency scaling factors for first- and second-row molecules were
derived from a comparison of a total of 900 individual vibrations for 111 molecules with available experimental frequencies.
Overall, the best performers were the hybrid density functional theory (DFT) methods, Becke's three-parameter exchange functional
with the Lee–Yang–Parr fit for the correlation functional (B3-LYP) and Becke's three-parameter exchange functional with Perdew
and Wang's gradient-corrected correlation functional (B3-PW91). The uniform scaling factors for use with the Sadlej pVTZ basis
set are 0.9066, 0.9946, 1.0047, 0.9726, 0.9674 and 0.9649 for Hartree–Fock, the Slater–Dirac exchange functional with the
Vosko–Wilk–Nusair fit for the correlation functional (S-VWN), Becke's gradient-corrected exchange functional with the Lee–Yang–Parr
fit for the correlation functional (B-LYP), B3-LYP, B3-PW91 and second-order M?ller–Plesset theory with frozen core (MP2(fc)),
respectively. In addition to uniform frequency scaling factors, dual scaling factors were determined to improve the agreement
between computed and observed frequencies. The scaling factors for the wavenumber regions below 1800 cm−1 and above 1800 cm−1 are 0.8981 and 0.9097, 1.0216 and 0.9857, 1.0352 and 0.9948, 0.9927 and 0.9659, 0.9873 and 0.9607, 0.9844 and 0.9584 for
Hartree–Fock, S-VWN, B-LYP, B3-LYP, B3-PW91 and MP2(fc), respectively. Hybrid DFT methods along with the Sadlej pVTZ basis
set provides reliable theoretical vibrational spectra in a cost-effective manner.
Received: 22 May 2000 / Accepted: 30 August 2000 / Published online: 28 February 2001 相似文献