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91.
A recently proposed perturbational approach to the electron correlation cusp problem 1 is tested in the context of three spherically symmetrical two‐electron systems: helium atom, hydride anion, and a solvable model system. The interelectronic interaction is partitioned into long‐ and short‐range components. The long‐range interaction, lacking the singularities responsible for the electron correlation cusp, is included in the reference Hamiltonian. Accelerated convergence of orbital‐based methods for this smooth reference Hamiltonian is shown by a detailed partial wave analysis. Contracted orbital basis sets constructed from atomic natural orbitals are shown to be significantly better for the new Hamiltonian than standard basis sets of the same size. The short‐range component becomes the perturbation. The low‐order perturbation equations are solved variationally using basis sets of correlated Gaussian geminals. Variational energies and low‐order perturbation wave functions for the model system are shown to be in excellent agreement with highly accurate numerical solutions for that system. Approximations of the reference wave functions, described by fewer basis functions, are tested for use in the perturbation equations and shown to provide significant computational advantages with tolerable loss of accuracy. Lower bounds for the radius of convergence of the resulting perturbation expansions are estimated. The proposed method is capable of achieving sub‐μHartree accuracy for all systems considered here. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 相似文献
92.
Pan J Song Q Shi H King M Junga H Zhou S Naidong W 《Rapid communications in mass spectrometry : RCM》2004,18(21):2549-2557
A highly sensitive bioanalytical method based on a simple liquid/liquid extraction and hydrophilic interaction liquid chromatography with tandem mass spectrometry (HILIC/MS/MS) analysis has been developed, validated and transferred for the determination of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), a tobacco-specific nitrosamine metabolite. Deuterated NNAL (NNAL-d(4)) was synthesized and used as the internal standard. This method can be used for the analysis of free and total NNAL (free NNAL plus NNAL-gluc) in K(3)-EDTA human plasma. Free NNAL and NNAL-d(4) are extracted from human plasma by liquid/liquid extraction. To analyze for total NNAL and the internal standard, a separate aliquot of the K(3)-EDTA human plasma is treated with beta-glucuronidase to deconjugate the NNAL-gluc; the total NNAL and internal standard are then extracted using liquid/liquid extraction. After drying down under nitrogen, the residue is reconstituted with acetonitrile and analyzed using positive ion electrospray and HILIC/MS/MS at a flow rate of 1.0 mL/min. The chromatographic run time is 1.0 min per injection, with retention time for both NNAL and NNAL-d(4) of 0.75 min with a capacity factor (k') of 2. The standard curve range for this assay is from 5.00-1000 pg/mL for both free and total NNAL, using a total plasma sample volume of 1.0 mL. The interday precision and accuracy of the quality control (QC) samples demonstrated <7.6% relative standard deviation (RSD) and <3.3% relative error (RE) for free NNAL. For total NNAL, the interday precision and accuracy of the QC samples demonstrated <11.7% RSD and <2.8% RE. Optimization of enzyme hydrolysis of NNAL-gluc is discussed in detail. The overall recoveries for free and total NNAL and IS were 68.2 and 71.5% (free) and 70.7 and 65.5% (total). No adverse matrix effects were noticed for this assay. 相似文献
93.
R. B. King 《Journal of mass spectrometry : JMS》1969,2(4):387-399
The positive-ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC5H4CH2Fe(CO)2C5H5, NC5H4CH2COMo(CO)2C5H5, NC5H4CH2W(CO)3C5H5, NC5H4CH2COMn(CO)4, C5H10NCH2CH2Fe(CO)2C5H5, (CH3)2NCH2CH2COFeCOC5H5 and (CH3)2NCH2CH2COMn(CO)4 obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C5H5Mo(CO)3CH2NCO; (iii) The arylazomolybdenum derivatives RN2Mo(CO)2C5H5 (R ? phenyl, p-tolyl, or p-anisyl); (iv) The compound (C6H5N)2COFe2(CO)6 obtained from Fe3(CO)12 and phenyl isocyanate; (v) The N,N,N′,N′-tetramethylethylenediamine complex (CH3)2NCH2CH2N(CH3)2W(CO)4. Further examples of eliminations of hydrogen, CO, and C2H2 fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC5H4CH2MC5H5]+ to give the ions [(C5H5)2M]+ (M ? Fe, Mo and W); (ii) Conversion of C5H5Mo(CO)3CH2NCO to C5H5Mo(CO)2CH2NCO within the mass spectrometer; (iii) Elimination of N2 from [RN2MoC5H5]+ to give [RMoC5H5]+; (iv) Novel eliminations of HNCO, FeNCO, and C6H5NC fragments in the mass spectrum of (C6H5N)2COFe2(CO)6; (v) Facile dehydrogenation of the N,N,N′,-N′-tetramethylethylenediamine ligand in the complex (CH3)2NCH2CH2N(CH3)2W(CO)4. 相似文献
94.
The renormalized perturbation expansion for the linewidth of the Van der Pol oscillator is extended to fifth order. The results of the previously obtained fourth order are thereby improved for pump strengthsa5. No indication of a breakdown of the expansion, even for strong pumping, is found. 相似文献
95.
S. B. Clough N. S. Schneider A. O. King 《Journal of Macromolecular Science: Physics》2013,52(4):641-648
Small-angle X-ray scattering is shown to be an effective technique, complementary to mechanical and thermal methods, for the study of structural ordering in polyurethane elastomers. Wide variations in intensity were found for different sample compositions and are interpreted in terms of the degree of hard segment aggregation. The results support previous conclusions regarding the organization in these samples based on analysis by scanning thermal methods. The polyether polyurethanes studied showed a higher degree of organization than the equivalent polyesters, and longer urethane segments enhance the extent of domain structure. Studies of the temperature dependence of scattering strengthen the previous assignment of a transition at about 150°C to the disordering of domain structure. 相似文献
96.
Xia Jingwen King Alistair W. T. Kilpeläinen Ilkka Aseyev Vladimir 《Cellulose (London, England)》2021,28(17):10921-10938
Cellulose - Cellulose is an historical polymer, for which its processing possibilities have been limited by the absence of a melting point and insolubility in all non-derivatizing molecular... 相似文献
97.
Dr. Valerie H. L. Wong Dr. Sai V. C. Vummaleti Prof. Luigi Cavallo Dr. Andrew J. P. White Prof. Steven P. Nolan Dr. King Kuok Hii 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13320-13327
A general synthetic route was used to prepare 15 new N‐heterocyclic carbene (NHC)–AgI complexes bearing anionic carboxylate ligands [Ag(NHC)(O2CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand‐accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–AgI complexes. 相似文献
98.
Steven S. Wesolowski Edward F. Valeev Rollin A. King Victor Baranovski Henry F. Schaefer III 《Molecular physics》2013,111(16):1227-1231
Atomic natural orbital (ANO) basis sets for calcium may produce surprisingly poor atomic and molecular properties and energetics. The weaknesses in these basis sets may be traced primarily to deficiencies within the sets of d functions which are incapable of effectively correlating the 3s and 3p electrons. Examples are given which show that addition of tight d functions to the ANO basis is required to achieve qualitatively correct energetics and structures for conventionally bonded calcium compounds. 相似文献
99.
100.
Bharat Kumar Ruth L. Viboh Margel C. Bonifacio William B. Thompson Jonathan C. Buttrick Babe C. Westlake Min‐Soo Kim Robert W. Zoellner Sergey A. Varganov Philipp Mrschel Jaroslav Teteruk Martin U. Schmidt Benjamin T. King 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2012,124(51):13071-13071