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71.
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
72.
Two dinuclear platinum(II) 4,6-diphenyl-2,2'-bipyridine (C^N^N) complexes (1 and 2) with a rigid bridging ligand cis-1,2-bis(diphenylphosphino)ethylene were synthesized and their photophysical properties were systematically investigated in solution for 1 and 2 and in LB film for 2. Similar to their corresponding mononuclear complexes, both complexes exhibit intense (1)π,π* absorption in the UV region and a broad, moderate absorption band in the visible region, which likely stems from the mixed (1)MLCT (metal-to-ligand charge transfer), (1)ILCT (intraligand charge transfer) and (1)π,π* transitions. Both complexes are emissive in solutions at room temperature and in glassy matrix at 77 K. The emitting state is tentatively assigned as (3)MLCT for 1 and (3)MLCT/(3)ILCT/(3)π,π* for 2 at room temperature. At 77 K, the emission observed for 1 is mainly from the emissive ground-state aggregates, which is concentration dependent; while in 2 the emission from the monomer dominates. Unlike the dinuclear platinum complex with flexible bridging ligand diphenylphosphinoethane, the electronic absorption and emission energies of 1 and 2 at room temperature are independent of their concentration, indicating a fixed conformation for these two complexes. In addition, the presence of alkoxyl substituents on the diphenylbipyridine ligands causes a bathochromic shift of the lowest-energy absorption band and the emission band at room temperature for 2, presumably due to the involvement of the ILCT character into the lowest excited states. The presence of alkoxyl substituents in 2 also makes 2 amphiphilic, allowing for the fabrication of LB films of 2. The electronic absorption and emission characteristics in the LB films of 2 are quite similar to those in solutions, indicating no intermolecular Pt-Pt interactions occur in the LB films. The dinuclear complex without alkoxyl substituent (1) exhibits vapochromic behavior to heteroatom-containing volatile organic compounds (VOC's). 相似文献
73.
Mehdi Jonoobi Jalaluddin Harun Aji P. Mathew Mohd Zobir B. Hussein Kristiina Oksman 《Cellulose (London, England)》2010,17(2):299-307
The aim of this study was to develop cellulose nanofibers with hydrophobic surface characteristics using chemical modification.
Kenaf fibers were modified using acetic anhydride and cellulose nanofibers were isolated from the acetylated kenaf using mechanical
isolation methods. Fourier transform infrared spectroscopy (FTIR) indicated acetylation of the hydroxyl groups of cellulose.
The study of the dispersion demonstrated that acetylated cellulose nanofibers formed stable, well-dispersed suspensions in
both acetone and ethanol. The contact angle measurements showed that the surface characteristics of nanofibers were changed
from hydrophilic to more hydrophobic when acetylated. The microscopy study showed that the acetylation caused a swelling of
the kenaf fiber cell wall and that the diameters of isolated nanofibers were between 5 and 50 nm. X-ray analysis showed that
the acetylation process reduced the crystallinity of the fibers, whereas mechanical isolation increased it. The method used
provides a novel processing route for producing cellulose nanofibers with hydrophobic surfaces. 相似文献
74.
Jun Zhang Ramona Rodila Eric Gage Mathew Hautman Leimin Fan Linda L. King Huaiqin Wu Tawakol A. El-Shourbagy 《Analytica chimica acta》2010,661(2):167-172
Simvastatin (SS) is an effective cholesterol-lowering medicine, and is hydrolyzed to simvastatin acid (SSA) after oral administration. Due to SS and SSA inter-conversion and its pH and temperature dependence, SS and SSA quantitation is analytically challenging. Here we report a high-throughput salting-out assisted liquid/liquid extraction (SALLE) method with acetonitrile and mass spectrometry compatible salts for simultaneous LC-MS/MS analysis of SS and SSA. The sample preparation of a 96-well plate using SALLE was completed within 20 min, and the SALLE extract was diluted and injected into an LC-MS/MS system with a cycle time of 2.0 min/sample. The seamless interface of SALLE and LC-MS eliminated drying down step and thus potential sample exposure to room or higher temperature. The stability of SS and SSA in various concentration ratios in plasma was evaluated at room and low (4 °C) temperature and the low temperature (4 °C) was found necessary to maintain sample integrity. The short sample preparation time along with controlled temperature (2-4 °C) and acidity (pH 4.5) throughout sample preparation minimized the conversion of SS → SSA to ≤0.10% and the conversion of SSA → SS to 0.00% The method was validated with a lower limit of quantitation (LLOQ) of 0.094 ng mL−1 for both SS and SSA and a sample volume of 100 μL. The method was used for a bioequivalence study with 4048 samples. Incurred sample reproducibility (ISR) analysis of 362 samples from the study exceeded ISR requirement with 99% re-analysis results within 100 ± 20% of the original analysis results. 相似文献
75.
Using a small-core single-mode fiber (SCSMF), a novel relative humidity (RH) sensor based on an SMF28-SCSMF-SMF28 fiber structure was proposed in this paper. By depositing a humidity sensitive material, such as poly (ethylene oxide) (PEO) on the bare SCSMF fiber, the proposed structure can act as an RH sensor with high sensitivity. Experiments demonstrated that the proposed RH sensor with PEO coating can achieve a sensitivity of 430 nm per relative humidity unit (RHU) in the RH range from 80% to 83% RH and a sensitivity of 50 nm per RHU in the RH range from 83% to 95% RH. 相似文献
76.
Mathew Baxter Robert A. Van Gorder 《Mathematical Methods in the Applied Sciences》2014,37(11):1642-1651
We consider wave solutions to nonlinear sigma models in n dimensions. First, we reduce the system of governing PDEs into a system of ODEs through a traveling wave assumption. Under a new transform, we then reduce this system into a single nonlinear ODE. Making use of the method of homotopy analysis, we are able to construct approximate analytical solutions to this nonlinear ODE. We apply two distinct auxiliary linear operators and show that one of these permits solutions with lower residual error than the other. This demonstrates the effectiveness of properly selecting the auxiliary linear operator when performing homotopy analysis of a nonlinear problem. From here, we then obtain residual error‐minimizing values of the convergence control parameter. We find that properly selecting the convergence control parameter makes a drastic difference in the magnitude of the residual error. Together, appropriate selection of the auxiliary linear operator and of the convergence control parameter is shown to allow approximate solutions that quickly converge to the true solution, which means that few terms are needed in the construction of such solution. This, in turn, greatly improves computational efficiency. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
77.
Analytical solutions for the Cahn-Hilliard initial value problem are obtained through an application of the homotopy analysis method. While there exist numerical results in the literature for the Cahn-Hilliard equation, a nonlinear partial differential equation, the present results are completely analytical. In order to obtain accurate approximate analytical solutions, we consider multiple auxiliary linear operators, in order to find the best operator which permits accuracy after relatively few terms are calculated. We also select the convergence control parameter optimally, through the construction of an optimal control problem for the minimization of the accumulated L 2-norm of the residual errors. In this way, we obtain optimal homotopy analysis solutions for this complicated nonlinear initial value problem. A variety of initial conditions are selected, in order to fully demonstrate the range of solutions possible. 相似文献
78.
Georges Assaf Gemma Cansell Doug Critcher Stuart Field Stewart Hayes Suju Mathew Alan Pettman 《Tetrahedron letters》2010,51(38):5048-5051
We report our results on the construction of a morpholine ring system from the corresponding epoxide and amino alcohol. From this study, we were able to convert a previous four-step synthesis into a more efficient two-step process. 相似文献
79.
The synthesis of alkyl-substituted 2-pyrrolecarboxylate esters has been accomplished by the condensation reaction of a symmetrical vinamidinium salt and glycine ester derivatives. 相似文献
80.
We complete the computation of spectral measures for SU(3) nimrep graphs arising in subfactor theory, namely the SU(3) ADE{SU(3) \mathcal{ADE}} graphs associated with SU(3) modular invariants and the McKay graphs of finite subgroups of SU(3). For the SU(2) graphs the spectral measures distill onto very special subsets of the semicircle/circle, whilst for the SU(3) graphs the spectral measures distill onto very special subsets of the discoid/torus. The theory of nimreps allows us to
compute these measures precisely. We have previously determined spectral measures for some nimrep graphs arising in subfactor
theory, particularly those associated with all SU(2) modular invariants, all subgroups of SU(2), the torus
\mathbbT2, SU(3){\mathbb{T}^2,\,SU(3)}, and some SU(3) graphs. 相似文献