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51.
A series of MP2 and CCSD(T) computations have been carried out with correlation consistent basis sets as large as aug-cc-pV5Z to determine the intrinsic equatorial-axial conformational preference of CH(3)-, F-, OCH(3)-, and OH-substituted cyclohexane and tetrahydropyran rings. The high-accuracy relative electronic energies reported here shed new light on the intrinsic energetics of these cyclic prototypes for the anomeric effect. At the CCSD(T) complete basis set (CBS) limit, the energy of the equatorial conformation relative to the axial position (DeltaE (CBS)(CCSD(T))) is -1.75, -0.20, -0.21, and -0.56 kcal mol(-1) in methyl-, fluoro-, methoxy-, and hydroxycyclohexane, respectively, while DeltaE(CBS)(CCSD(T) is -2.83, +2.45, +1.27, and +0.86 kcal mol(-1) for 2-methyl-, 2-fluoro-, 2-methoxy-, and 2-hydroxytetrahydropyran, respectively. Note that the equatorial and axial conformers are nearly electronically isoenergetic in both fluoro- and methoxycyclohexane. For all eight cyclic species, a zero-point vibrational energy correction decreases Delta by a few tenths of a kilocalorie per mole. Relative energies obtained with popular methods and basis sets are unreliable, including Hartree-Fock theory, the B3LYP density functional, and the 6-31G and 6-311G families of split-valence basis sets. Even with the massive pentuple-zeta basis sets, the HF and B3LYP methods substantially overestimate the stability of the equatorial conformers (by as much as 0.99 and 0.73 kcal mol(-1), respectively, for 2-methoxytetrahydropyran). Only because of a consistent cancellation of errors do these popular approaches sometimes provide reasonable estimates of the anomeric effect. 相似文献
52.
53.
V. Weldon P. Pineda-Vadillo M. Lynch R. Phelan J. F. Donegan 《Applied physics. B, Lasers and optics》2012,109(3):433-440
The characteristics of a novel Discrete Mode laser diode are described with particular reference to its capability in spectroscopic based gas sensing. In this regard, its emission linewidth, Side Mode Suppression Ratio and tuneability are of particular note. The measured narrow linewidth of 550?kHz has applications with respect to spectrally narrow absorption features found, for example, in saturated absorption lines, in hyperfine structure of some rotational manifolds and in whispering gallery mode features associated with optical microspheres. Other notable measured characteristics show mode-hop-free temperature tuning of 11 nm at a linear tuning rate of 0.1 nm/°C and a Side Mode Suppression Ratio in the range 56 to 46 dB and a long term (72?hours) wavelength stability of 1?pm per day. In essence, this novel Discrete Mode laser displays excellent potential for diode laser based sensing applications in the near infrared. 相似文献
54.
H. Arthur Weldon 《Zeitschrift fur Physik C Particles and Fields》1992,54(3):431-437
The energy dependence of the pion and kaon collision rates at finite-temperature are calculated in the approximation that resonances dominate the scattering, as for example, ππ→?→ππ andKπ→K *→Kπ. A general formula is derived for the contribution of resonances with arbitrary spin and isospin. Numerical results are given. For very narrow resonances the calculation is performed analytically. 相似文献
55.
Weldon James Wilson 《Physics letters. A》1980,75(3):156-158
The nonintegrable phase factor approach to interactions is generalized in the case of a Dirac particle. The results differ significantly from those obtained in the Schrödinger theory and allow Dirac particles to be characterized by two fundamental couplings. 相似文献
56.
57.
Driga M. D. Nasar S. A. Rylander H. G. Weldon W. F. Woodson H. H. 《IEEE transactions on plasma science. IEEE Nuclear and Plasma Sciences Society》1975,3(4):209-215
Fusion research experiments require high energy short duration pulses. A homopolar machine, as an inertial energy storage system, offers an attractive source of energy meeting these requirements. The Energy Storage Group at The University of Texas at Austin has investigated the fundamental limitations to the discharge time of homopolar machines of various topological configurations. This paper presents a mathematical model for fast discharge homopolar machines. Based on this model, various machine configurations are analyzed. A new configuration - the spool type machine - is also discussed, criteria for the evaluation of different alternatives are presented, and it is concluded that highly efficient (? 95%), high energy (? gigajoules), fast-discharge (? 5 to 30 milliseconds) homopolar inertial energy storage systems are technically feasible. Brief reference is also made to some of the experimental results obtained from the existing laboratory models. 相似文献
58.
Phantipa Thipwiwatpotjana Weldon A. Lodwick 《Fuzzy Optimization and Decision Making》2014,13(2):151-171
Uncertain data appearing as parameters in linear programs can be categorized variously. This paper deals with merely probability, belief (necessity), plausibility (possibility), and random set information of uncertainties. However, most theoretical approaches and models limit themselves to the analysis involving merely one kind of uncertainty within a problem. Moreover, none of the approaches concerns itself with the fact that random set, belief (necessity), and plausibility (possibility) convey the same information. This paper presents comprehensive methods for handling linear programs with mixed uncertainties which also preserve all details about uncertain data. We handle mixed uncertainties as sets of probabilities which lead to optimistic, pessimistic, and minimax regret in optimization criteria. 相似文献
59.
Natural products from the integument of nonavian reptiles 总被引:1,自引:0,他引:1
This review describes the epidermal and glandular chemistry of nonavian reptiles in relation to proposed functions, and includes more than 170 references. The results are presented according to the different reptile taxa. 相似文献
60.
Weldon V McInerney D Phelan R Lynch M Donegan J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(5):1013-1020
Tuneable laser diodes were characterized and compared for use as tuneable sources in gas absorption spectroscopy. Specifically, the characteristics of monolithic widely tuneable single frequency lasers, such as sampled grating distributed Bragg reflector laser and modulated grating Y-branch laser diodes, recently developed for optical communications, with operating wavelengths in the 1,520 nm相似文献