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By W Roy Mason

ISBN-10: 0470069783

ISBN-13: 9780470069783

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The signal-to-noise ratio in a measurement limits the ultimate sensitivity of the measurement and is often limited by the light flux that passes through the sample and reaches the PMT detector. The greater the flux, the better will be the signal-to-noise ratio. Light flux is limited by such experimental parameters as source brightness, the cross-sectional area of the light beam, and the various apertures, including the entrance and exit slits, which limit light passage through the spectrometer.

Again the use of these factors assumes that the underlying assumptions as to basis functions remain the same throughout. The MCD-term equations are given here for simply reducible groups (single-valued irreps) for the transition A ! J for A and C terms and for A ! J and A ! K for B terms in Eqs. 4). 4. MCD-TERM EQUATIONS INVOLVING RMEs & f0 C0 ¼ (MCD factor) 2{J}=(mB jAj)kAkm kAl à J f0 f Aà f Aà 49 '  kAkm f kJlkJkm f kAl (5:4) In these equations the MCD factor expresses the m0 and m+1 operators in terms of the symmetry group basis operators and is given by MCD factor ¼ k f 0 f00 jm0 lk f f1 jm1 lk f fÀ1 jmÀ1 l  f0 f00 f f f À 1 f1  (5:5) where the factors k f 0 f00 jm0 l, k ff1 jm01 l, and k f fÀ1 jm  À1 l are the operator basis f f f transformation coefficients and is a 3jm&for the operator ' f00 f À 1 f1 f f0 f — irreps and partners.

PARAMETER EVALUATION. METHOD OF MOMENTS 35 and then the n moments are calculated about E: ð E0 ka(E)ln ¼ a(E)(E À E)n dE The method assumes the BO – FC approximation to be valid. MCD and absorption parameters are then given by moments determined about E in the following expressions (c ¼ molar concentration and l ¼ path length in cm); the zeroth and first MCD moments are given by (g ¼ 326:6 D2 and mB ¼ 0:4669 cmÀ1 TÀ1 ): E0 kDA=ElE0 0 ¼ kD1c‘=El0 ¼ gmB B(B0 þ C0 =kT) ¼ 152:5Bc‘(B0 þ C0 =(kT)) E0 kDA=ElE0 1 ¼ kD1c‘=El1 ¼ gmB BA1 ¼ 152:5Bc‘A1 and for zeroth absorption moment: E0 kA=ElE0 0 ¼ k1c‘=El0 ¼ gD0 ¼ 326:6c‘D0 4 Measurement of MCD Spectra The measurement of MCD spectra requires that the sample be placed in a strong magnetic field oriented along the light path of a sensitive CD spectrometer.

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A practical guide to magnetic circular dichroism spectroscopy by W Roy Mason


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