Download PDF by W Roy Mason: A practical guide to magnetic circular dichroism

By W Roy Mason

ISBN-10: 0470069783

ISBN-13: 9780470069783

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Adapted from ref. 9. There are complications if the ground-state basis is subject to orientational averaging. The matrix elements kAai jmz jAai l are, in general, orientation-dependent, and molecules with different orientations with respect to the field direction will have different Zeeman energies and wavefunctions because of the exponentials. The problem is simplified for isotropic Zeeman splitting. Then the exponentials become orientation-independent. Finally, it may be remarked that saturation effects are much less important for A and B terms.

8) are for the oriented or isotropic case. If the molecule of interest does not belong to a cubic group (O, Oh , or Td ) or is in an oriented matrix environment, then space-averaged term equations must be used [see Eqs. 26)]. The MCD equations for the space-averaged case involving 50 THE INTERPRETATION OF MCD SPECTRA simply reducible groups are given below in Eqs. 13). & 0 X fi fj 0 A1 ¼ 1ijk (MCDijk factor){A}=(3mB jAj)kJkm fi kJl à A Jà ijk ! ' fj fk fi fi0 fj fk kAkm kJlkKkm kAl  kJkm kKl à A Kà Jà & 0 ' X fi fj fk fi0 C0 ¼ 1ijk (MCDijk factor){J}=(3mB jAj)kAkm kAl à J Aà Aà ijk  kAkm fj kJlkJkm fk kAl X D0 ¼ À{A}=(3jAjÞ 1=j f j jd(Aà f j J){Aà f j J}kAkm fj kJlkJkm fj kAl (5:10) (5:11) (5:12) j where the ijk sums are over i, j, and k, each equal to 21, 0, and 1, respectively, and 1ijk is an alternating tensor as defined for Eq.

The value of a blank is further emphasized here, because any small stray birefringence in the sample matrix can immediately be determined. 5. CALIBRATION The calibration of CD and MCD spectrometers is usually performed by measuring DA for standard solutions. A typical and convenient standard for the UV–vis region is camphor sulfonic acid (CSA), which is a stable optically active organic compound that exhibits a strong positive CD at 290 nm (D1 ¼ þ3:37 L molÀ1 cmÀ1 ) and a strong negative CD at 192 nm (D1 % À6:7 L molÀ1 cmÀ1 ) (see ref.

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


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