Reduction of linear birefringence in vibrational circular dichroism measurement: use of a rotating half-wave plate

Xiaolin Cao; Dukor, Rina K.; Nafie, Laurence A.
January 2008
Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Jan2008, Vol. 119 Issue 1-3, p69
Academic Journal
A new method has been developed to suppress the effects of linear birefringence (LB) associated with sample cells in the measurement of vibrational circular dichroism (VCD) spectra by adding a rotating half-wave plate (RHWP) to the optical train. The method functions in combination with the previously developed dual polarization modulation (DPM) technique and involves placing the RHWP after the second photo-elastic modulator (PEM) of the DPM setup. In the DPM setup without the RHWP, all sources of LB terms are first reduced and then further cancelled by real time electronic subtraction, except for one remaining LB term associated with sample cell. Not infrequently, however, this remaining source of LB between the two PEMs with axes at 45° relative to the stress axes of the PEMs leads to noticeable deviations of the VCD baseline that cannot be eliminated. The new method described here depends on the use of an achromatic half-wave plate which is currently available in the near-infrared region with a low-frequency cut off near 2,000 cm−1. It is demonstrated theoretically, and experimentally in the CH stretching region, that the addition of a RHWP eliminates this last remaining source of LB from the VCD measurement.


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