Circular dichroism of (+)-2-butanol in the vacuum ultraviolet. A comparison of theoretical and experimental values

The circular dichroism and absorption spectra of (+)-(S)-2 butanol have now been measured to 1350 Å. Theoretical rotational strengths calculated using an independent systems approach are compared to the measured values. The results support use of the extended Kirkwood theory for calculation of rotational strengths. Our method for applying the theory is described in detail. Using a model in which the first three electronic transitions in simple alcohols are assigned as n → σOH*, n → σCO*, n → 3sO, we obtain good agreement in sign and magnitude between calculated and experimental rotational strengths. The importance of including the generally ignored gij type term of Kirkwood is clearly illustrated. It is expected to dominate for transitions which are both magnetically and electrically allowed when the static fields are small.