To evaluate the quantitative agreement between the observed and predicted properties of specific rotation, vibrational absorption, and vibrational circular dichroism (VCD), (+)-3-chloro-1-butyne, which is one of the smallest single conformer chiral molecules, has been synthesized for the first time and its intrinsic rotation (specific rotation at infinite dilution), vibrational absorption, and VCD have been measured. These properties have also been predicted using density functional theory (DFT) and large basis sets, namely aug-cc-pVDZ, 6-311++G(2d,2p), and aug-cc-pVTZ. Using these experimental and predicted properties, the absolute configuration of (+)-3-chloro-1-butyne is established as (R). The observed intrinsic rotation and predicted specific rotation are observed to be in excellent quantitative agreement. The predicted vibrational absorption and VCD spectra are in good qualitative agreement with the corresponding observed spectra; however, the root-mean-square percent differences in integrated intensities are similar to20%-30%. The conformer populations of (-)-3-butyn-2-ol in CCl4 have then been analyzed using experimental intrinsic rotation, vibrational absorption, and VCD; the corresponding predicted properties were also obtained, using DFT and large basis sets, as for 3-chloro-1-butyne. All three properties indicate that (-)-3-butyn-2-ol exists predominantly in two different conformations in dilute CCl4 solutions. Populations of these conformers determined from the three methods are in reasonable agreement. However, the errors in populations determined from vibrational absorption and VCD are fairly large, which indicates the need for better quantitative accuracy in the predicted vibrational absorption and VCD intensities.