Vibrational circular dichroism of matrix-isolated molecules

Vibrational circular dichroism (VCD) spectra are reported for (+), (?) and (±) α-pinene, and (?) ß-pinine, isolated in argon matrices at ≈ 18 K. These are the first observations of VCD of matrix-isolated molecules. Spectra are limited to the CH stretching region (2800–3100 cm^?1). In all cases, the VCD spectra are substantially more structured than the corresponding room-temperature spectra, as a result of much narrower linewidths. Further, VCD magnitudes are greater due to decreased cancellation of overlapping transitions with oppositely signed VCD. The largest anisotropy ratios observed are >5 × 10^?4 and are larger than any reported for room-temperature solutions of organic molecules. This technique will permit substantially more definitive evaluations of theoretical calculations of VCD.