The computationally predicted presence of two structurally distinct minima in the first triplet excited (T-1) state of 2-thiouracil (2TU) is substantiated by sub-picosecond transient vibrational absorption spectroscopy (TVAS) in deuterated acetonitrile solution. Following 300 nm ultraviolet excitation to the second singlet excited state of 2TU, a transient infrared absorption band centered at 1643 cm(-1) is observed within our minimum time resolution of 0.3 ps. It is assigned either to 2TU molecules in the S-1 state or to vibrationally hot T-1-state molecules, with the latter assignment more consistent with recent computational and experimental studies. The 1643 cm(-1) band decays with a time constant of 7.2 +/- 0.8 ps, and there is corresponding growth of several further bands centered at 1234, 1410, 1424, 1443, 1511, 1626, and 1660 cm-1 which show no decline in intensity over the 1 ns time limit of our measurements. These spectral features are assigned to two different conformations of 2TU, corresponding to separate energy minima on the T-1-state potential energy surface, on the basis of their extended lifetimes, computed infrared frequencies, and the observed quenching of the bands by addition of styrene. Corresponding measurements for the 4-thiouracil (4TU) isomer show sub-picosecond population of the T-1 state, which vibrationally cools with a time constant of 5.2 +/- 0.6 ps. However, TVAS measurements in the carbonyl stretching region do not distinguish the two computed T-1-state conformers of 4TU because of the similarity of their vibrational frequencies.