S 1 ←S 0 vibronic spectrum and the structure of the chloral molecule in theS 1 stateS 0 vibronic spectrum and the structure of the chloral molecule in theS 1 state

The vibronic absorption spectrum of chloral (CCl₃COH) vapors is studied in the region of S₁ ← S₀ electron transition (32,000–28,700 cm⁻¹). The 29,070 cm⁻¹ vibronic transition (not observed because of low intensity) is believed to be the ‘start’ of the electron transition. Several fundamentals are found in the S₀ and S₁ states. Inversion splitting of the zero vibrational level in the S₁ state of chloral, indicating a nonplanar structure of the carbonyl fragment, is found. The intensity ratio of the torsional transition bands indicates that the S₁ ← S₀ electronic excitation of the chloral molecule causes significant changes in the orientation of the −CCl₃ group relative to the molecular framework. The potential functions of internal rotation (S₀ and S₁ states) and inversion (S₁ state) of the chloral molecule are determined from experimental data. The potential barriers of internal rotation (S₀ and S₁ states) and inversion (S₁ state) are 380, 780, and 760 cm⁻¹ (4.5, 9.3, and 9.1 kJ/mole), respectively. M. V. Lomonosov Moscow State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 3, pp. 507–513, May–June, 1998.