Vibrational spectroscopy of triacetone triperoxide (TATP): Anharmonic fundamentals, overtones and combination bands

The vibrational spectrum of triacetone triperoxide (TATP) is studied by the correlation-corrected vibrational self-consistent field (CC-VSCF) method which incorporates anharmonic effects. Fundamental, overtone, and combination band frequencies are obtained by using a potential based on the PM3 method and yielding the same harmonic frequencies as DFT/cc-pVDZ calculations. Fundamentals and overtones are also studied with anharmonic single-mode (without coupling) DFT/cc-pVDZ calculations. Average deviations from experiment are similar for all methods: 2.1–2.5%. Groups of degenerate vibrations form regions of numerous combination bands with low intensity: the 5600–5800 cm−1 region contains ca. 70 overtones and combinations of CH stretches. Anharmonic interactions are analyzed.