tert-Butyl peroxy radical: ground and first excited state energetics and fundamental frequencies

Abstract

Alkylperoxy radicals (RO₂˙) are key intermediates in combustion and atmospheric oxidation processes. As such, reliable detection and monitoring of these radicals can provide a wealth of information about the underlying chemistry. The tert-butyl peroxy radical is the archetypal tertiary peroxy radical, yet its vibrational spectroscopy is largely unexplored. To aid in future experimental investigations, we have performed high-level theoretical studies of the fundamental vibrational frequencies of the ground- and first excited states. A conformer search on both electronic surfaces reveals single minimum-energy structures. We predict an òA′ ← ²A′′ adiabatic excitation energy of 7738 cm⁻¹via focal point analysis, approximating the CCSDT(Q)/CBS level of theory. This excitation energy agrees to within 17 cm⁻¹ of the most accurate experimental measurement. We compute CCSD(T) fundamental vibrational frequencies via second-order vibrational perturbation theory (VPT2), using a hybrid force field in which the quadratic (cubic/quartic) force constants are evaluated with the ANO1 (ANO0) basis set. Anharmonic resonance polyads are treated with the VPT2 + K effective Hamiltonian approach. Among the predicted fundamental frequencies, the ground state O–O stretch, excited state O–O stretch, and excited state C–O–O bend fundamentals are predicted at 1138, 959, and 490 cm⁻¹, respectively. Basis set sensitivity is found to be particularly great for the O–O stretches, similar to what has already been noted in smaller, unbranched peroxy radicals. Exempting these O–O stretches, agreement with the available experimental fundamentals is generally good (±10 cm⁻¹).