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Title:TERT-BUTYL PEROXY RADICAL:GROUND AND FIRST EXCITED STATE ENERGETICS AND FUNDAMENTAL FREQUENCIES
Author(s):Bercaw, Ronald M.
Contributor(s):Douberly, Gary E.; Schaefer III., Henry F. ; Moore III, Kevin B.; Franke, Peter R.
Subject(s):Theory and Computation
Abstract:Alkylperoxy radicals \chem{(RO_2\kern .25ex ^{.})} 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 $\mathrm{\tilde{A}^{2} A' \leftarrow \tilde{X} ^{2} A''}$ adiabatic excitation energy of 7738 \wn via focal point analysis, approximating the CCSDT(Q)/CBS level of theory. This excitation energy agrees to within 17 \wn 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 $\text{O}\!-\!\text{O}$ stretch, excited state $\text{O}\!-\!\text{O}$ stretch, and excited state $\text{C}\!-\!\text{O}\!-\!\text{O}$ bend fundamentals are predicted at 1138, 959, and 490 \wn, respectively. Basis set sensitivity is found to be particularly great for the $\text{O}\!-\!\text{O}$ stretches, similar to what has already been noted in smaller, unbranched peroxy radicals. Exempting these $\text{O}\!-\!\text{O}$ stretches, agreement with the available experimental fundamentals is generally good ($\pm$ 10 \wn).
Issue Date:23-Jun-20
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:APS
Genre:CONFERENCE PAPER/PRESENTATION
Type:Text
Language:English
URI:http://hdl.handle.net/2142/107592
Date Available in IDEALS:2020-06-26


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