Energetics of H-atom addition to naphthalene: A thermochemical cycle from tetralin to naphthalene

摘要

The C-H bond dissociation enthalpies (BDEs) of molecules related to naphthalene radical chemistry were investigated using quantum chemistry calculations (CBS-QB3 and CCSD(T*)-F12), and the C-H BDE in 1,2-dihydronaphthalene was determined using time-resolved photoacoustic calorimetry. A thermodynamically consistent data set of the energetics (C-H BDEs and enthalpies of formation) of the molecules involved (naphthalene, 1- and 2-hydronaphthyl radicals, 1,2- and 1,4-dihydronaphthalene, tetralyl radical, and tetralin) is presented. It was constructed using a thermodynamic cycle based on the simple notion that BDEs represent the difference between two states, bridging accurate experimental enthalpies of formation of the parent compounds with theoretical and experimental C-H BDEs leading to, and from, the radicals.