Helium droplet infrared spectroscopy of the butyl radicals

Abstract

Butyl radicals ( n-, s-, i-, and tert-butyl) are formed from the pyrolysis of stable precursors (1-pentyl nitrite, 2-methyl-1-butyl nitrite, isopentyl nitrite, and azo- tert-butane, respectively). The radicals are doped into a beam of liquid helium droplets and probed with infrared action spectroscopy from 2700 to 3125 cm−1, allowing for a low temperature measurement of the CH stretching region. The presence of anharmonic resonance polyads in the 2800–3000 cm−1 region complicates its interpretation. To facilitate spectral assignment, the anharmonic resonances are modeled with two model Hamiltonian approaches that explicitly couple CH stretch fundamentals to HCH bend overtones and combinations: a VPT2+K normal mode model based on coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] quartic force fields and a semi-empirical local mode model. Both of these computational methods provide generally good agreement with the experimental spectra.