skip to main content

DOE PAGESDOE PAGES

Title: Conformation-specific spectroscopy of alkyl benzyl radicals: Effects of a radical center on the CH stretch infrared spectrum of an alkyl chain

An important initial step in the combustion of gasoline and diesel fuels is the abstraction of hydrogen from alkylbenzenes to form resonance-stabilized alkyl benzyl radicals. This work uses, for the first time, double resonance spectroscopy methods to explore the conformation-specific vibronic and infrared spectroscopy of the α-ethylbenzyl (αEtBz) and α-propylbenzyl (αPrBz) radicals. Local mode Hamiltonian modeling enables assignment of the alkyl CH stretch IR spectra, accounting for Fermi resonance that complicates aliphatic alkyl CH stretch IR spectroscopy. The ground state conformational preferences of the ethyl and propyl chains are changed from those in the alkylbenzenes themselves, with global minima occurring for an in-plane orientation of the alkyl chain (trans) about its first dihedral angle (Φ f123, numbers are alkyl C atoms. C 1 is CH radical site). This in-plane structure is the only observed conformer for the α-EtBz radical, while two conformers, tt and tg' share this orientation at the first dihedral, but differ in the second (Φ 1234) for the αPrBz radical. The in-plane orientation lowers the local site frequencies of the CH 2 group stretches immediately adjacent to the benzylic radical site by about 50 cm -1 relative to those in pure alkyl chains or alkylbenzenes. This effectmore » of the radical site is localized on the first CH 2 group, with little effect on subsequent members of the alkyl chain. In the D 1 excited electronic state, an out-of-plane orientation is preferred for the alkyl chains, leading to torsional mode Franck-Condon activity in the D 0-D 1 spectra that is both conformer-specific and diagnostic of the conformational change.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
  2. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry and Theoretical Chemistry Inst.
Publication Date:
Grant/Contract Number:
FG02-96ER14656; CHE-1213449
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1468933
Alternate Identifier(s):
OSTI ID: 1328551