Anharmonic modeling of the conformation-specific IR spectra of ethyl, n-propyl, and n-butylbenzene.
Conformation-specific UV-IR double resonance spectra are presented for ethyl, n-propyl, and n-butylbenzene. With the aid of a local mode Hamiltonian that includes the effects of stretch-scissor Fermi resonance, the spectra can be accurately modeled for specific conformers. These molecules allow for further development of a first principles method for calculating alkyl stretch spectra. Across all chain lengths, certain dihedral patterns impart particular spectral motifs at the quadratic level. However, the anharmonic contributions are consistent from molecule to molecule and conformer to conformer. This transferability of anharmonicities allows for the Hamiltonian to be constructed from only a harmonic frequency calculation, reducing the cost of the model. The phenyl ring alters the frequencies of the CH2 stretches by about 15 cm(-1) compared to their n-alkane counterparts in trans configurations. Conformational changes in the chain can lead to shifts in frequency of up to 30 cm(-1).
Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA.
Daniel P
DP
Tabor
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Daniel M
DM
Hewett
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Sebastian
S
Bocklitz
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Joseph A
JA
Korn
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Anthony J
AJ
Tomaine
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Arun K
AK
Ghosh
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Timothy S
TS
Zwier
Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA.
Edwin L
EL
Sibert