Anharmonic modeling of the conformation-specific IR spectra of ethyl, n-propyl, and n-butylbenzene

作者：Tabor Daniel P; Hewett Daniel M; Bocklitz Sebastian; Korn Joseph A; Tomaine Anthony J; Ghosh Arun K; Zwier Timothy S^*; Sibert Edwin L III

来源：Journal of Chemical Physics, 2016, 144(22): 224310.

DOI：10.1063/1.4953181

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). Published by AIP Publishing.

• 出版日期2016-6-14