TY - JOUR
T1 - Infrared Spectrum of Toluene
T2 - Comparison of Anharmonic Isolated-Molecule Calculations and Experiments in Liquid Phase and in a Ne Matrix
AU - Knaanie, Roie
AU - Šebek, Jiří
AU - Tsuge, Masashi
AU - Myllys, Nanna
AU - Khriachtchev, Leonid
AU - Räsänen, Markku
AU - Albee, Brian
AU - Potma, Eric O.
AU - Gerber, R. Benny
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/5/19
Y1 - 2016/5/19
N2 - First-principles anharmonic calculations are carried out for the CH stretching vibrations of isolated toluene and compared with the experimental infrared spectra of isotopologues of toluene in a Ne matrix at 3 K and of liquid toluene at room temperature. The calculations use the vibrational self-consistent field method and the B3LYP potential surface. In general, good agreement is found between the calculations and experiments. However, the spectrum of toluene in a Ne matrix is more complicated than that predicted theoretically. This distinction is discussed in terms of matrix-site and resonance effects. Interestingly, the strongest peak in the CH stretching spectrum has similar widths in the liquid phase and in a Ne matrix, despite the very different temperatures. Implications of this observation to the broadening mechanism are discussed. Finally, our results show that the B3LYP potential offers a good description of the anharmonic CH stretching band in toluene, but a proper description of matrix-site and resonance effects remains a challenge.
AB - First-principles anharmonic calculations are carried out for the CH stretching vibrations of isolated toluene and compared with the experimental infrared spectra of isotopologues of toluene in a Ne matrix at 3 K and of liquid toluene at room temperature. The calculations use the vibrational self-consistent field method and the B3LYP potential surface. In general, good agreement is found between the calculations and experiments. However, the spectrum of toluene in a Ne matrix is more complicated than that predicted theoretically. This distinction is discussed in terms of matrix-site and resonance effects. Interestingly, the strongest peak in the CH stretching spectrum has similar widths in the liquid phase and in a Ne matrix, despite the very different temperatures. Implications of this observation to the broadening mechanism are discussed. Finally, our results show that the B3LYP potential offers a good description of the anharmonic CH stretching band in toluene, but a proper description of matrix-site and resonance effects remains a challenge.
UR - http://www.scopus.com/inward/record.url?scp=84971225594&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.6b01604
DO - 10.1021/acs.jpca.6b01604
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:84971225594
SN - 1089-5639
VL - 120
SP - 3380
EP - 3389
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 19
ER -