TY - JOUR
T1 - Solvation-induced σ-complex structure formation in the gas phase
T2 - A revisit to the infrared spectroscopy of [C 6H 6-(CH 3OH) 2] +
AU - Mizuse, Kenta
AU - Suzuki, Yuta
AU - Mikami, Naohiko
AU - Fujii, Asuka
PY - 2011/10/20
Y1 - 2011/10/20
N2 - Structures of the [C 6H 6-(CH 3OH) 2] + cluster cation are investigated with infrared (IR) spectroscopy. While the noncovalent type structure has been confirmed for the n = 1 cluster of [C 6H 6-(CH 3OH) n] +, only contradictory interpretations have been given for the spectra of n = 2, in which significant changes have been observed with the Ar tagging. In the present study, we revisit IR spectroscopy of the n = 2 cluster from the viewpoint of the σ-complex structure, which includes a covalent bond formation between the benzene and methanol moieties. The observed spectral range is extended to the lower-frequency region, and the spectrum is measured with and without Ar and N 2 tagging. A strongly hydrogen-bonded OH stretch band, which is characteristic to the σ-complex structure, is newly found with the tagging. The remarkable spectral changes with the tagging are interpreted by the competition between the σ-complex and noncovalent complex structures in the [C 6H 6-(CH 3OH) 2] + system. This result shows that the microsolvation only with one methanol molecule can induce the σ-complex structure formation.
AB - Structures of the [C 6H 6-(CH 3OH) 2] + cluster cation are investigated with infrared (IR) spectroscopy. While the noncovalent type structure has been confirmed for the n = 1 cluster of [C 6H 6-(CH 3OH) n] +, only contradictory interpretations have been given for the spectra of n = 2, in which significant changes have been observed with the Ar tagging. In the present study, we revisit IR spectroscopy of the n = 2 cluster from the viewpoint of the σ-complex structure, which includes a covalent bond formation between the benzene and methanol moieties. The observed spectral range is extended to the lower-frequency region, and the spectrum is measured with and without Ar and N 2 tagging. A strongly hydrogen-bonded OH stretch band, which is characteristic to the σ-complex structure, is newly found with the tagging. The remarkable spectral changes with the tagging are interpreted by the competition between the σ-complex and noncovalent complex structures in the [C 6H 6-(CH 3OH) 2] + system. This result shows that the microsolvation only with one methanol molecule can induce the σ-complex structure formation.
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U2 - 10.1021/jp202680x
DO - 10.1021/jp202680x
M3 - Article
C2 - 21657262
AN - SCOPUS:80054708932
SN - 1089-5639
VL - 115
SP - 11156
EP - 11161
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 41
ER -