TY - JOUR
T1 - The terahertz spectrum and quantum chemical assignment of 2,2′-bithiophene in cyclohexane
AU - Fedor, Anna M.
AU - Allis, Damian G.
AU - Korter, Timothy M.
PY - 2009/3/18
Y1 - 2009/3/18
N2 - The room temperature solution-phase terahertz (THz, 7 to 165 cm-1) spectrum of 2,2′-bithiophene in cyclohexane is reported. Density functional theory (B3LYP) and ab initio (MP2) methods employing the 6-311++G(2d,2p) and aug-cc-pVDZ basis sets are used to assign the THz vibrational structure and determine the relative populations of the cis and trans conformations, as well as the trans-trans rotational barrier height and the effects of the cyclohexane solvent on the predicted molecular geometries and vibrational frequencies. Significant differences are seen in the performance of the different theoretical methods, with the best performing method dependent upon the molecular property of interest. The best fit model of the experimental THz spectrum is achieved using MP2/aug-cc-pVDZ, which places the relative trans and cis populations at 54% and 46%, respectively.
AB - The room temperature solution-phase terahertz (THz, 7 to 165 cm-1) spectrum of 2,2′-bithiophene in cyclohexane is reported. Density functional theory (B3LYP) and ab initio (MP2) methods employing the 6-311++G(2d,2p) and aug-cc-pVDZ basis sets are used to assign the THz vibrational structure and determine the relative populations of the cis and trans conformations, as well as the trans-trans rotational barrier height and the effects of the cyclohexane solvent on the predicted molecular geometries and vibrational frequencies. Significant differences are seen in the performance of the different theoretical methods, with the best performing method dependent upon the molecular property of interest. The best fit model of the experimental THz spectrum is achieved using MP2/aug-cc-pVDZ, which places the relative trans and cis populations at 54% and 46%, respectively.
KW - Bithiophene
KW - Density functional theory
KW - Far-infrared
KW - Terahertz spectroscopy
KW - Torsional potential
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U2 - 10.1016/j.vibspec.2008.06.001
DO - 10.1016/j.vibspec.2008.06.001
M3 - Article
AN - SCOPUS:60249098198
VL - 49
SP - 124
EP - 132
JO - Vibrational Spectroscopy
JF - Vibrational Spectroscopy
SN - 0924-2031
IS - 2
ER -