Mid-infrared spectra of an O-H···π hydrogen-bonded 1:1 complex between formic acid and benzene were measured by isolating the complex in an argon matrix at a temperature of 8 K. The O-H stretching fundamental of formic acid (νO-H) undergoes a red shift of 120 cm(-1), which is the largest among the known π-hydrogen bonded complexes of an O-H donor with respect to benzene as acceptor. Electronic structure theory methods were used extensively to suggest a suitable geometry of the complex that is consistent with a recent study performed at CCSD(T)/CBS level by Zhao et al. (J. Chem. Theory Comput. 2009, 5, 2726-2733), as well as with the measured IR spectral shifts of the present study. It has been determined that density functional theory (DFT) D functionals as well as parametrized DFT functionals like M06-2X, in conjunction with modestly sized basis sets like 6-31G (d, p), are sufficient for correct predictions of the spectral shifts observed in our measurement and also for reproducing the value of the binding energy reported by Zhao et al. We also verified that these low-cost methods are sufficient in predicting the νO-H spectral shifts of an analogous O-H···π hydrogen-bonded complex between phenol and benzene. However, some inconsistencies with respect to shifts of νO-H arise when diffuse functions are included in the basis sets, and the origin of this anomaly is shown to lie in the predicted geometry of the complex. Natural bond orbital (NBO) and atoms-in-molecule (AIM) analyses were performed to correlate the spectral behavior of the complex with its geometric parameters.

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Mid-infrared spectra of difluoroacetic acid (DFAA) have been measured by isolating the molecule in argon and nitrogen matrices at 8 K and also in the vapor phase at room temperature. In argon matrix, the O–H stretching fundamental (νO–H) of −COOH group appears as a doublet with band maxima at 3554 and 3558 cm–1, and a similar doublet for CO stretching fundamental appears at 1800 and 1810 cm–1. In the vapor phase, the νO–H transition is featured with multiple peaks, and the observed band shape has been deconvoluted as superposition of two transitions both having A-type rotational band contours. We have attributed these transitions to the two internal rotational isomers corresponding to the two distinct minima along −CHF2 torsional coordinate of the molecule. Natural bond orbital (NBO) analysis reveals that these torsional minima are the manifestations of different second order interactions involving bonding and antibonding orbitals corresponding to the rotor −CHF2 and COOH groups of the molecule. By use of the theoretically predicted rotational constants of the rotamers, the band profile for νO–H has been simulated satisfactorily by means of the PGOPHER method, and this has allowed estimating accurately the energy difference between the two rotamers as 0.54 kcal/mol. The predicted energy barrier for interconversion between the rotamers is very small, ∼0.5 kcal/mol from rotamer II to rotamer I, which implies that the molecule could hop almost freely between the two rotameric forms at room temperature. As a result, the frequencies of the key stretching vibrational modes, like νO–H, νCO, and νC–H, undergo modulation with internal rotation of the rotor −CHF2 group. Such modulation of high frequency modes could be an efficient mechanism for acceleration of rotor-induced IVR (intramolecular vibrational redistribution) well documented in the literature. Furthermore, the spectra measured in matrix isolated environment show signatures for an energetically higher third rotamer, where −OH and −CO groups are in anti orientation. It has also been shown that DFAA can easily form weak hydrogen bonded dimeric complexes with molecular nitrogen (N2), which causes νO–H to undergo a red shift of ∼30 cm–1 in argon matrix for all three DFAA monomers.

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