Intermolecular dissociation energies of hydrogen-bonded 1-naphthol complexes

Knochenmuss, Richard; Sinha, Rajeev K.; Poblotzki, Anja; Den, Takuya; Leutwyler, Samuel (2018). Intermolecular dissociation energies of hydrogen-bonded 1-naphthol complexes. The Journal of Chemical Physics, 149(20), p. 204311. American Institute of Physics 10.1063/1.5055720

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We have measured the intermolecular dissociation energiesD0of supersonically cooled 1-naphthol(1NpOH) complexes with solvents S = furan, thiophene, 2,5-dimethylfuran, and tetrahydrofuran. Thenaphthol OH forms non-classical H-bonds with the aromaticπ-electrons of furan, thiophene, and2,5-dimethylfuran and a classical H-bond with the tetrahydrofuran O atom. Using the stimulated-emission pumping resonant two-photon ionization method, the ground-stateD0(S0) values werebracketed as 21.8±0.3 kJ/mol for furan, 26.6±0.6 kJ/mol for thiophene, 36.5±2.3 kJ/mol for2,5-dimethylfuran, and 37.6±1.3 kJ/mol for tetrahydrofuran. The dispersion-corrected density func-tional theory methods B97-D3, B3LYP-D3 (using the def2-TZVPP basis set), andωB97X-D [usingthe 6-311++G(d,p) basis set] predict that the H-bonded (edge) isomers are more stable than the faceisomers bound by dispersion; experimentally, we only observe edge isomers. We compare the cal-culated and experimentalD0values and extend the comparison to the previously measured 1NpOHcomplexes with cyclopropane, benzene, water, alcohols, and cyclic ethers. The dissociation energiesof the nonclassically H-bonded complexes increase roughly linearly with the average polarizabilityof the solvent, ̄α(S). By contrast, theD0values of the classically H-bonded complexes are larger,increase more rapidly at low ̄α(S), but saturate for large ̄α(S). The calculatedD0(S0) values forthe cyclopropane, benzene, furan, and tetrahydrofuran complexes agree with experiment to within1 kJ/mol and those of thiophene and 2,5-dimethylfuran are∼3 kJ/mol smaller than experiment. TheB3LYP-D3 calculatedD0values exhibit the lowest mean absolute deviation (MAD) relative toexperiment (MAD = 1.7 kJ/mol), and the B97-D3 andωB97X-D MADs are 2.2 and 2.6 kJ/mol,respectively.

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