Intermolecular dissociation energies of dispersively bound complexes of aromatics with noble gases and nitrogen

Knochenmuss, Richard; Sinha, Rajeev K.; Leutwyler, Samuel (2018). Intermolecular dissociation energies of dispersively bound complexes of aromatics with noble gases and nitrogen. The Journal of Chemical Physics, 148(13), p. 134302. American Institute of Physics 10.1063/1.5019432

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We measured accurate intermolecular dissociation energiesD0of the supersonic jet-cooled complexesof 1-naphthol (1NpOH) with the noble gases Ne, Ar, Kr, and Xe and with N2, using the stimulated-emission pumping resonant two-photon ionization method. The ground-state valuesD0(S0) for the1NpOH·S complexes with S= Ar, Kr, Xe, and N2were bracketed to be within±3.5%; they are 5.67±0.05 kJ/mol for S = Ar, 7.34±0.07 kJ/mol for S = Kr, 10.8±0.28 kJ/mol for S = Xe, 6.67±0.08kJ/mol for isomer 1 of the 1NpOH·N2complex, and 6.62±0.22 kJ/mol for the corresponding isomer2. For S = Ne, the upper limit isD0<3.36 kJ/mol. The dissociation energies increase by 1%-5% uponS0→S1excitation of the complexes. Three dispersion-corrected density functional theory (DFT-D)methods (B97-D3, B3LYP-D3, andωB97X-D) predict that the most stable form of these complexesinvolves dispersive binding to the naphthalene “face.” A more weakly bound edge isomer is predictedin which the S moiety is H-bonded to the OH group of 1NpOH; however, no edge isomers wereobserved experimentally. The B97-D3 calculated dissociation energiesD0(S0) of the face complexeswith Ar, Kr, and N2agree with the experimental values within<5%, but theD0(S0) for Xe is 12%too low. The B3LYP-D3 andωB97X-D calculatedD0(S0) values exhibit larger deviations to bothlarger and smaller dissociation energies. For comparison to 1-naphthol, we calculated theD0(S0)of the carbazole complexes with S = Ne, Ar, Kr, Xe, and N2using the same DFT-D methods. Therespective experimental values have been previously determined to be within<2%. Again, the B97-D3 results are in the best overall agreement with experiment.

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