Benchmark experimental gas-phase intermolecular dissociation energies by the SEP-R2PI method

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Annual Review of Physical Chemistry


The gas-phase ground-state dissociation energy D (S ) of an isolated and cold bimolecular complex is a fundamental measure of the intermolecular interaction strength between its constituents. Accurate D values are important for the understanding of intermolecular bonding, for benchmarking high-level theoretical calculations, and for the parameterization of dispersion-corrected density functionals or force-field models that are used in fields ranging from crystallography to biochemistry. We review experimental measurements of the gas-phase D (S ) and D (S ) values of 55 different M⋅S complexes, where M is a (hetero)aromatic molecule and S is a closed-shell solvent atom or molecule. The experiments employ the triply resonant SEP-R2PI laser method, which involves M-centered (S → S ) electronic excitation, followed by S → S stimulated emission spanning a range of S state vibrational levels. At sufficiently high vibrational energy, vibrational predissociation of the M⋅S complex occurs. A total of 49 dissociation energies were bracketed to within ≤1.0 kJ/mol, providing a large experimental database of accurate noncovalent interactions. 0 0 0 0 0 0 1 0 1 1 0 0

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