Sinha, Rajeev K (2020) Benchmark Experimental Gas-Phase Intermolecular Dissociation Energies by the SEP-R2PI Method. Annual Review of Physical Chemistry, 71. pp. 189-211. ISSN 0066-426X

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Abstract

The gas-phase ground-state dissociation energy D0(S0) of an isolated and cold bimolecular complex is a fundamental measure of the intermolecular interaction strength between its constituents. Accurate D0 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 D0(S0) and D0(S1) 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 (S0 → S1)electronic excitation, followed by S1 → S0 stimulated emission spanning a range of S0 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

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