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.

中文翻译：

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通过SEP-R2PI方法进行的基准实验气相分子间离解能。

分离的冷双分子配合物的气相基态解离能D0（S0）是其成分之间的分子间相互作用强度的基本量度。准确的D0值对于理解分子间键合，基准化高级理论计算以及对从晶体学到生物化学等领域中使用的色散校正后的密度泛函或力场模型进行参数化至关重要。我们回顾了55种不同M·S配合物的气相D0（S0）和D0（S1）值的实验测量结果，其中M为（杂）芳族分子，S为闭壳溶剂原子或分子。实验采用三重共振SEP-R2PI激光方法，该方法涉及M中心（S0→S1）电子激发，随后是S1→S0受激发射，跨越了S0状态的振动水平。在足够高的振动能量下，会发生M⋅S配合物的振动预离解。总共49个解离能被包围在≤1.0kJ / mol以内，提供了一个准确的非共价相互作用的大型实验数据库。