The two hydrogen bond solvation sites exhibited by the carbonyl group in acetophenone are influenced by alkylation of the methyl group in both the acetophenone and in the prototype solvent methanol, largely due to London dispersion forces. Phenyl docking and alkyl docking preferences can be realized at will by appropriate substitution. In particular, cyclopropylation helps to stabilize the opposite phenyl docking site. In all cases, the energy gap is small enough to allow for a simultaneous detection even under low temperature conditions. This density functional prediction is checked experimentally by jet FTIR spectroscopy and largely confirmed. A spurious out-of-plane solvation preference predicted for cyclopropylphenylketone with tert-butyl alcohol by B3LYP-D3 calculations is not confirmed experimentally. It is unlikely that this discrepancy is due to zero-point energy effects. Instead, the second most stable alkyl-side solvation motif predicted with a more in-plane coordination is found in the jet expansion. Overall, the ability of carbonyl solvation balances to benchmark subtle electronic structure effects for non-covalent interactions without major nuclear motion corrections is supported.

中文翻译：

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醇与酮的三维对接：基于苯乙酮溶剂化能量平衡的实验基准。

苯乙酮和原型溶剂甲醇中的甲基烷基化会影响苯乙酮中羰基显示的两个氢键溶剂化位点，这主要是由于伦敦的分散力。苯基对接和烷基对接的偏好可以通过适当的取代任意实现。特别地，环丙基化有助于稳定相反的苯基对接位点。在所有情况下，能隙都足够小，即使在低温条件下也可以同时进行检测。通过喷射FTIR光谱对这种密度泛函功能预测进行了实验检验，并得到了充分证实。通过实验未确定通过B3LYP-D3计算预测的环丙基苯基酮与叔丁醇的杂散平面外溶剂化偏好。这种差异不太可能归因于零点能量效应。取而代之的是，在射流膨胀中发现了第二个最稳定的烷基侧溶剂化基序，其具有更多的平面内配位。总体而言，支持了羰基溶剂化平衡为非共价相互作用进行基准微妙电子结构效应的基准而无需进行重大核运动校正的能力。