通过 3D IR 交换光谱法测试无记忆光谱坐标。
Testing for memory-free spectroscopic coordinates by 3D IR exchange spectroscopy.
机构信息
Department of Chemistry, University of Zurich, CH-8057 Zurich, Switzerland.
Department of Chemistry, University of Zurich, CH-8057 Zurich, Switzerland
出版信息
Proc Natl Acad Sci U S A. 2014 Jul 22;111(29):10462-7. doi: 10.1073/pnas.1406967111. Epub 2014 Jul 7.
Using 3D infrared (IR) exchange spectroscopy, the ultrafast hydrogen-bond forming and breaking (i.e., complexation) kinetics of phenol to benzene in a benzene/CCl4 mixture is investigated. By introducing a third time point at which the hydrogen-bonding state of phenol is measured (in comparison with 2D IR exchange spectroscopy), the spectroscopic method can serve as a critical test of whether the spectroscopic coordinate used to observe the exchange process is a memory-free, or Markovian, coordinate. For the system under investigation, the 3D IR results suggest that this is not the case. This conclusion is reconfirmed by accompanying molecular dynamics simulations, which furthermore reveal that the non-Markovian kinetics is caused by the heterogeneous structure of the mixed solvent.
利用三维红外（IR）交换光谱，研究了在苯/CCl4 混合物中苯酚与苯之间超快氢键形成和断裂（即络合）的动力学。通过引入第三个时间点来测量苯酚的氢键状态（与二维 IR 交换光谱相比），该光谱方法可以作为对用于观察交换过程的光谱坐标是否为无记忆或马尔可夫坐标的关键测试。对于所研究的系统，3D IR 结果表明并非如此。这一结论通过伴随的分子动力学模拟得到了进一步证实，该模拟进一步表明，非马尔可夫动力学是由混合溶剂的非均相结构引起的。
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