Molecular Simulation Analysis of the Vibrationally Sensitized Reaction through the Hydrogen Bonding Interaction

根据玻尔兹曼分布定律，两分子之间的能量传递效率在液相中通常较低。相反，如果我们能在给体分子和受体分子之间进行选择性的能量流动，就能实现高效的能量传递体系。我们已经发现，被激发的2-氨基蒽醌通过选择性氢键相互作用被醇分子失活。通过对反应的分析，失活过程有两种模式，即辐射失活过程（面内模式）和辐射失活过程（面外模式）。发现异丙四氢过氧化物的分解反应只发生在非辐射过程中。通过理论计算对这一过程进行了分析。以1,2,3,4氨基- 9-氨基芴酮和2-氨基蒽醌为能量供体分子，甲醇、乙醇、异丙苯氢过氧化物和二醇为能量受体分子。得到了平面内模态和面外模态的稳定结构。在二醇的情况下，我们讨论了链的长度与淬火过程的关系。评价了羟基的接触分子表面积，讨论了其猝灭能力。通过振动分析计算，证实了氨基氟离子羰基存在面外模振动。通过理论计算对实验事实进行了分析和证实。

The energy transfer efficiency between two molecules under the Boltzmann distribution law is usually low in the liquid phase. On the contrary, if we could make the selective energy flow between the donor molecules and the accepter molecules, so that we'll be realized the high efficiency energy transfer system. We already found that the excited 2-aminoanthraquione was deactivated by the alcohol molecule through the selective hydrogen bonding interaction. By the analysis of the reaction, there are two modes of deactivation process, radiation deactivate process (in-plane mode) and radiation deactivate process (out-of-plane mode). We found the decomposition reaction of the cumenhydroperoxcide only occurs at the nonradiational process. We analyzed this process by the theoretical calculation. We used 1,2,3,4 amino 9-aminofluorenone and 2-aminoanthraquinone as the energy donor molecules, methanol, ethanol, cumenhydroperoxcide and the diols as the energy accepter molecules. We found the stable structures both the in-plane mode and the out-of-plane mode. In the case of the diols we discussed about the relation between the length of the chain and the quenching process. The evaluation of the contact molecular surface area of the hydroxyl group, we discussed about ability of the quenching. We confirmed the existence of the out-of-plane mode vibration of the carbonyl group of the aminofluorenons by the vibrational analysis calculation. We analyzed and confirmed the experimental facts by the theoretical calculations.