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

在液相中，玻尔兹曼分布定律下的两个分子之间的能量传递效率通常较低。反之，如果能使能量在供体分子和受体分子之间选择性流动，就能实现高效的能量传递系统。我们已经发现，激发态的2-氨基蒽醌通过选择性氢键相互作用被醇分子钝化。通过对反应过程的分析，发现了两种失活方式：面内辐射失活和面外辐射失活。发现过氧化氢异丙苯的分解反应只发生在非辐照过程中。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-氨基蒽醌为供能分子，甲醇、乙醇、过氧化氢异丙苯和二元醇为受能分子。我们发现了面内模和面外模的稳定结构。在二元醇的情况下，我们讨论了链长和猝灭过程之间的关系。通过对羟基接触分子表面积的评价，讨论了其猝灭能力。通过振动分析计算，证实了氨基芴羰基的面外振动模式的存在。通过理论计算分析和验证了实验事实。

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.