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首页> 外文期刊>Physical chemistry chemical physics: PCCP >H-bonded network rearrangements in the S0, S1 and D0 states of neutral and cationic p-cresol(H2O)(NH3) complexes
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H-bonded network rearrangements in the S0, S1 and D0 states of neutral and cationic p-cresol(H2O)(NH3) complexes

机译：中性和阳离子对甲酚（H2O）（NH3）配合物在S0，S1和D0状态下的H键网络重排

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摘要

The H-bonded network rearrangements in the S0, S1 and D0 states of the neutral and cationic p-CreOH(H2O)(NH3) complexes were studied experimentally by means of (1 + 1)/(1 + 1') REMPI (Resonantly Enhanced MultiPhoton Ionization) and time resolved LIF (Laser Induced Fluorescence) spectroscopies combined with DFT (Density Functional Theory) calculations at the B3LYP/ 6-311G++(d,p) level. A comparison of the rearrangement process of the H-bonded network in the three states is given. Two cyclic H-bonded isomers were found on the S0 potential energy surface and the results indicate that the rearrangement in this state is unlikely at the temperature of the supersonic expansion due to the presence of a high-energy barrier (7503 cm~(-1)). On the other hand, the re-determination of the S1 excited state lifetimes confirms that neither the H-bonded rearrangement nor the excited state hydrogen transfer (ESHT) reaction takes place in the S1 state at the excitation energies of this work. Thus, it is concluded that the absorption of the second photon to reach the D0 state takes place from the S1 state of the cychc-(OH-OH2-NH3) isomer. A preferential evaporation of H2O upon vertical ionization of the cyclic-(OH-OH2-NH3) isomer is observed which is consistent with a statistical redistribution of the internal energy. Nevertheless, our theoretical calculations suggest that initial excitation of the H-bonded network rearrangement modes may also play a role to leave the H2O molecule as a terminal moiety in a chain-(OH-NH3-OH2)~+ isomer. The reaction pathway for the solvent rearrangement involves a double proton transfer process with a very low energy barrier (575 cm~(-1)) that is overcome at the vertical ionization energy of the complex.
机译：通过（1 +1）/（1 +1'）REMPI（共振）实验研究了中性和阳离子p-CreOH（H2O）（NH3）配合物在S0，S1和D0状态下的H键网络重排在B3LYP / 6-311G ++（d，p）水平上结合DFT（密度泛函理论）计算和增强的多光子电离）和时间分辨LIF（激光诱导荧光）光谱。给出了三种状态下H键网络重排过程的比较。在S0势能面上发现了两个环状的H键键异构体，结果表明，由于存在高能垒（7503 cm〜（-1），在超音速膨胀的温度下，这种状态下的重排不太可能））。另一方面，S1激发态寿命的重新确定证实了在这项工作的激发能下，S键态既没有发生H键重排也没有发生激发态氢转移（ESHT）反应。因此，可以得出结论，第二光子的吸收达到D0状态是从cychc-（OH-OH2-NH3）异构体的S1状态发生的。观察到在环-（OH-OH2-NH3）异构体垂直电离时H2O优先蒸发，这与内部能量的统计重新分布是一致的。然而，我们的理论计算表明，H键网络重排模式的初始激发也可能起到使H2O分子作为链-（OH-NH3-OH2）〜+异构体中的末端部分的作用。溶剂重排的反应途径涉及双质子转移过程，该过程具有非常低的能垒（575 cm〜（-1）），可以在配合物的垂直电离能下克服它。

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