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Excited-State Dynamics Affected by Switching of a Hydrogen-Bond Network in Hydrated Aminopyrazine Clusters
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-11-18 , DOI: 10.1021/acs.jpca.0c08808 Yuji Yamada 1 , Yuji Goto 1 , Yuki Fukuda 1 , Hiroumi Ohba 1 , Yoshinori Nibu 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-11-18 , DOI: 10.1021/acs.jpca.0c08808 Yuji Yamada 1 , Yuji Goto 1 , Yuki Fukuda 1 , Hiroumi Ohba 1 , Yoshinori Nibu 1
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The cluster structures of hydrated aminopyrazines, APz–(H2O)n=2–4, in supersonic jets have been investigated measuring the size-selected electronic and vibrational spectra and determined with the aid of quantum chemical calculations. The APz–(H2O)2 structure is assigned as a cyclic N1 type where a homodromic hydrogen-bond chain starts from the amino group and ends at the 1-position nitrogen atom of the pyrazine moiety, corresponding to 2-aminopyridine–(H2O)2. On the other hand, APz–(H2O)n=3,4 has a linear hydrogen-bond network ending at the 4-position one (N4), which resembles 3-aminopyridine–(H2O)n=3,4. The hydrogen-bond network switching from the N1 type to the N4 one provides the accompanying red shifts of the S1–S0 electronic transition that are entirely consistent with those of the corresponding 2-aminopyridine and 3-aminopyridine clusters and also shows the drastically strengthened fluorescence intensity of origin bands in the electronic spectrum. The significant change in the excited-state dynamics is explored by the fluorescence lifetime measurement and the time-dependent density functional theory (TD-DFT) calculation. It is suggested that the drastic elongation of fluorescence lifetimes is due to the change in the electronic structure of the first excited state from nπ* to ππ*, resulting in the decreasing spin–orbit coupling to T1 (ππ*).
中文翻译：
水合氨基吡嗪团簇中氢键网络的转换对激发态动力学的影响
在超声速射流中，水合氨基吡嗪类APz–（H 2 O）n = 2-4的簇结构已进行了研究，测量了尺寸选择的电子光谱和振动光谱，并借助量子化学计算进行了确定。APz–（H 2 O）2结构被指定为环状N1类型，其中同质氢键链从氨基开始并在吡嗪部分的1位氮原子处终止，对应于2-氨基吡啶–（ H 2 O）2。另一方面，APz–（H 2 O）n = 3,4具有一个线性氢键网络，其末端为4位（N4），类似于3-氨基吡啶–（H2 O）n = 3.4。从N1型转变为N4的氢键网络提供了伴随的S 1 –S 0电子跃迁的红移，与相应的2-氨基吡啶和3-氨基吡啶簇的红移完全一致，并且显示出剧烈的变化。增强了电子光谱中原始谱带的荧光强度。通过荧光寿命测量和时变密度泛函理论（TD-DFT）计算探索了激发态动力学的显着变化。有人建议，荧光寿命的急剧伸长是由于从所述第一激发态的电子结构的变化Ñπ*到ππ*，导致与T 1（ππ*）耦合的自旋轨道减小。
更新日期：2020-12-03
中文翻译：
水合氨基吡嗪团簇中氢键网络的转换对激发态动力学的影响
在超声速射流中，水合氨基吡嗪类APz–（H 2 O）n = 2-4的簇结构已进行了研究，测量了尺寸选择的电子光谱和振动光谱，并借助量子化学计算进行了确定。APz–（H 2 O）2结构被指定为环状N1类型，其中同质氢键链从氨基开始并在吡嗪部分的1位氮原子处终止，对应于2-氨基吡啶–（ H 2 O）2。另一方面，APz–（H 2 O）n = 3,4具有一个线性氢键网络，其末端为4位（N4），类似于3-氨基吡啶–（H2 O）n = 3.4。从N1型转变为N4的氢键网络提供了伴随的S 1 –S 0电子跃迁的红移，与相应的2-氨基吡啶和3-氨基吡啶簇的红移完全一致，并且显示出剧烈的变化。增强了电子光谱中原始谱带的荧光强度。通过荧光寿命测量和时变密度泛函理论（TD-DFT）计算探索了激发态动力学的显着变化。有人建议，荧光寿命的急剧伸长是由于从所述第一激发态的电子结构的变化Ñπ*到ππ*，导致与T 1（ππ*）耦合的自旋轨道减小。
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