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Photoisomerization is a prototypical photophysical and photochemical reaction, and the reaction quantum yield depends on its excited-state dynamic. Changing the evolution path of molecular excited states to achieve precise control over photochemical reactions has long been a dream pursued by physicists and chemists. To investigate the effect of femtosecond laser pulse on the ultrafast reaction, the ultrafast photoisomerization of 1, 1'-diethyl-2, 2'-cyanine iodide (1122C) in methanol is studied using pump-dump-probe spectroscopy. A third femtosecond pulse (Dump) at 1030 nm, which is delayed by 1 ps relative to the initial pump pulse, is Introduced into the traditional pump-probe experiment. The recovery of ground state bleaching (GSB) and decrease of the cis product are observed in the pump-dump-probe experiment. It indicates that the dump pulse successfully promotes the initial transform: skipping the trans-cis isomerization pathway in the excited state and returning to the ground state directly through stimulated emission. It is found that the cis yield is reduced by approximately 12.1% under irradiation of the dump pulse. Our research shows that the quantum yields of a typic ultrafast photoisomerization reaction is successfully regulated by using femtosecond laser pulse, demonstrating the potential of femtosecond multi-pulse spectroscopy in modifying excited-state evolution pathways and optimizing photochemical reaction yields. This study provides theoretical and technical support for precisely controlling complex photochemical reactions in the future.
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Keywords:
- femtosecond transient absorption spectroscopy /
- photoisomerization /
- excited state dynamics /
- pump-dump-probe
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图 1 1122C分子光致异构化示意图
Figure 1. Schematic diagram of the photo-isomerization process for 1122C.
图 2 泵浦-探测和泵浦-受激亏蚀-探测实验光路图
Figure 2. Diagram of pump-probe and pump-dump-probe experiments.
图 3 1122C分子甲醇溶液的稳态吸收光谱图(蓝色箭头表示瞬态实验的激发波长450 nm)
Figure 3. Steady-state absorption spectrum of 1122C in methanol (the blue arrow indicates the 450 nm is selected as the excitation wavelength for the following transient experiment).
图 4 1122C分子甲醇溶液的Pump-Probe实验结果 (a)二维瞬态吸收光谱图(激发波长为450 nm); (b)不同延迟时刻下的瞬态吸收光谱; (c)几个具有代表性的不同探测波长的动力学轨迹; (d)探测波长为550 nm的动力学轨迹以及拟合结果
Figure 4. (a) Two-dimensional Pump-Probe transient absorption spectrum of 1122C in methanol (pump = 450 nm); (b) time-resolved transient absorption in the different delay times; (c) representative transient absorption kinetic trace for various probe wavelengths; (d) the kinetic curve and fitted results at 550 nm.
图 5 1122C分子激发态波包演化动力学示意图.
Figure 5. Schematic wavepacket motion in the 1122C photoismerization reaction.
图 6 1122C分子甲醇溶液的泵浦-受激亏蚀-探测实验结果 (a) 二维瞬态吸收光谱图(激发波长为450 nm, 受激亏蚀延迟为1 ps, 受激亏蚀波长为1030 nm); (b), (c) 2 ps和78 ps延迟时刻下受激亏蚀光作用前后的瞬态吸收光谱图(PP为泵浦-探测, PDP为泵浦-受激亏蚀-探测); (d), (e) 探测波长为525 nm和550 nm的DP, PP和PDP动力学曲线(DP为受激亏蚀-探测); (f) 1122C分子在受激亏蚀光作用下波包运动示意图
Figure 6. Pump-dump-probe transient absorption of 1122C in methanol: (a) Two-dimensional spectrum (pump: 450 nm, dump: 1030 nm, and dump at 1 ps delay time); (b), (c) transient absorption spectra at the 2 ps (b) and 78 ps (c) delay times in the presence (PDP) and absence (PP) of a dump pulse; (d), (e) selected DP, PP and PDP kinetic traces at 525 nm (d) and 550 nm (e); (f) schematic wavepacket motion of 1122C in the pump-dump-probe experiment.
图 7 泵浦-探测和泵浦-受激亏蚀-探测吸收谱在545 nm的动力学轨迹以及拟合曲线
Figure 7. Kinetic traces and fitting curves at 545 nm of pump-probe and pump-dump-probe spectra.
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