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首页> 外文期刊>The Journal of Chemical Physics >Evidence of pure L-1(b) fluorescence from redshifted indole-polar solvent complexes in a supersonic jet
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Evidence of pure L-1(b) fluorescence from redshifted indole-polar solvent complexes in a supersonic jet

机译：超音速喷射中红移的吲哚-极性溶剂络合物的纯L-1（b）荧光证据

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摘要

Two-photon polarized fluorescence excitation and vibronically resolved one-photon dispersed fluorescence spectra of the long-wavelength absorbing van der Waals complexes of indole with water, methanol, and formamide were examined for the purpose of firmly assigning the nature of the lowest singlet excited electronic state. The two-photon spectra for all of these complexes have circular/linear polarization ratios of absorptivity (Omega-values) that show that excitation is to the L-1(b) state. Analysis of the Franck-Condon (FC) patterns of the dispersed fluorescence for these indole-polar solvent complexes show that emission is also from the L-1(b) State in each case. In the emission spectra, the intensity ratios of the origin and v(26) lines are about 2:1, which is the value expected for L-1(b) emission. The v(26) vibration is the most intense nonorigin vibronic line, as expected for L-1(b) emission. Finally, there is little or no intensity from the v(8), y(9), and v(10) vibrations, which would be strongly active with emission from the L-1(a) state. These results show unequivocally that for these indole-polar solvent complexes the L-1(a) state does not shift in energy below the L-1(b) state-contrary to the interpretation of several recent papers. Further support is given to the assignment of L-1(b) emission by spectral simulations. The jet-cooled complexes do not exhibit excited state complex (exciplex) characteristics, wherein the solvent is much more strongly bound in the excited state than in the ground state. (C) 1998 American Institute of Physics. [References: 39]
机译：考察了吲哚与水，甲醇和甲酰胺的长波长吸收范德华配合物的双光子偏振荧光激发和被光子分辨的单光子分散荧光光谱，目的是确定最低单线激发电子的性质。州。所有这些配合物的双光子光谱具有吸收率的圆/线性极化比（Ω值），表明激发是在L-1（b）状态。对这些吲哚-极性溶剂络合物的分散荧光的弗兰克-康登（FC）模式进行的分析表明，在每种情况下，发射都来自L-1（b）状态。在发射光谱中，原点和v（26）线的强度比约为2：1，这是L-1（b）发射的预期值。如预期的L-1（b）发射，v（26）振动是最强烈的非原点振动线。最后，来自v（8），y（9）和v（10）振动的强度很小或没有强度，这在L-1（a）状态的发射中会非常活跃。这些结果清楚地表明，对于这些吲哚-极性溶剂配合物，L-1（a）状态的能量转移不会低于L-1（b）状态，这与最近几篇论文的解释相反。通过频谱模拟进一步支持了L-1（b）发射的分配。喷射冷却的配合物不表现出激发态配合物（激态）特性，其中在激发态下的溶剂比基态更牢固地结合。 （C）1998美国物理研究所。 [参考：39]

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