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Fourier Transform Fluorescence-Encoded Infrared Spectroscopy
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-01-03 00:00:00 , DOI: 10.1021/acs.jpca.7b10305 Joseph N. Mastron 1 , Andrei Tokmakoff 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-01-03 00:00:00 , DOI: 10.1021/acs.jpca.7b10305 Joseph N. Mastron 1 , Andrei Tokmakoff 1
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While time-resolved infrared (IR) vibrational spectroscopy provides insight on structural dynamics of solution-phase systems, current techniques are limited to high concentrations. Fluorescence-encoded infrared spectroscopy (FEIR) can be used to encode IR-driven vibrational excitations into excited electronic states that fluoresce, which can be detected at lower concentrations than a coherently detected IR signal. Here, we report on the development of Fourier transform FEIR as an alternate approach for high-sensitivity IR spectroscopy. Upon driving vibrational excitation with a pair of IR fields with a variable time delay, an interferometric component was observed in the encoded fluorescence. This signal can be Fourier transformed to obtain a vibrational spectrum. By additionally varying the time delay of the encoding pulse following the second IR pulse, we observed frequency-difference oscillations, allowing us to construct a 2D correlation spectrum of coupled vibrations. Response functions for this experiment have been modeled, which reproduce the observed spectral features and relate them to excitation pathways using diagrammatic perturbation theory. The pathways observed in a 2D FEIR spectrum arise from the excitation of vibrational populations and coherences between coupled vibrations.
中文翻译：
傅里叶变换荧光编码红外光谱
尽管时间分辨红外（IR）振动光谱学可以洞悉溶液相系统的结构动力学，但目前的技术仅限于高浓度。荧光编码的红外光谱（FEIR）可用于将IR驱动的振动激发编码为发荧光的激发电子态，可以以比连贯检测到的IR信号更低的浓度检测到这种状态。在这里，我们报告傅立叶变换FEIR的发展，作为高灵敏度红外光谱的另一种方法。在使用一对具有可变时间延迟的IR场驱动振动激发时，在编码的荧光中观察到干涉分量。可以对该信号进行傅立叶变换以获得振动频谱。通过另外改变第二个IR脉冲之后的编码脉冲的时间延迟，我们观察到了频差振荡，从而使我们能够构建耦合振动的二维相关频谱。已对该实验的响应函数进行了建模，该函数重现了观察到的光谱特征，并使用图解扰动理论将它们与激发路径相关联。在二维FEIR频谱中观察到的路径来自振动种群的激发以及耦合振动之间的相干性。
更新日期：2018-01-03
中文翻译：
傅里叶变换荧光编码红外光谱
尽管时间分辨红外（IR）振动光谱学可以洞悉溶液相系统的结构动力学，但目前的技术仅限于高浓度。荧光编码的红外光谱（FEIR）可用于将IR驱动的振动激发编码为发荧光的激发电子态，可以以比连贯检测到的IR信号更低的浓度检测到这种状态。在这里，我们报告傅立叶变换FEIR的发展，作为高灵敏度红外光谱的另一种方法。在使用一对具有可变时间延迟的IR场驱动振动激发时，在编码的荧光中观察到干涉分量。可以对该信号进行傅立叶变换以获得振动频谱。通过另外改变第二个IR脉冲之后的编码脉冲的时间延迟，我们观察到了频差振荡，从而使我们能够构建耦合振动的二维相关频谱。已对该实验的响应函数进行了建模，该函数重现了观察到的光谱特征，并使用图解扰动理论将它们与激发路径相关联。在二维FEIR频谱中观察到的路径来自振动种群的激发以及耦合振动之间的相干性。
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