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首页> 外文期刊>The Journal of Chemical Physics >Effective chromophore potential,dissipative trajectories,and vibrational energy relaxation: Br_2 in Ar matrix
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Effective chromophore potential,dissipative trajectories,and vibrational energy relaxation: Br_2 in Ar matrix

机译：有效发色团势，耗散轨迹和振动能弛豫：Ar矩阵中的Br_2

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摘要

The intramolecular wave packet dynamics on the electronic B (~3II_0) potential of Br_2 in solid argon is induced and interrogated by femtosecond pump-probe spectroscopy.An effective potential of the chromophore in the solid is derived from the wave packet period for different excitation photon energies.Deep in the potential well,it is consistent with vibrational energies from wavelength-resolved spectra.It extends to higher energies,where the vibrational bands merge to a continuum,and even beyond the dissociation limit,thus quantifying the cage effect of the argon matrix.This advantage of pump-probe spectroscopy is related to a reduced contribution of homogeneous and inhomogeneous line broadenings.The vibrational energy relaxation rates are determined by a variation of the probe window spatial position via the probe quantum energy.A very large energy loss in the first excursion of the wave packet is observed near the dissociation limit.This strong interaction with the argon matrix is directly displayed in an experimental trajectory.
机译：飞秒泵浦-探针光谱法诱导并询问了固体氩中Br_2的电子B（〜3II_0）势的分子内波包动力学。固体的发色团的有效电势源自不同激发光子的波包周期在势阱的深处，它与来自波长分辨光谱的振动能量一致。它扩展到较高的能量，在该处振动带合并成一个连续体，甚至超过了解离极限，从而量化了氩的笼形效应泵浦探针光谱法的这一优势与减少均匀和不均匀的谱线展宽有关。振动能量的松弛率取决于探针窗口空间位置通过探针量子能量的变化。在离解极限附近观察到了波包的第一次偏移。与氩矩阵的强相互作用为d正确显示在实验轨迹中。

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