Multiple quantum coherence spectroscopy.
Multiple quantum coherence spectroscopy.
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多重量子相干光谱。
DOI：
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发表时间：
2009
影响因子：
2.9
通讯作者：
J. C. Wright
中科院分区：
文献类型：
--
作者：
N. Mathew;Lena A. Yurs;S. Block;Andrei V. Pakoulev;K. Kornau;J. C. Wright
多量子相干为复杂系统的研究提供了一种强有力的方法，因为增加量子力学叠加态中的量子态数量增加了光谱测量的选择性。我们证明了频域多量子相干多维光谱可以利用不同频率的激发脉冲产生这些叠加态。利用两种激发频率激发二羰基铑螯合物的对称和非对称拉伸模式，并利用动态斯塔克效应攀登不同泛音和组合带态的振动阶梯，形成叠加态。单色仪解决了构成叠加态的不同相干的自由感应衰减。三个光谱维度提供了观察19种不同光谱特征所需的选择性，这些特征与涉及多达11种与激发场相互作用的完全相干非线性过程相关。不同的特征作为分子势能超表面对角线和非对角线部分的光谱探针。这种方法可以看作是相干泵-探针光谱，其中泵是一系列激发脉冲，用于制备多量子相干性，探针是另一系列脉冲，用于产生输出相干性。
Multiple quantum coherences provide a powerful approach for studies of complex systems because increasing the number of quantum states in a quantum mechanical superposition state increases the selectivity of a spectroscopic measurement. We show that frequency domain multiple quantum coherence multidimensional spectroscopy can create these superposition states using different frequency excitation pulses. The superposition state is created using two excitation frequencies to excite the symmetric and asymmetric stretch modes in a rhodium dicarbonyl chelate and the dynamic Stark effect to climb the vibrational ladders involving different overtone and combination band states. A monochromator resolves the free induction decay of different coherences comprising the superposition state. The three spectral dimensions provide the selectivity required to observe 19 different spectral features associated with fully coherent nonlinear processes involving up to 11 interactions with the excitation fields. The different features act as spectroscopic probes of the diagonal and off-diagonal parts of the molecular potential energy hypersurface. This approach can be considered as a coherent pump-probe spectroscopy where the pump is a series of excitation pulses that prepares a multiple quantum coherence and the probe is another series of pulses that creates the output coherence.