论文标题
二维光谱超过扰动极限:有限脉冲和检测模式的影响
Two-dimensional spectroscopy beyond the perturbative limit: the influence of finite pulses and detection modes
论文作者
论文摘要
超快速和多维光谱使得有力的玻璃使得分子系统的动力学。特别是二维电子光谱(2DES)提供了量子系统中连贯性和能量流的探针,而更常规的技术是不可能的。虽然杂尼检测(HD)2DE越来越普遍,但最近荧光检测(FD)2DE提供了新的机会,包括单分子实验。但是,在这两种技术中,可能很难明确地识别主导信号的途径。因此,使用2DE的数值建模至关重要,进而需要在某种程度上近似脉冲方案。在这里,我们采用非实验性时间演变来研究有限的脉冲宽度和振幅对2DES信号的影响。在此过程中,我们确定了HD和FD检测方案响应的关键差异,以及参数空间的区域,在任何一种技术中,信号被不必要的伪像遮盖了。以这种方式绘制参数空间为选择实验条件提供了指南,并显示了哪些限制通常的理论近似良好工作,并且需要哪些限制更复杂的方法。
Ultra-fast and multi-dimensional spectroscopy gives a powerful looking glass into the dynamics of molecular systems. In particular two-dimensional electronic spectroscopy (2DES) provides a probe of coherence and the flow of energy within quantum systems which is not possible with more conventional techniques. While heterodyne-detected (HD) 2DES is increasingly common, more recently fluorescence-detected (FD) 2DES offers new opportunities, including single-molecule experiments. However in both techniques it can be difficult to unambiguously identify the pathways which dominate the signal. Therefore the use of numerically modelling of 2DES is vitally important, which in turn requires approximating the pulsing scheme to some degree. Here we employ non-pertubative time evolution to investigate the effects of finite pulse width and amplitude on 2DES signals. In doing so we identify key differences in the response of HD and FD detection schemes, as well as the regions of parameter space where the signal is obscured by unwanted artefacts in either technique. Mapping out parameter space in this way provides a guide to choosing experimental conditions and also shows in which limits the usual theoretical approximations work well and which limits more sophisticated approaches are required.