Two-dimensional spectroscopy beyond the perturbative limit: the influence of finite pulses and detection modes
arXiv:2011.04343 · doi:10.1063/5.0038550
Abstract
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.
28 pages, 10 figures + appendix
References in corpus (18)
- Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer
- Spatially-resolved Fluorescence-detected Two-dimensional Electronic Spectroscopy Probes Varying Electronic Couplings in Photosynthetic Bacteria
- Origin of long-lived oscillations in 2D-spectra of a Quantum Vibronic Model: Electronic vs Vibrational coherence
- Two-dimensional electronic spectroscopy for the quantum-optics enthusiast
- Room-temperature ultrafast non-linear spectroscopy of a single molecule
- Nonlinear optical spectroscopy of single, few, and many molecules; nonequilibrium Green's function QED approach
- Incoherent population mixing contributions to phase-modulation two-dimensional coherent excitation spectra
- Using Fluorescence Detected Two-Dimensional Spectroscopy to Investigate Initial Exciton Delocalization Between Coupled Chromophores
- Efficient isolation of multiphoton processes and detection of collective states in dilute samples
- Strongly Coupled Bacteriochlorophyll Dyad Studied Using Two-dimensional Phase-modulated Fluorescence-detected Electronic Spectroscopy
- Phase-modulated electronic wave-packet interferometry reveals high resolution vibronic spectra of free Rb atoms and Rb*He molecules
- Automatic Feynman diagram generation for nonlinear optical spectroscopies
- Efficient numerical method for predicting nonlinear optical spectroscopies of open systems
- Compressed Sensing for Reconstructing Coherent Multidimensional Spectra
- Signatures of spatially correlated noise and non-secular effects in two-dimensional electronic spectroscopy
- Multi-color quantum control for suppressing ground state coherences in two-dimensional electronic spectroscopy
- Numerical Method for Nonlinear Optical Spectroscopies: Ultrafast Ultrafast Spectroscopy
- Effect of disorder and polarization sequences on two-dimensional spectra of light harvesting complexes