Signatures of Exciton Delocalization and Exciton–Exciton Annihilation in Fluorescence-Detected Two-Dimensional Coherent Spectroscopy

Malý, Pavel; Mančal, Tomáš

doi:10.1021/acs.jpclett.8b02271

Cited by 52 publications

(61 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8 Other two-dimensional spectroscopy methods with incoherent detection, such as two-dimensional nanoscopy 9 relying on photoelectron microscopy for detection and current-detected two-dimensional spectroscopy, 10 have been demonstrated and provide distinct advantages for different types of applications. Although a number of fluorescence-detected two-dimensional electronic spectroscopy (F-2DES) experiments 1−5 and related theory 4,11−13 have been reported, the understanding of the features in F-2DES spectra is still at an early stage. This is particularly true for multichromophoric systems, for which theory has only been developed for monomer and dimer systems.…”

Section: Introductionmentioning

confidence: 99%

“…This is particularly true for multichromophoric systems, for which theory has only been developed for monomer and dimer systems. 4,11−13 The aim of this paper is to develop a relatively simple theory framework to model the spectra of multichromophoric systems such as the Q y band of light-harvesting system 2 (LH2). Using this framework, we aim to understand the origin of the unexpected large cross-peaks reported in such experiments 7,12,14 as well as the observed differences in line shapes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems

et al. 2018

View full text Add to dashboard Cite

We present a theory for modeling fluorescence-detected two-dimensional electronic spectroscopy of multichromophoric systems. The theory is tested by comparison of the predicted spectra of the light-harvesting complex LH2 with experimental data. A qualitative explanation of the strong cross-peaks as compared to conventional two-dimensional electronic spectra is given. The strong cross-peaks are attributed to the clean ground-state signal that is revealed when the annihilation of exciton pairs created on the same LH2 complex cancels oppositely signed signals from the doubly excited state. This annihilation process occurs much faster than the nonradiative relaxation. Furthermore, the line shape difference is attributed to slow dynamics, exciton delocalization within the bands, and intraband exciton–exciton annihilation. This is in line with existing theories presented for model systems. We further propose the use of time-resolved fluorescence-detected two-dimensional spectroscopy to study state-resolved exciton–exciton annihilation.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems

et al. 2018

View full text Add to dashboard Cite

show abstract

Section: Figurementioning

confidence: 99%

“…However, it has been pointed out that the cross peak behaviour is not trivial. 19,20 For example, the cross peak amplitude can increase while the coupling strength is decreasing. Still, if structure is known, the exciton mixing angle can be evaluated.Alternatively, instead of focusing on the cross peak amplitude/strength, one could construct a signal analogous to the so-called two colour photon echo peak-shift experiment.…”

mentioning

confidence: 99%

“…13,36 On the other hand, the ESA2 -ESA1 cancellation (which reveals the cross peaks) takes place due to the exciton-exciton annihilation and thereby the cross peaks can be taken as signatures of the annihilation. 20,21 In case of individual LH2s where perfect annihilation is a well-established fact, the latter aspect is less of interest while the potential of the method for evaluating delocalization is more relevant. However, connectivity in large antenna complexes 48 can be possibly investigated via existence of annihilation witnessed by the F-2DES cross peaks.Finally, we point out that our considerations here may be relevant for the discussion of the twoparticle DQC signal observed in dilute gases.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Interpreting Fluorescence Detected Two-Dimensional Electronic Spectroscopy

Kühn

Mančal

Pullerits

2020

J. Phys. Chem. Lett.

Self Cite

View full text Add to dashboard Cite

Electronic coherent multidimensional spectroscopy (CMDS) allows detailed studies of ultrafast dynamics in systems with highly congested complicated spectral bands. 1,2,3 A wide variety of experimental implementations have been developed 4 emphasising different strengths of the methodology. Originally, the 2D electronic spectroscopy (2DES) was based on phase-sensitive detection of a coherent photon-echo type signal generated by three laser pulses. 5,6 During the last decade four-pulse generated incoherent action detection has become popular. The concept was originally developed for fluorescence detected 2DES (F-2DES). 7 Later numerous other incoherent action detection methods have been used, e.g., based on photoelectrons, 8 photocurrents 9,10 and photo ions. 11 Even though 2DES and F-2DES are analogous coherent techniques providing detailed information on ultrafast dynamics in two spectral dimensions, the methods have important differences and the measured spectra do not look the same. 12,13,14,15 While the "anatomy" of the 2DES has been studied in numerous articles 16,17,18 and is quite well understood, interpretation of the F-2DES spectra 19,20,21,22,23 has not reached similar maturity and is currently being debated in literature. In this Viewpoint we briefly summarize the various approaches to interpreting the F-2DES and present our view with the intension to resolve at least some of the existing controversial issues. We start from a brief summary of the two methods.In 2DES the third order macroscopic polarization induced by three short laser pulses generates various coherent light fields in different phase-matched directions. For phase-sensitive detection the coherent field of a certain phase-matched direction is mixed with a fourth, so called local oscillator pulse and spectrally dispersed in a spectrometer. The Fourier transform of the delay between the first two pulses provides the excitation frequency axis (usually horizontal) and the spectrum of the coherent photon echo and free induction decay type signal fields give the detection axis (usually vertical).In F-2DES four laser pulses bring the system to a fourth-order excited state population which is detected via the emitted fluorescence. For disentangling the detected signal into the components of interest, phase modulation of the pulses together with lock-in detection is used. 24,25 Alternatively, in phase cycling, a certain set of phase combinations of the pulses is applied thereby allowing to uniquely determine the signals of interest. 26 Conceptually, there are three important differences between 2DES and F-2DES: 1) Since F-2DES has one more excitation pulse, there is an additional signal generating Liouville pathway as can be seen in Figure 1. 2) After the fourth pulse, fluorescence is usually emitted over long time period during which various processes can occur that influence the fluorescence yield and can mix two-pulse modulations. 27 3) Since in F-2DES disentangling of the signals is achieved by phase modulation and corresponding Fourier filteri...

show abstract

Theory of Center‐Line Slope in 2D Electronic Spectroscopy with Static Disorder

Sun,

Yao,

et al. 2023

Adv Quantum Tech

View full text Add to dashboard Cite

Abstract2D electronic spectroscopy (2DES) is a powerful tool for investigating the dynamics of complex systems. However, analyzing the resulting spectra can be challenging, and thus may require the use of theoretical modeling techniques. The center‐line slope (CLS) method is one of such approaches, which aims to extract the time correlation function (TCF) from 2DES with minimal error. Since static disorder is widely observed in complex systems, it may be interesting to ask whether the CLS approach still work in the presence of the static disorder. In this paper, the effect of the static disorder on the TCF obtained through the CLS method is investigated. It is found that the steady‐state value of the CLS increases monotonically with respect to the static disorder, which suggests that the amplitude of the static disorder can be determined using the CLS in the long‐time limit. Additionally, as the static disorder rises, the decay rate of the CLS first decreases to a certain value and remains at this value until the static disorder is sufficiently large. Afterward, the CLS begins to fluctuate significantly and thus results in obtaining the decay rate through the CLS method unreliable. Based on these discoveries, the authors propose a method to fix the error and obtain the TCF. The findings may pave the way for obtaining reliable system‐bath information by analyzing 2DES in the practical situations.

show abstract

Signatures of Exciton Delocalization and Exciton–Exciton Annihilation in Fluorescence-Detected Two-Dimensional Coherent Spectroscopy

Cited by 52 publications

References 31 publications

Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems

Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems

Interpreting Fluorescence Detected Two-Dimensional Electronic Spectroscopy

Theory of Center‐Line Slope in 2D Electronic Spectroscopy with Static Disorder

Contact Info

Product

Resources

About