Multidimensional Incoherent Time‐Resolved Spectroscopy and Complex Kinetics

Berg, Mark A.

doi:10.1002/9781118197714.ch1

Cited by 19 publications

(39 citation statements)

References 125 publications

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“…The Hilbert-space pathway formalism for calculating multidimensional incoherent experiments has been discussed in detail previously. 5,6,10 In this formalism, as the number of states in the system increases, the number of pathways increases combinatorially. This section seeks to simplify such calculations.…”

Section: Theory For Multistate Systemsmentioning

confidence: 99%

“…It is essentially similar to the 2D correlation function previously studied in two-level systems. 3,8,10 If the decay is nonexponential due to homogeneous causes, the 2D correlation function is the product of 1D correlation functions,…”

Section: B Diagonal Correlation Functionsmentioning

confidence: 99%

“…In a two-level system, these two cuts are identical. 2,8,10 Thus, the asymmetry in τ 1 and τ 2 is diagnostic of a biexciton contribution to the signal. Because the two contributions have opposite signs, the cut along τ 1 = 0 may not be monotonic: it can rise as the negative biexciton contribution decays.…”

Section: A Separating Exciton and Biexciton Dynamicsmentioning

confidence: 99%

“…This idea has been thoroughly discussed in two-level systems. 2,3,[8][9][10] The new feature in excitonic systems is the exciton-biexciton function C 2 1 (τ 2 , τ 1 ), which reports on correlations between two different transitions. To illustrate the behavior of this function, we will calculate the 2D-MUPPETS signal for four limiting models: homogeneous or heterogeneous exciton kinetics combined with either correlated or uncorrelated excitonbiexciton kinetics.…”

Section: Measuring Exciton-biexciton Correlationsmentioning

confidence: 99%

“…Our group has been exploring multidimensional kinetics in which there is more than one perturbation, and thus, more than one period of time evolution. [1][2][3][4][5][6][7][8][9][10] We have called our approach, which uses weak optical perturbations, multiple population-period transient spectroscopy (MUPPETS). So far, its focus has been on nonexponential relaxation (rate dispersion) in two-level systems.…”

Section: Introductionmentioning

confidence: 99%

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Multiple population-period transient spectroscopy (MUPPETS) in excitonic systems

Berg

2013

The Journal of Chemical Physics

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Time-resolved experiments with more than one period of incoherent time evolution are becoming increasingly accessible. When applied to a two-level system, these experiments separate homogeneous and heterogeneous contributions to kinetic dispersion, i.e., to nonexponential relaxation. Here, the theory of two-dimensional (2D) multiple population-period transient spectroscopy (MUPPETS) is extended to multilevel, excitonic systems. A nonorthogonal basis set is introduced to simplify pathway calculations in multilevel systems. Because the exciton and biexciton signals have different signs, 2D MUPPETS cleanly separates the exciton and biexciton decays. In addition to separating homogeneous and heterogeneous dispersion of the exciton, correlations between the exciton and biexciton decays are measurable. Such correlations indicate shared features in the two relaxation mechanisms. Examples are calculated as both 2D time decays and as 2D rate spectra. The effect of solvent heating (i.e., thermal gratings) is also calculated in multidimensional experiments on multilevel systems.

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Section: Theory For Multistate Systemsmentioning

confidence: 99%

Section: B Diagonal Correlation Functionsmentioning

confidence: 99%

Section: A Separating Exciton and Biexciton Dynamicsmentioning

confidence: 99%

Section: Measuring Exciton-biexciton Correlationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Multiple population-period transient spectroscopy (MUPPETS) in excitonic systems

Berg

2013

The Journal of Chemical Physics

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Rate and Amplitude Heterogeneity in the Solvation Response of an Ionic Liquid

Verma

Corcelli

Berg

2016

J. Phys. Chem. Lett.

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In contrast with conventional liquids, ionic liquids have solvation dynamics with more rate dispersion and with average times that do not agree with dielectric measurements. A kinetic analog of multidimensional spectroscopy is introduced and used to look for heterogeneity in simulations of coumarin 153 in [Im12][BF4]. Strong heterogeneity is found in the diffusive solvation rate. An unanticipated heterogeneity in the amplitude of the inertial solvation is also seen. Both heterogeneities exchange at the same rate. This rate is similar to the mean diffusive solvation time, putting it in the intermediate-exchange region. Overall, there are multiple violations of the assumptions usually invoked in the theory of reaction dynamics.

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