Factorized time correlation diagram analysis of paired causal systems excited by twin stochastic driving functions

Howey²,

Sutor³

et al. 2012

J. Phys. Chem. A

Self Cite

Electronic energy transfer in photosynthesis occurs over a range of time scales and under a variety of intermolecular coupling conditions. Recent work has shown that electronic coupling between chromophores can lead to coherent oscillations in two-dimensional electronic spectroscopy measurements of pigment-protein complexes measured with femtosecond laser pulses. A persistent issue in the field is to reconcile the results of measurements performed using femtosecond laser pulses with physiological illumination conditions. Noisy-light spectroscopy can begin to address this question. In this work we present the theoretical analysis of incoherent two-dimensional electronic spectroscopy, I(4) 2D ES. Simulations reveal diagonal peaks, cross peaks, and coherent oscillations similar to those observed in femtosecond two-dimensional electronic spectroscopy experiments. The results also expose fundamental differences between the femtosecond-pulse and noisy-light techniques; the differences lead to new challenges and new opportunities.

Section: Appendixmentioning

confidence: 99%

Two-Dimensional Electronic Spectroscopy Using Incoherent Light: Theoretical Analysis

Howey²,

Sutor³

et al. 2012

J. Phys. Chem. A

Self Cite

“…FTC diagram analysis has been applied to many noisy-light spectroscopies and also explored in a more general context to elucidate the underlying mathematical structure of the diagrams. In all but one previous work, the noisy-light signal was homodyne-detected.…”

Section: Resultsmentioning

confidence: 99%

Coherent Two-Quantum Two-Dimensional Electronic Spectroscopy Using Incoherent Light

Ulness

2017

J. Phys. Chem. A

Self Cite

Two-quantum two-dimensional electronic spectroscopy (2Q 2D ES) may provide a measure of electron-correlation energies in molecules. Attempts to obtain this profound but elusive signal have relied on experimental implementations using femtosecond laser pulses, which induce an overwhelming background signal of nonresonant response. Here we explore theoretically the signatures of electron correlation in coherent 2Q 2D ES measurements that use spectrally incoherent light, I 2Q 2D ES. One can use such fields to suppress nonresonant response, and therefore this method may better isolate the desired signature of electron correlation. Using an appropriate treatment of the multilevel Bloch electronic system, we find that I 2Q 2D ES presents an opportunity to measure electron-correlation energies in molecules.

“…64 Two of these tools, accumulation and color-locking, will be particularly important for the FTC diagram analysis of I (3) RIKES given below. Although discussions of accumulation and color-locking can be found elsewhere, 63,64,70 these two concepts will be briefly presented here because of their utility in the remainder of this work.…”

Section: The Ftc Diagramsmentioning

confidence: 99%

“…These FTC diagrams also appear as symmetric pairs ͑for example IVa and Xa͒ so collectively these terms must contribute a symmetric signal. It should be noted that some of the FTC diagrams of column a look as though there might be a potential for indirect correlation; 70 diagram IIIa is one of these. In all cases indirect correlation will force a separation of the first two tick marks on one of the timelines and hence has a rapid decay factor which kills off the term before probing the slow librational decay.…”

Section: Ftc Diagram Analysis Of the I "3… Rikes Signalmentioning

confidence: 99%

See 1 more Smart Citation

Factorized time correlation diagram analysis of Raman induced Kerr effect spectroscopy using noisy light

The Journal of Chemical Physics

Ulness

2003

Self Cite

Articles you may be interested inLow-frequency collective dynamics in deep eutectic solvents of acetamide and electrolytes: A femtosecond Raman-induced Kerr effect spectroscopic study J. Chem. Phys. 141, 134506 (2014); 10.1063/1.4897207Isotropic and anisotropic Raman scattering from molecular liquids measured by spatially masked optical Kerr effect spectroscopy A combined instantaneous normal mode and time correlation function description of the optical Kerr effect and Raman spectroscopy of liquid CS 2The factorized time correlation ͑FTC͒ diagram analysis of Raman induced Kerr effect spectroscopy from noisy light is presented. The complete set of FTC diagrams is given. This process requires a more sophisticated FTC diagram analysis than is typical because of the important role color-locking plays for this spectroscopy. A physical understanding of the terms that give rise to the slow decaying asymmetric interferograms seen in the experimental literature can be gleaned from these FTC diagrams. The interferograms carry information about the decay of the librational coherences.