Two-Dimensional Electronic Spectroscopy Using Incoherent Light: Theoretical Analysis

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-07, Vol.117 (29), p.5926-5954
• Main Authors: Turner, Daniel B, Howey, Dylan J, Sutor, Erika J, Hendrickson, Rebecca A, Gealy, M. W, Ulness, Darin J
• Format: Article
• Language: English
• Subjects: Biological and medical sciences; Coherence; Color; Coupling (molecular); Electron Transport; Electrons; Energy transfer; Femtosecond; Fundamental and applied biological sciences. Psychology; Lasers; Light; Models, Molecular; Molecular biophysics; Molecular Conformation; Oscillations; Photochemistry. Photosynthesis. Bioluminescence; Photosynthesis; Radiation-biomolecule interaction; Spectroscopy; Spectrum Analysis; Time Factors; Two dimensional
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp310477y

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.