2014/06/04 by Joachim Seibt, Seibt, Joachim, Tõnu Pullerits +2
Chemistry · Physics and Astronomy · #Chemical Physics (physics.chem-ph) #Electrochemical Analysis and Applications #FOS: Physical sciences #Quantum and electron transport phenomena #Spectroscopy and Quantum Chemical Studies #physics.chem-ph
paper · pdf · doi:10.48550/arxiv.1406.0984
arxiv created 2014/06/04 · openalex publication_date 2014/06/04 · arxiv updated 2014/06/05 · openalex created_date 2022/09/01 · openalex updated_date 2026/07/28
Two-dimensional (2D) spectroscopy provides information about dissipative processes subsequent to electronic excitation, which play a functional role in energy harvesting materials and devices. This technique is particularly sensitive to electronic and vibronic coherence dynamics. While the theoretical treatment of relaxation in the context of 2D-spectroscopy is well-developed under the assumption of different timescales of population transfer and fluctuation dynamics, the interplay between both kinds of processes lacks a comprehensive description in terms of line shape functions. To bridge this gap, we use the cumulant expansion approach to derive response functions, which account for fluctuation dynamics and population transfer simultaneously. We compare 2D-spectra from calculations with different model assumptions about correlations between fluctuations and point out under which conditions a simplified treatment is justified. Our study shows that population transfer and dissipative fluctuation dynamics cannot be described independent of each other in general. Advantages and limitations of the proposed calculation method and its compatibility with the modified Redfield description are discussed.