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Two-dimensional electronic spectroscopy

Nature Reviews Methods Primers volume 3, Article number: 84 (2023) Cite this article

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Abstract

Two-dimensional electronic spectroscopy (2DES) is a popular technique that can track ultrafast coherent and incoherent processes in real time. Since its development in the late 1990s, 2DES has become a powerful tool for investigating ultrafast dynamics in a range of systems, including nanomaterials and optoelectronic devices. This Primer explains the underlying physical principles of 2DES and how it can be applied to study dynamic photophysical processes. The article discusses how to collect, process and analyse data, with a summary of currently available experimental configurations. Common issues and challenges are considered, focusing on the limitations and reproducibility of the technique, finishing with an exploration of potential future advances and applications.

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Fig. 1: Overview of two-dimensional electronic spectroscopy.
Fig. 2: Interpretation of signals in two-dimensional electronic spectroscopy maps S(3)
Fig. 3: Excitation geometries.
Fig. 4: Data processing.
Fig. 5: Schematic of data analysis procedures.
Fig. 6: Pictorial representation of the phase modulation pulse sequence and detection scheme.

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Acknowledgements

The authors thank K. Watters for scientific editing. E.C. acknowledges financial support from the University of Padova (P-DiSC#04BIRD2022-UNIPD grant) and the Ministero dell’Università e della Ricerca through the Project NEST-Spoke 9, code PE0000021 (CUP C93C22005230007). G.S.E. acknowledges financial support from the National Science Foundation (NSF) through Quantum sensing for Biophysics and Bioengineering (QuBBE) Quantum Leap Challenge Institutes (QLCI) (NSF OMA-2121044), through grant no. 1900359, and the Department of Energy through award no. DE-SC0020131. C.C.B. acknowledges support from a Department of Defense National Defense Science and Engineering Graduate (DoD NDSEG) Fellowship. G.C. acknowledges support from the PRIN 2017 Project 201795SBA3−HARVEST. T.P. acknowledges the Swedish Research Council grant 2021–05207 and Swedish Energy Agency grant 2020–005224.

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Authors and Affiliations

  1. Department of Chemical Sciences, University of Padova, Padova, Italy

    Elisa Fresch & Elisabetta Collini

  2. Istituto di Fotonica e Nanotecnologie-CNR, Milano, Italy

    Franco V. A. Camargo & Giulio Cerullo

  3. Department of Chemistry, University of Chicago, Chicago, IL, USA

    Qijie Shen, Caitlin C. Bellora & Gregory S. Engel

  4. Division of Chemical Physics and NanoLund, Lund University, Lund, Sweden

    Tõnu Pullerits

  5. Department of Physics, Politecnico di Milano, Milano, Italy

    Giulio Cerullo

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  1. Elisa Fresch
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  4. Caitlin C. Bellora
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Contributions

Introduction (E.C.); Experimentation (F.V.A.C., G.C. and E.C.); Results (E.F. and E.C.); Applications (T.P. and E.C.); Reproducibility and data deposition (Q.S., C.C.B., G.S.E. and E.C.); Limitations and optimizations (Q.S., C.C.B., G.S.E. and E.C.); Outlook (Q.S., C.C.B., G.S.E. and E.C.); overview of the Primer (all authors).

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Correspondence to Elisabetta Collini.

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Competing interests

G.C. discloses financial association with the company NIREOS (www.nireos.com), which manufactures the TWINS interferometer. All other authors declare no competing interests.

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Nature Reviews Methods Primers thanks Darius Abramavicius and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Glossary

2D decay-associated spectra

Two-dimensional plots obtained by a multiexponential global fitting procedure, in which the amplitude associated with a specific decay time component is reported as a function of the excitation and detection frequencies.

Dephasing times

The characterization of the randomization of the phase within an ensemble because of intermolecular interactions and determines how long a system maintains its coherence.

Four-wave-mixing

Techniques that are third-order nonlinear optical processes that involve the interaction of three electric fields with a system, resulting in the creation of a fourth field, the signal, according to momentum and energy conservation principles.

Gradient-assisted photon echo spectroscopy

An experimental configuration used to record two-dimensional electronic spectroscopy spectra. Rather than systematically scanning t1 for each value of population time t2, the variation in t1 is created by a temporal gradient of slope created geometrically by tilting the wavefront of one beam relative to another.

Heterodyne detection

A detection method for which the weak signal emitted by the sample is mixed with a second phase-coherent light beam, called the local oscillator. This enhances the detected signal and retrieves phase information to reveal the real or imaginary part of the nonlinear response.

Interferometric stability

A type of stability achieved by maintaining well-defined phase relationships between two or more interfering electric fields over time.

Phase cycling

The exciting pulse sequence is tailored to the desired interpulse delays and relative phases. To isolate the desired signal, several measurements are taken with the appropriate delays and phases and then combined.

Phase modulation

In this approach, a pulse-to-pulse carrier-envelope phase shift is created. Detecting signals modulated at the correct frequency combination enables linear and nonlinear spectroscopic signals to be isolated.

Pulse shaping

Tailors the temporal profile of ultrashort optical pulses by physically manipulating the phase and amplitude of the frequency components.

Relaxation dynamics

The ensemble of kinetic pathways that a system in an excited state follows to return to its equilibrium position (ground state). Each relaxation process has a corresponding relaxation time τ, which is the reciprocal of the associated kinetic constant (k = 1/τ).

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Fresch, E., Camargo, F.V.A., Shen, Q. et al. Two-dimensional electronic spectroscopy. Nat Rev Methods Primers 3, 84 (2023). https://doi.org/10.1038/s43586-023-00267-2

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