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Two-Dimensional Femtosecond Spectroscopy
Abstract
▪ Abstract The simplest two-dimensional (2D) spectra show how excitation with one (variable) frequency affects the spectrum at all other frequencies, thus revealing the molecular connections between transitions. Femtosecond 2D Fourier transform (2D FT) spectra are more flexible and share some of the remarkable properties of their conceptual parent, 2D FT nuclear magnetic resonance. When 2D FT spectra are experimentally separated into real absorptive and imaginary refractive parts, the time resolution and frequency resolution can both reach the uncertainty limit set for each resonance by the sample itself. Coherent four-level contributions to the signal provide new molecular phase information, such as relative signs of transition dipoles. The nonlinear response can be picked apart by selecting a single coherence pathway (e.g., specifying the relative signs of energy level difference frequencies during different time intervals as in the photon echo). Because molecules are frozen on the femtosecond timescale, femtosecond 2D FT experiments can separate a distribution of instantaneous molecular environments and intramolecular geometries as inhomogeneous broadening. This review provides an introduction to two-dimensional Fourier transform experiments exploiting second- and third-order vibrational and electronic nonlinearities.
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Metadata
- Authors
- Jonas, D. M.
- Affiliations
- University of Colorado Boulder (US)
- Corresponding author
- Jonas, David M.
- ORCID
- Jonas, David M.
- Venue
- Annual Review of Physical Chemistry
- Publisher
- Annual Reviews
- Published
- 2003-10
- Volume
- 54
- Issue
- 1
- Pages
- 425-463
- ISSN
- 0066-426X (ISSN-L)
- 1545-1593
- OpenAlex
- W2105576535
- Cited by
- 1,198
- References
- 133
- Citations by year
- 2026: 43 · 2025: 60 · 2024: 54 · 2023: 47 · 2022: 45 · 2021: 55 · 2020: 59 · 2019: 65 · 2018: 57 · 2017: 74 · 2016: 44 · 2015: 54 · 2014: 50 · 2013: 60 · 2012: 46
- FWCI
- 1.96
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Annual Review of Physical Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Laser-Matter Interactions and Applications
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Keywords
- two-dimensional spectroscopy, femtosecond spectroscopy, electronic nonlinearity, photon echo, inhomogeneous broadening, nonlinear optical properties
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
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