How to turn your pump–probe instrument into a multidimensional spectrometer: 2D IR and Vis spectroscopies via pulse shaping

Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706-1396, USA.
Physical Chemistry Chemical Physics (Impact Factor: 4.49). 03/2009; 11(5):748-61. DOI: 10.1039/b813817f
Source: PubMed

ABSTRACT We have recently developed a new and simple way of collecting 2D infrared and visible spectra that utilizes a pulse shaper and a partly collinear beam geometry. 2D IR and Vis spectroscopies are powerful tools for studying molecular structures and their dynamics. They can be used to correlate vibrational or electronic eigenstates, measure energy transfer rates, and quantify the dynamics of lineshapes, for instance, all with femtosecond time-resolution. As a result, they are finding use in systems that exhibit fast dynamics, such as sub-millisecond chemical and biological dynamics, and in hard-to-study environments, such as in membranes. While powerful, these techniques have been difficult to implement because they require a series of femtosecond pulses to be spatially and temporally overlapped with precise time-resolution and interferometric phase stability. However, many of the difficulties associated with implementing 2D spectroscopies are eliminated by using a pulse shaper and a simple beam geometry, which substantially lowers the technical barriers required for researchers to enter this exciting field while simultaneously providing many new capabilities. The aim of this paper is to provide an overview of the methods for collecting 2D spectra so that an outsider considering using 2D spectroscopy in their own research can judge which approach would be most suitable for their research aims. This paper focuses primarily on 2D IR spectroscopy, but also includes our recent work on adapting this technology to collecting 2D Vis spectra. We review work that has already been published as well as cover several topics that we have not reported previously, including phase cycling methods to remove background signals, eliminate unwanted scatter, and shift data collection into the rotating frame.

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    • "Coherent control techniques, which utilize optimally shaped pulses to study the quantum interference and select quantum pathways [1] [2] [3] [4], have been widely used to manipulate molecular stucture[4] [5] [6] [7] [8], control chemical reactions[6] [9] [10] and to infer the electronic and vibrational motions in molecules. Pulse shaping techniques utilize the phase φ(ω) of the field˜E "
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    ABSTRACT: We calculate the frequency-dispersed nonlinear transmission signal of a phase-shaped visible pulse to fourth order in the field. Two phase profiles, a phase-step and phase-pulse, are considered. Two dimensional signals obtained by varying the detected frequency and phase parameters are presented for a three electronic band model system. We demonstrate how two-photon and stimulated Raman resonances can be manipulated by the phase profile and sign, and selected quantum pathways can be suppressed. (C) 2014 AIP Publishing LLC.
    The Journal of Chemical Physics 04/2014; 140(14):144105. DOI:10.1063/1.4869750 · 2.95 Impact Factor
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    • "The pump–probe geometry approach to 2D-IR spectroscopy is not without its drawbacks however. One lies in the practical challenge of aligning a mid-IR interferometer if a pulse shaper is not used, but perhaps chief among them is the reduced control over the intensity and arrival time of the local oscillator pulse and the lack of a zero background detection method, which can limit experimental sensitivity in comparison to the boxcar method, though approaches using different polarization geometries of the various pulses can be used to address this [47]. "
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    ABSTRACT: Recent advances in the methodology and application of ultrafast two-dimensional infrared (2D-IR) spectroscopy to biomolecular systems are reviewed. A description of the 2D-IR technique and the molecular contributions to the observed spectra are presented followed by a discussion of recent literature relating to the use of 2D-IR and associated approaches for measuring protein dynamics. In particular, these include the use of diatomic ligand groups for measuring haem protein dynamics, isotopic labelling strategies and the use of vibrational probe groups. The final section reports on the current state of the art regarding the use of 2D-IR methods to provide insights into biological reaction mechanisms.
    Measurement Science and Technology 06/2012; 23(6). DOI:10.1088/0957-0233/23/6/062001 · 1.43 Impact Factor
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    ABSTRACT: We present the utility of 2-D electronic spectroscopy for the investigation of energy transfer dynamics in photosyn-thetic light-harvesting systems. Elucidating ultrafast energy trans-fer within photosynthetic systems is difficult due to the large number of molecules and complex environments involved in the process. In many spectroscopic methods, these systems appear as overlapping peaks with broad linewidths, obscuring the details of the dynamics. 2-D spectroscopy is a nonlinear, ultrafast method that yields a correlation map between excitation and emission energies, and can track incoherent and coherent energy trans-fer processes with femtosecond resolution. A 2-D spectrum can provide important insight into the structure and the mechanisms behind the excited state dynamics. We review the principles be-hind 2-D spectroscopy and describe the content of a 2-D elec-tronic spectrum. Several recent applications of this technique to the major light-harvesting complex of Photosystem II are pre-sented, including monitoring the time scales of energy transfer pro-cesses, investigation of the excited state energies, and determina-tion of the relative orientations of the excited state transition dipole moments. Index Terms—Four-wave mixing, nonlinear optics, ultrafast optics.
    IEEE Journal of Selected Topics in Quantum Electronics 01/2012; 1(1). DOI:10.1109/JSTQE.2011.2112640 · 2.83 Impact Factor
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