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Coherent two-dimensional terahertz-terahertz-Raman spectroscopy

Finneran, Ian A. and Welsch, Ralph and Allodi, Marco A. and Miller, Thomas F., III and Blake, Geoffrey A. (2016) Coherent two-dimensional terahertz-terahertz-Raman spectroscopy. Proceedings of the National Academy of Sciences of the United States of America, 113 (25). pp. 6857-6861. ISSN 0027-8424. PMCID PMC4922159. doi:10.1073/pnas.1605631113.

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We present 2D terahertz-terahertz-Raman (2D TTR) spectroscopy, the first technique, to our knowledge, to interrogate a liquid with multiple pulses of terahertz (THz) light. This hybrid approach isolates nonlinear signatures in isotropic media, and is sensitive to the coupling and anharmonicity of thermally activated THz modes that play a central role in liquid-phase chemistry. Specifically, by varying the timing between two intense THz pulses, we control the orientational alignment of molecules in a liquid, and nonlinearly excite vibrational coherences. A comparison of experimental and simulated 2D TTR spectra of bromoform (CHBr_3), carbon tetrachloride (CCl_4), and dibromodichloromethane (CBr_2Cl_2) shows previously unobserved off-diagonal anharmonic coupling between thermally populated vibrational modes.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle
Finneran, Ian A.0000-0003-2506-4652
Allodi, Marco A.0000-0002-3289-1659
Miller, Thomas F., III0000-0002-1882-5380
Blake, Geoffrey A.0000-0003-0787-1610
Additional Information:© 2016 National Academy of Sciences. Edited by Michael L. Klein, Temple University, Philadelphia, PA, and approved May 6, 2016 (received for review April 7, 2016). Published ahead of print June 6, 2016. The authors acknowledge the National Science Foundation (Grants CHE-1214123 and CHE-1057112 and the Graduate Research Fellowship Program) for financial support. R.W. acknowledges financial support from the Deutsche Forschungsgemeinschaft under Grant WE 5762/1-1. M.A.A. acknowledges current support from a Yen Postdoctoral Fellowship from the Institute for Biophysical Dynamics at the University of Chicago. Author contributions: I.A.F., M.A.A., and G.A.B. designed research; I.A.F. and R.W. performed research; I.A.F., R.W., M.A.A., T.F.M., and G.A.B. analyzed data; and I.A.F., R.W., M.A.A., T.F.M., and G.A.B. wrote the paper. The authors declare no conflict of interest. This article is a PNAS Direct Submission. This article contains supporting information online at
Funding AgencyGrant Number
NSF Graduate Research FellowshipUNSPECIFIED
Deutsche Forschungsgemeinschaft (DFG)WE 5762/1-1
University of ChicagoUNSPECIFIED
Subject Keywords:ultrafast dynamics; terahertz; coherent multidimensional spectroscopy
Issue or Number:25
PubMed Central ID:PMC4922159
Record Number:CaltechAUTHORS:20160607-073544202
Persistent URL:
Official Citation:Ian A. Finneran, Ralph Welsch, Marco A. Allodi, Thomas F. Miller III, and Geoffrey A. Blake Coherent two-dimensional terahertz-terahertz-Raman spectroscopy PNAS 2016 113 (25) 6857-6861; published ahead of print June 6, 2016, doi:10.1073/pnas.1605631113
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67707
Deposited By: Tony Diaz
Deposited On:07 Jun 2016 16:39
Last Modified:11 Nov 2021 03:53

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