Skip to main content

Main menu

  • Home
  • Articles
    • Current
    • Special Feature Articles - Most Recent
    • Special Features
    • Colloquia
    • Collected Articles
    • PNAS Classics
    • List of Issues
  • Front Matter
    • Front Matter Portal
    • Journal Club
  • News
    • For the Press
    • This Week In PNAS
    • PNAS in the News
  • Podcasts
  • Authors
    • Information for Authors
    • Editorial and Journal Policies
    • Submission Procedures
    • Fees and Licenses
  • Submit
  • Submit
  • About
    • Editorial Board
    • PNAS Staff
    • FAQ
    • Accessibility Statement
    • Rights and Permissions
    • Site Map
  • Contact
  • Journal Club
  • Subscribe
    • Subscription Rates
    • Subscriptions FAQ
    • Open Access
    • Recommend PNAS to Your Librarian

User menu

  • Log in
  • My Cart

Search

  • Advanced search
Home
Home
  • Log in
  • My Cart

Advanced Search

  • Home
  • Articles
    • Current
    • Special Feature Articles - Most Recent
    • Special Features
    • Colloquia
    • Collected Articles
    • PNAS Classics
    • List of Issues
  • Front Matter
    • Front Matter Portal
    • Journal Club
  • News
    • For the Press
    • This Week In PNAS
    • PNAS in the News
  • Podcasts
  • Authors
    • Information for Authors
    • Editorial and Journal Policies
    • Submission Procedures
    • Fees and Licenses
  • Submit
Research Article

Correlating the motion of electrons and nuclei with two-dimensional electronic–vibrational spectroscopy

Thomas A. A. Oliver, Nicholas H. C. Lewis, and Graham R. Fleming
  1. aDepartment of Chemistry, University of California, Berkeley, CA 94720; and
  2. bPhysical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720

See allHide authors and affiliations

PNAS first published June 9, 2014; https://doi.org/10.1073/pnas.1409207111
Thomas A. A. Oliver
aDepartment of Chemistry, University of California, Berkeley, CA 94720; and
bPhysical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
  • Find this author on Google Scholar
  • Find this author on PubMed
  • Search for this author on this site
Nicholas H. C. Lewis
aDepartment of Chemistry, University of California, Berkeley, CA 94720; and
bPhysical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
  • Find this author on Google Scholar
  • Find this author on PubMed
  • Search for this author on this site
Graham R. Fleming
aDepartment of Chemistry, University of California, Berkeley, CA 94720; and
bPhysical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
  • Find this author on Google Scholar
  • Find this author on PubMed
  • Search for this author on this site
  • For correspondence: grfleming@lbl.gov
  1. Contributed by Graham R. Fleming, May 16, 2014 (sent for review March 24, 2014)

  • Article
  • Figures & SI
  • Info & Metrics
  • PDF
Loading

Significance

To have a full understanding of the role of nuclear motions involved in nonradiative relaxation dynamics of complex molecular systems such as carotenoids, nanomaterials, and molecular photoswitches, the ability to correlate the electronic and nuclear degrees of freedom is imperative. We have developed 2D electronic–vibrational spectroscopy to observe this correlation, and this new spectroscopic technique will provide a direct probe of the coupling between electronic and nuclear dynamics at conical intersections, and thus the underlying mechanisms driving the ensuing photochemistry.

Abstract

Multidimensional nonlinear spectroscopy, in the electronic and vibrational regimes, has reached maturity. To date, no experimental technique has combined the advantages of 2D electronic spectroscopy and 2D infrared spectroscopy, monitoring the evolution of the electronic and nuclear degrees of freedom simultaneously. The interplay and coupling between the electronic state and vibrational manifold is fundamental to understanding ensuing nonradiative pathways, especially those that involve conical intersections. We have developed a new experimental technique that is capable of correlating the electronic and vibrational degrees of freedom: 2D electronic–vibrational spectroscopy (2D-EV). We apply this new technique to the study of the 4-(di-cyanomethylene)-2-methyl-6-p-(dimethylamino)styryl-4H-pyran (DCM) laser dye in deuterated dimethyl sulfoxide and its excited state relaxation pathways. From 2D-EV spectra, we elucidate a ballistic mechanism on the excited state potential energy surface whereby molecules are almost instantaneously projected uphill in energy toward a transition state between locally excited and charge-transfer states, as evidenced by a rapid blue shift on the electronic axis of our 2D-EV spectra. The change in minimum energy structure in this excited state nonradiative crossing is evident as the central frequency of a specific vibrational mode changes on a many-picoseconds timescale. The underlying electronic dynamics, which occur on the hundreds of femtoseconds timescale, drive the far slower ensuing nuclear motions on the excited state potential surface, and serve as a excellent illustration for the unprecedented detail that 2D-EV will afford to photochemical reaction dynamics.

  • photon echo
  • ultrafast dynamics
  • electronic–vibrational coupling

Footnotes

  • ↵1To whom correspondence should be addressed. E-mail: grfleming{at}lbl.gov.
  • Author contributions: T.A.A.O., N.H.C.L., and G.R.F. designed research; T.A.A.O. and N.H.C.L. performed research; T.A.A.O. and N.H.C.L. analyzed data; and T.A.A.O. wrote the paper.

  • The authors declare no conflict of interest.

  • This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1409207111/-/DCSupplemental.

Freely available online through the PNAS open access option.

Next
Back to top
Article Alerts
Email Article

Thank you for your interest in spreading the word on PNAS.

NOTE: We only request your email address so that the person you are recommending the page to knows that you wanted them to see it, and that it is not junk mail. We do not capture any email address.

Enter multiple addresses on separate lines or separate them with commas.
Correlating the motion of electrons and nuclei with two-dimensional electronic–vibrational spectroscopy
(Your Name) has sent you a message from PNAS
(Your Name) thought you would like to see the PNAS web site.
CAPTCHA
This question is for testing whether or not you are a human visitor and to prevent automated spam submissions.
Citation Tools
Two-dimensional electronic–vibrational spectroscopy
Thomas A. A. Oliver, Nicholas H. C. Lewis, Graham R. Fleming
Proceedings of the National Academy of Sciences Jun 2014, 201409207; DOI: 10.1073/pnas.1409207111

Citation Manager Formats

  • BibTeX
  • Bookends
  • EasyBib
  • EndNote (tagged)
  • EndNote 8 (xml)
  • Medlars
  • Mendeley
  • Papers
  • RefWorks Tagged
  • Ref Manager
  • RIS
  • Zotero
Request Permissions
Share
Two-dimensional electronic–vibrational spectroscopy
Thomas A. A. Oliver, Nicholas H. C. Lewis, Graham R. Fleming
Proceedings of the National Academy of Sciences Jun 2014, 201409207; DOI: 10.1073/pnas.1409207111
del.icio.us logo Digg logo Reddit logo Twitter logo CiteULike logo Facebook logo Google logo Mendeley logo
  • Tweet Widget
  • Facebook Like
  • Mendeley logo Mendeley

See related content:

  • Extreme cross-peak 2D spectroscopy
    - Jul 07, 2014
Proceedings of the National Academy of Sciences: 118 (9)
Current Issue

Submit

Sign up for Article Alerts

Jump to section

  • Article
  • Figures & SI
  • Info & Metrics
  • PDF

You May Also be Interested in

Setting sun over a sun-baked dirt landscape
Core Concept: Popular integrated assessment climate policy models have key caveats
Better explicating the strengths and shortcomings of these models will help refine projections and improve transparency in the years ahead.
Image credit: Witsawat.S.
Model of the Amazon forest
News Feature: A sea in the Amazon
Did the Caribbean sweep into the western Amazon millions of years ago, shaping the region’s rich biodiversity?
Image credit: Tacio Cordeiro Bicudo (University of São Paulo, São Paulo, Brazil), Victor Sacek (University of São Paulo, São Paulo, Brazil), and Lucy Reading-Ikkanda (artist).
Syrian archaeological site
Journal Club: In Mesopotamia, early cities may have faltered before climate-driven collapse
Settlements 4,200 years ago may have suffered from overpopulation before drought and lower temperatures ultimately made them unsustainable.
Image credit: Andrea Ricci.
Steamboat Geyser eruption.
Eruption of Steamboat Geyser
Mara Reed and Michael Manga explore why Yellowstone's Steamboat Geyser resumed erupting in 2018.
Listen
Past PodcastsSubscribe
Birds nestling on tree branches
Parent–offspring conflict in songbird fledging
Some songbird parents might improve their own fitness by manipulating their offspring into leaving the nest early, at the cost of fledgling survival, a study finds.
Image credit: Gil Eckrich (photographer).

Similar Articles

Site Logo
Powered by HighWire
  • Submit Manuscript
  • Twitter
  • Facebook
  • RSS Feeds
  • Email Alerts

Articles

  • Current Issue
  • Special Feature Articles – Most Recent
  • List of Issues

PNAS Portals

  • Anthropology
  • Chemistry
  • Classics
  • Front Matter
  • Physics
  • Sustainability Science
  • Teaching Resources

Information

  • Authors
  • Editorial Board
  • Reviewers
  • Subscribers
  • Librarians
  • Press
  • Site Map
  • PNAS Updates
  • FAQs
  • Accessibility Statement
  • Rights & Permissions
  • About
  • Contact

Feedback    Privacy/Legal

Copyright © 2021 National Academy of Sciences. Online ISSN 1091-6490