Broad-Band Pump-Probe Spectroscopy Quantifies Ultrafast Solvation Dynamics of Proteins and Molecules

Chanelle C. Jumper, Paul C. Arpin, Daniel B. Turner, Scott D. McClure, Shahnawaz Rafiq, Jacob C. Dean, Jeffrey A. Cina, Philip A. Kovac, Tihana Mirkovic, Gregory D. Scholes

Research output: Contribution to journalArticlepeer-review

48 Scopus citations


In this work, we demonstrate the use of broad-band pump-probe spectroscopy to measure femtosecond solvation dynamics. We report studies of a rhodamine dye in methanol and cryptophyte algae light-harvesting proteins in aqueous suspension. Broad-band impulsive excitation generates a vibrational wavepacket that oscillates on the excited-state potential energy surface, destructively interfering with itself at the minimum of the surface. This destructive interference gives rise to a node at a certain probe wavelength that varies with time. This reveals the Gibbs free-energy changes of the excited-state potential energy surface, which equates to the solvation time correlation function. This method captures the inertial solvent response of water (∼40 fs) and the bimodal inertial response of methanol (∼40 and ∼150 fs) and reveals how protein-buried chromophores are sensitive to the solvent dynamics inside and outside of the protein environment.

Original languageEnglish
Pages (from-to)4722-4731
Number of pages10
JournalJournal of Physical Chemistry Letters
Issue number22
StatePublished - Nov 17 2016

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry


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