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

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

Research output: Contribution to journalArticle

Abstract

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 (US)
Pages (from-to)4722-4731
Number of pages10
JournalJournal of Physical Chemistry Letters
Volume7
Issue number22
DOIs
StatePublished - Nov 17 2016

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Solvation
solvation
Potential energy surfaces
Pumps
Spectroscopy
pumps
broadband
proteins
Proteins
Excited states
Molecules
Methanol
probes
methyl alcohol
potential energy
spectroscopy
excitation
molecules
Rhodamines
algae

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Broad-Band Pump-Probe Spectroscopy Quantifies Ultrafast Solvation Dynamics of Proteins and Molecules. / Jumper, Chanelle C.; Arpin, Paul C.; Turner, Daniel; McClure, Scott D.; Rafiq, Shahnawaz; Dean, Jacob C.; Cina, Jeffrey A.; Kovac, Philip A.; Mirkovic, Tihana; Scholes, Gregory D.

In: Journal of Physical Chemistry Letters, Vol. 7, No. 22, 17.11.2016, p. 4722-4731.

Research output: Contribution to journalArticle

Jumper, CC, Arpin, PC, Turner, D, McClure, SD, Rafiq, S, Dean, JC, Cina, JA, Kovac, PA, Mirkovic, T & Scholes, GD 2016, 'Broad-Band Pump-Probe Spectroscopy Quantifies Ultrafast Solvation Dynamics of Proteins and Molecules', Journal of Physical Chemistry Letters, vol. 7, no. 22, pp. 4722-4731. https://doi.org/10.1021/acs.jpclett.6b02237
Jumper, Chanelle C. ; Arpin, Paul C. ; Turner, Daniel ; McClure, Scott D. ; Rafiq, Shahnawaz ; Dean, Jacob C. ; Cina, Jeffrey A. ; Kovac, Philip A. ; Mirkovic, Tihana ; Scholes, Gregory D. / Broad-Band Pump-Probe Spectroscopy Quantifies Ultrafast Solvation Dynamics of Proteins and Molecules. In: Journal of Physical Chemistry Letters. 2016 ; Vol. 7, No. 22. pp. 4722-4731.
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AU - Rafiq, Shahnawaz

AU - Dean, Jacob C.

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