Broadband two-dimensional electronic spectroscopy (2DES) can assist in understanding complex electronic and vibrational signatures. In this paper, we use 2DES to examine the electronic structure and dynamics of a long chain cyanine dye (1,1-diethyl-4,4-dicarbocyanine iodide, or DDCI-4), a system with a vibrational progression. Using broadband pulses that span the resonant electronic transition, we measure two-dimensional spectra that show a characteristic six peak pattern from coherently excited ground and excited state vibrational modes. We model these features using a spectral density formalism and the vibronic features are assigned to Feynman pathways. We also examine the dynamics of a particular set of peaks demonstrating anticorrelated peak motion, a signature of oscillatory wavepacket dynamics on the ground and excited states. These dynamics, in concert with the general structure of vibronic two-dimensional spectra, can be used to distinguish between pure electronic and vibrational quantum coherences.
Skip Nav Destination
Article navigation
14 July 2012
Research Article|
July 12 2012
Excited and ground state vibrational dynamics revealed by two-dimensional electronic spectroscopy
Justin R. Caram;
Justin R. Caram
Department of Chemistry and The James Franck Institute,
The University of Chicago
, Chicago, Illinois 60637, USA
Search for other works by this author on:
Andrew F. Fidler;
Andrew F. Fidler
Department of Chemistry and The James Franck Institute,
The University of Chicago
, Chicago, Illinois 60637, USA
Search for other works by this author on:
Gregory S. Engel
Gregory S. Engel
Department of Chemistry and The James Franck Institute,
The University of Chicago
, Chicago, Illinois 60637, USA
Search for other works by this author on:
J. Chem. Phys. 137, 024507 (2012)
Article history
Received:
April 25 2012
Accepted:
June 21 2012
Citation
Justin R. Caram, Andrew F. Fidler, Gregory S. Engel; Excited and ground state vibrational dynamics revealed by two-dimensional electronic spectroscopy. J. Chem. Phys. 14 July 2012; 137 (2): 024507. https://doi.org/10.1063/1.4733710
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Freezing point depression of salt aqueous solutions using the Madrid-2019 model
Cintia P. Lamas, Carlos Vega, et al.
Related Content
Low-lying excited states of model proteins: Performances of the CC2 method versus multireference methods
J. Chem. Phys. (May 2018)
Magnetic gaps in organic tri-radicals: From a simple model to accurate estimates
J. Chem. Phys. (March 2017)
Additional global internal contraction in variations of multireference equation of motion coupled cluster theory
J. Chem. Phys. (April 2013)
A regionally contracted multireference configuration interaction method: General theory and results of an incremental version
J. Chem. Phys. (February 2011)
Multi-scale multireference configuration interaction calculations for large systems using localized orbitals: Partition in zones
J. Chem. Phys. (September 2012)