Chiroptical nature of two-exciton states of light-harvesting complex: Doubly resonant three-wave-mixing spectroscopy

Hochan Lee, Sangheon Cheon, Minhaeng Cho

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Photosynthetic light-harvesting complex is a coupled multichromophore system. Due to electronic couplings between neighboring chlorophylls in the complex, the one- and two-exciton states are delocalized and they can be written as linear combinations of singly and doubly excited configurations, respectively. Despite that the chiroptical properties of one-exciton states in such a multichromophore system have been investigated by using linear optical activity measurement techniques; those of two-exciton states have not been studied before due to a lack of appropriate measurement methods. Here, we present a theoretical description on chiroptical (2) spectroscopy and show that it can be used to investigate such properties of a photosynthetic light-harvesting system, which is the Fenna-Matthews-Olson complex, consisting of seven bacteriochlorophylls in its protein subunit. To simulate the doubly resonant sum- and difference-frequency-generation spectra of the complex, one- and two-exciton transition dipoles were calculated. Carrying out quantum chemistry calculations of electronically excited states of a model bacteriochlorophyll system and taking into account the dipole-induced dipole electronic transition processes between the ground state and two-exciton states, we could calculate the two-dimensional sum-frequency-generation spectra revealing dominant second-order chiroptical transition pathways and involved one- and two-exciton states. It is believed that the present computational scheme and the theoretically proposed doubly resonant two-dimensional three-wave-mixing spectroscopy would be of use to shed light on the chiroptical natures of two-exciton states of arbitrary coupled multichromophore systems.

Original languageEnglish
Article number225102
JournalJournal of Chemical Physics
Volume132
Issue number22
DOIs
Publication statusPublished - 2010 Jun 14

Fingerprint

excitons
Spectroscopy
spectroscopy
Bacteriochlorophylls
dipoles
LDS 751
Quantum chemistry
optical activity
Protein Subunits
quantum chemistry
chlorophylls
Chlorophyll
Electron transitions
electronics
Excited states
Ground state
proteins
ground state
configurations
excitation

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Chiroptical nature of two-exciton states of light-harvesting complex : Doubly resonant three-wave-mixing spectroscopy. / Lee, Hochan; Cheon, Sangheon; Cho, Minhaeng.

In: Journal of Chemical Physics, Vol. 132, No. 22, 225102, 14.06.2010.

Research output: Contribution to journalArticle

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