Chiroptical nature of two-exciton states of light-harvesting complex: Doubly resonant three-wave-mixing spectroscopy
- Authors
- Lee, Hochan; Cheon, Sangheon; Cho, Minhaeng
- Issue Date
- 14-6월-2010
- Publisher
- AMER INST PHYSICS
- Citation
- JOURNAL OF CHEMICAL PHYSICS, v.132, no.22
- Indexed
- SCIE
SCOPUS
- Journal Title
- JOURNAL OF CHEMICAL PHYSICS
- Volume
- 132
- Number
- 22
- URI
- https://scholar.korea.ac.kr/handle/2021.sw.korea/116242
- DOI
- 10.1063/1.3432624
- ISSN
- 0021-9606
- 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 chi((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. (C) 2010 American Institute of Physics. [doi:10.1063/1.3432624]
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