Quadrupole contribution to the third-order optical activity spectroscopy

Jun Ho Choi, Minhaeng Cho

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)


Time-resolved nonlinear optical activity measurement spectroscopy can be a useful tool for studying biomolecular and chemical reaction dynamics of chiral molecules. Only recently, the two-dimensional (2D) circularly polarized photon echo (CP-PE) spectroscopy of polypeptides and a photosynthetic light-harvesting complex were discussed, where the beam configuration was specifically controlled in such a way to eliminate the quadrupole contribution to the CP-PE signal. In this paper, we generalize the CP-PE spectroscopy by including the transition quadrupole contributions from peptide amide I vibrational transition and chlorophyll electronic transition. By using a density functional theory calculation method, the corresponding amide I vibrational and chlorophyll Qy electronic transition quadrupole tensor elements are determined. Amplitude of nonlinear optical transition pathway involving a quadrupole transition is found to be comparable to those of magnetic dipole terms for two different cases considered, i.e., dipeptides and photosynthetic antenna complex. However, due to the rotational averaging factors, the overall quadrupole contribution is an order of magnitude smaller than the magnetic dipole contribution. This suggests that the conventional 2D photon echo method and experimental scheme can be directly used to measure the 2D CP-PE signal from proteins and molecular complexes and that the 2D CP-PE signal is mainly dictated by the magnetic dipole contribution.

Original languageEnglish
Article number024507
JournalJournal of Chemical Physics
Issue number2
Publication statusPublished - 2007

Bibliographical note

Funding Information:
This work was supported by the CRI Program ofKOSEF (Korea Science and Engineering Foundation, MOST).

ASJC Scopus subject areas

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


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