4.7 Article

Femtosecond spectral interferometry of optical activity: Theory

Journal

JOURNAL OF CHEMICAL PHYSICS
Volume 129, Issue 9, Pages -

Publisher

AMER INST PHYSICS
DOI: 10.1063/1.2968130

Keywords

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Funding

  1. Creative Research Initiatives (CMDS) of MEST/KOSEF
  2. Ministry of Education, Science & Technology (MoST), Republic of Korea [N28030] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
  3. National Research Foundation of Korea [R16-2000-004-01001-0, R11-1998-051-05001-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)

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Optical activities such as circular dichroism (CD) and optical rotatory dispersion (ORD) are manifested by almost all natural products. However, the CD is an extremely weak effect so that time-resolved CD spectroscopy has been found to be experimentally difficult and even impossible for vibrational CD with current technology. Here, we show that the weak-signal and nonzero background problems can be overcome by heterodyned spectral interferometric detection of the phase and amplitude of optical activity free-induction-decay (OA FID) field. A detailed theoretical description and a cross-polarization scheme for selectively measuring the OA FID are presented and discussed. It is shown that the parallel and perpendicular electric fields when the solution sample contains chiral molecules are coupled to each other. Therefore, simultaneous spectral interferometric measurements of the parallel and perpendicular FID fields can provide the complex susceptibility, which is associated with the circular dichroism and optical rotatory dispersion as its imaginary and real parts, respectively. On the basis of the theoretical results, to examine its experimental possibility, we present numerical simulations for a model system. We anticipate the method discussed here to be a valuable tool for detecting electronic or vibrational optical activity in femtosecond time scale. (C) 2008 American Institute of Physics.

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