Infrared optical activity

Electric field approaches in time domain

Hanju Rhee, Jun Ho Choi, Minhaeng Cho

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Vibrational circular dichroism (VCD) spectroscopy provides detailed information about the absolute configurations of chiral molecules including biomolecules and synthetic drugs. This method is the infrared (IR) analogue of the more popular electronic CD spectroscopy that uses the ultraviolet and visible ranges of the electromagnetic spectrum. Because conventional electronic CD spectroscopy measures the difference in signal intensity, problems such as weak signal and low time-resolution can limit its utility. To overcome the difficulties associated with that approach, we have recently developed femtosecond IR optical activity (IOA) spectrometry, which directly measures the IOA free-induction-decay (FID), the impulsive chiroptical IR response that occurs over time. In this Account, we review the time-domain electric field measurement and calculation methods used to simultaneously characterize VCD and related vibrational optical rotatory dispersion (VORD) spectra. Although conventional methods measure the electric field intensity, this vibrational technique is based on a direct phase-and-amplitude measurement of the electric field of the chiroptical signal over time. This method uses a cross-polarization analyzer to carry out heterodyned spectral interferometry. The cross-polarization scheme enables us to selectively remove the achiral background signal, which is the dominant noise component present in differential intensity measurement techniques. Because we can detect the IOA FID signal in a phase-amplitude-sensitive manner, we can directly characterize the time-dependent electric dipole/magnetic dipole response function and the complex chiral susceptibility that contain information about the angular oscillations of charged particles. These parameters yield information about the VCD and VORD spectra. In parallel with such experimental developments, we have also calculated the IOA FID signal and the resulting VCD spectrum. These simulations use a quantum mechanical/molecular mechanical molecular dynamics (QM/MM MD) method and calculate the electric dipole/magnetic dipole cross-correlation function in the time domain. Although many quantum chemistry calculation approaches can only consider a limited number of geometry-optimized conformations of chiral molecules in a gas phase, this computational method includes the solute-solvent interactions and the inhomogeneous distributions of solute conformers in condensed phases. A subsequent Fourier transformation of the chiral response function produced a theoretical VCD spectrum in the entire mid-IR frequency range. Directly comparing theory and experiment, we demonstrate quantitative agreement between frequency-tunable femtosecond IOA measurements and QM/MM MD simulations of (1S)-β- pinene in CCl 4 solution. We anticipate that these direct IOA measurement and calculation methods will be applied to the studies of equilibrium chiroptical properties and structure determinations. These methods provide tools to investigate ultrafast structural dynamics of chiral systems with unprecedented time resolution.

Original languageEnglish
Pages (from-to)1527-1536
Number of pages10
JournalAccounts of Chemical Research
Volume43
Issue number12
DOIs
Publication statusPublished - 2010 Dec 21

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Electric fields
Infrared radiation
Molecular dynamics
Electric field measurement
Spectroscopy
Polarization
Circular dichroism spectroscopy
Quantum chemistry
Vibrational spectroscopy
Molecules
Structural dynamics
Biomolecules
Charged particles
Computational methods
Interferometry
Spectrometry
Conformations
Gases
Circular Dichroism
Geometry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Infrared optical activity : Electric field approaches in time domain. / Rhee, Hanju; Choi, Jun Ho; Cho, Minhaeng.

In: Accounts of Chemical Research, Vol. 43, No. 12, 21.12.2010, p. 1527-1536.

Research output: Contribution to journalArticle

Rhee, Hanju ; Choi, Jun Ho ; Cho, Minhaeng. / Infrared optical activity : Electric field approaches in time domain. In: Accounts of Chemical Research. 2010 ; Vol. 43, No. 12. pp. 1527-1536.
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