Cavity ring-down polarimetry (CRDP): theoretical and experimental characterization

Detailed theoretical analyses are presented for cavity ring-down polarimetry, a recently developed scheme for probing circular birefringence (nonresonant rotatory dispersion) and circular dichroism (resonant differential absorption) with unprecedented sensitivity. Aside from elucidating the nature of time-resolved signals generated by various modes of operation, the influence of instrumental imperfections on polarimetric response is examined. The unique ability of cavity ring-down polarimetry to interrogate nonresonant optical activity in low-pressure chiral vapors is demonstrated by extracting specific rotation parameters at two complementary excitation wavelengths (355 nm and 633 nm) for gaseous samples of α-pinene, β-pinene, and cis-pinane. The resulting isolated-molecule properties are contrasted with those derived from conventional solution-phase experiments and state-of-the-art ab initio calculations.

[1]  M. Frisch,et al.  Calculation of Optical Rotation Using Density Functional Theory , 2001 .

[2]  Patrick H. Vaccaro,et al.  Cavity Ring-Down Polarimetry (CRDP): A New Scheme for Probing Circular Birefringence and Circular Dichroism in the Gas Phase , 2000 .

[3]  W. Ubachs,et al.  Experimental verification of Rayleigh scattering cross sections. , 2000, Optics letters.

[4]  M. Frisch,et al.  Hartree−Fock and Density Functional Theory ab Initio Calculation of Optical Rotation Using GIAOs: Basis Set Dependence , 2000 .

[5]  M. Vallet,et al.  Resonant cavity gas-phase polarimeter. , 1998, Analytical chemistry.

[6]  C. Brosseau.  Fundamentals of Polarized Light: A Statistical Optics Approach , 1998 .

[7]  M. Frisch,et al.  Ab Initio Prediction of Vibrational Absorption and Circular Dichroism Spectra of Chiral Natural Products Using Density Functional Theory: Camphor and Fenchone , 1997 .

[8]  G. Berden,et al.  Polarization dependent cavity ring down spectroscopy , 1997 .

[9]  Daniele Romanini,et al.  Diode laser cavity ring down spectroscopy , 1997 .

[10]  J. B. Paul,et al.  Cavity Ringdown Laser Absorption Spectroscopy: History, Development, and Application to Pulsed Molecular Beams. , 1997, Chemical reviews.

[11]  Richard N. Zare,et al.  Cavity ring-down spectroscopy for quantitative absorption measurements , 1995 .

[12]  Robert A. Goldbeck,et al.  Optical analysis of an ellipsometric technique for time-resolved magnetic circular dichroism spectroscopy , 1994 .

[13]  Kevin K. Lehmann,et al.  Ring-down cavity absorption spectroscopy of the very weak HCN overtone bands with six, seven, and eight stretching quanta , 1993 .

[14]  Teresa B. Freedman,et al.  Vibrational Circular Dichroism Of Simple Chiral Molecules In The Gas Phase , 1989, Other Conferences.

[15]  A. O’Keefe,et al.  Cavity ring‐down optical spectrometer for absorption measurements using pulsed laser sources , 1988 .

[16]  J. Schellman,et al.  Optical spectroscopy of oriented molecules , 1987 .

[17]  D. Michalska,et al.  Vibrational circular dichroism in (S)-(−)-epoxypropane. Measurement in vapor phase and verification of the perturbed degenerate mode theory , 1983 .

[18]  A. Gedanken,et al.  Circular dichroism of an optically active olefin chromophore: (R)-3-methylcyclopentene , 1980 .

[19]  T. Keiderling,et al.  VIBRATIONAL CIRCULAR DICHROISM , 1976 .

[20]  O. Schnepp,et al.  Circular dichroism spectra of straight chain mono-olefins. Assignment of ethylene transitions☆ , 1975 .

[21]  M. Mason,et al.  Absorption and circular dichroism spectra of ethylenic chromophores‐trans‐cyclooctene, α‐ and β‐pinene , 1973 .

[22]  W. C. Johnson,et al.  A circular dichroism spectrometer for the vacuum ultraviolet. , 1971, The Review of scientific instruments.

[23]  S. Allen,et al.  The Measurement of Circular Dichroism in the Vacuum Ultraviolet , 1970 .

[24]  M. J. Walker.  Matrix Calculus and the Stokes Parameters of Polarized Radiation , 1954 .

[25]  R. Jones.  A New Calculus for the Treatment of Optical SystemsI. Description and Discussion of the Calculus , 1941 .

[26]  E. Condon,et al.  Theories of Optical Rotatory Power , 1937 .

[27]  T. Lowry,et al.  Optical Rotatory Power of Vapours. Part I. Rotatory Dispersion of Camphor and of Camphorquinone, Especially in the Region of Absorption , 1932 .

[28]  Michael N. R. Ashfold,et al.  Cavity ring-down spectroscopy , 1998 .

[29]  L. Nafie.  Infrared and Raman vibrational optical activity: theoretical and experimental aspects. , 1997, Annual review of physical chemistry.

[30]  C. Reichardt.  Solvents and Solvent Effects in Organic Chemistry , 1988 .

[31]  G. Fowles,et al.  Introduction to modern optics , 1968 .

[32]  P. Crabbé.  3 – Optical Rotatory Dispersion and Circular Dichroism in Organic Chemistry , 1965 .

[33]  D. Gernez.  Recherches sur le pouvoir rotatoire des liquides actifs et de leurs vapeurs , 1864 .