Valence photoionization dynamics in circular dichroism of chiral free molecules: the methyl-oxirane.

The dynamical behavior of circular dichroism for valence photoionization processes in pure enantiomers of randomly oriented methyl-oxirane molecules has been studied by circularly polarized synchrotron radiation. Experimental results of the dichroism coefficient obtained for valence photoionization processes as a function of photon energy have been compared with theoretical values predicted by state-of-the-art ab initio density-functional theory. The circular dichroism measured at low electron kinetic energies was as large as 11%. Trends in the experimental dynamical behavior of the dichroism coefficients D(i)(omega) have been observed. Agreement between experimental and theoretical results permits unambiguous identification of the enantiomer and of the individual orbitals.

[1]  B. Ritchie.  Theory of the angular distribution of photoelectrons ejected from optically active molecules and molecular negative ions , 1976 .

[2]  W. Bonner.  Origins of Chiral Homogeneity in Nature , 2007 .

[3]  G. Ertl,et al.  Handbook of Heterogeneous Catalysis , 1997 .

[4]  I. Powis,et al.  Circular dichroism in the photoelectron angular distribution from randomly oriented enantiomers of camphor , 2003 .

[5]  P. Decleva,et al.  Convergence of the multicenter B-spline DFT approach for the continuum , 2002 .

[6]  M. Stener,et al.  Density functional study on the circular dichroism of photoelectron angular distribution from chiral derivatives of oxirane. , 2004, The Journal of chemical physics.

[7]  N. Chandra.  Photoelectron spectroscopic studies of polyatomic molecules. I. Theory , 1987 .

[8]  R. Walker,et al.  Studies of insertion devices for producing circularly polarized radiation with variable helicity in ELETTRA , 1992 .

[9]  N. Cherepkov.  Circular dichroism of molecules in the continuous absorption region , 1982 .

[10]  F. Martín,et al.  Applications of B-splines in atomic and molecular physics , 2001 .

[11]  H.-J. Weigmann,et al.  Determination of the Horny Layer Profile by Tape Stripping in Combination with Optical Spectroscopy in the Visible Range as a Prerequisite to Quantify Percutaneous Absorption , 1999, Skin Pharmacology and Physiology.

[12]  R. Raval,et al.  Extended surface chirality from supramolecular assemblies of adsorbed chiral molecules , 2000, Nature.

[13]  Jurriaan Huskens,et al.  Complete asymmetric chirality in a hydrogen-bonded assembly , 1999 .

[14]  R. Leeuwen,et al.  Exchange-correlation potential with correct asymptotic behavior. , 1994, Physical review. A, Atomic, molecular, and optical physics.

[15]  J. M. Rivera,et al.  Chiral spaces: dissymmetric capsules through self-assembly. , 1998, Science.

[16]  G. Fasman.  Circular Dichroism and the Conformational Analysis of Biomolecules , 1996, Springer US.

[17]  Mark E. Davis,et al.  Design and synthesis of a heterogeneous asymmetric catalyst , 1994, Nature.

[18]  Evert Jan Baerends,et al.  Towards an order , 1998 .

[19]  U. Heinzmann,et al.  Circular dichroism in valence photoelectron spectroscopy of free unoriented chiral molecules: Camphor and bromocamphor , 2004 .

[20]  U. Heinzmann,et al.  Asymmetry in photoelectron emission from chiral molecules induced by circularly polarized light. , 2001, Physical review letters.

[21]  I. Powis.  Photoelectron Spectroscopy and Circular Dichroism in Chiral Biomolecules: l-Alanine , 2000 .

[22]  Michele Alagia,et al.  Circular dichroism in photoelectron spectroscopy of free chiral molecules: Experiment and theory on methyl-oxirane , 2004 .

[23]  W. Bonner,et al.  The origin and amplification of biomolecular chirality , 2005, Origins of life and evolution of the biosphere.

[24]  J. Atwood,et al.  A chiral spherical molecular assembly held together by 60 hydrogen bonds , 1997, Nature.

[25]  I. Powis,et al.  Photoelectron circular dichroism in core level ionization of randomly oriented pure enantiomers of the chiral molecule camphor. , 2004, The Journal of chemical physics.

[26]  I. Powis.  Photoelectron circular dichroism of the randomly oriented chiral molecules glyceraldehyde and lactic acid , 2000 .