On circular dichroism and the separation between chromophore and chiral center: the near carbon K-edge X-ray absorption and circular dichroism spectra of noradrenaline and L-DOPA.

The near carbon K-edge X-ray absorption and circular dichroism spectra of noradrenaline (neutral and protonated forms) and L-DOPA (protonated form) have been determined with use of the complex polarization propagator method in conjunction with Kohn-Sham density functional theory. A Coulomb attenuated exchange-correlation functional and London atomic orbitals have been employed to address the issues of hole-electron interactions and gauge-origin dependence of the magnetic-dipole operator, respectively. Results show that the characteristics of the chromophore part of the circular dichroism spectra are shared for all three considered systems, whereas protonation qualitatively alters the part of the spectrum assigned to the chiral side chain. The comparatively larger spatial separation of chromophore and chiral center in L-DOPA inflicts larger differences in spectral intensities between the chromophore and chiral center part of the circular dichroism spectra. (c) 2009 Wiley-Liss, Inc.