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- Valence structures of aromatic bioactive compounds: a combined theoretical and experimental study
- Wickrama Arachchilage, Anoja Pushpamali; Feyer, Vitaliy; Plekan, Oksana; Iakhnenko, Marianna; Prince, Kevin C.; Wang, Feng
- Valence electronic structures of three recently isolated aryl bioactive compounds, namely 2-phenylethanol (2PE), p-hydroxyphenylethanol (HPE) and 4-hydroxybenzaldehyde (HBA), are studied using a combined theoretical and experimental method. Density functional theory-based calculations indicate that the side chains cause electron charge redistribution and therefore influence the aromaticity of the benzene derivatives. The simulated IR spectra further reveal features induced by the side chains. Solvent effects on the IR spectra are simulated using the polarizable continuum model, which exhibits enhancement of the O—H stretch vibrations with significant red-shift of 464 cm−1 in 2PE. A significant spectral peak splitting of 94 cm−1 between O(4)—H and O(8)—H of HPE is revealed in an aqueous environment. Experimental measurements for valence binding energy spectra for 2PE, HPE and HBA are presented and analyzed using outer-valence Green function calculations. The experimental (predicted) first ionization energies are measured as 9.19 (8.79), 8.47 (8.27) and 8.97 (8.82) eV for 2PE, HPE and HBA, respectively. The frontier orbitals (highest occupied molecular orbitals, HOMOs, and lowest unoccupied molecular orbitals, LUMOs) have similar atomic orbital characters although the HOMO–LUMO energy gaps are quite different.
- Publication type
- Journal article
- Research centre
- Swinburne University of Technology. Faculty of Life and Social Sciences
- Journal of Synchrotron Radiation, Vol. 19, no. 5 (Sep 2012), pp. 773-781
- Publication year
- International Union of Crystallography
- Publisher URL
- Copyright © 2012 International Union of Crystallography. The author's electronic reprint is reproduced in accordance with the copyright policy of the publisher.