Interpretation of Indirect Nuclear Spin_Spin Couplings in Isomers of Adenine: Novel Approach to Analyze Coupling Electron Deformation Density Using Localized Molecular Orbitals

Warning

This publication doesn't include Faculty of Economics and Administration. It includes Faculty of Science. Official publication website can be found on muni.cz.

Authors	MAREK Radek KŘÍSTKOVÁ Anežka MALIŇÁKOVÁ Kateřina TOUŠEK Jaromír MAREK Jaromír HOCEK Michal MALKINA Olga L. MALKIN Vladimir G.
Year of publication	2010
Type	Article in Periodical
Magazine / Source	The Journal of Physical Chemistry A
MU Faculty or unit	Faculty of Science
Citation
Web	DOI: 10.1021/jp102186r
Field	Physical chemistry and theoretical chemistry
Keywords	coupling constant; coupling electron deformation density; localized molecular orbitals; adenine
Description	In this study, long_range 1H_13C and 1H_15N coupling constants for N_alkyl derivatives related to four tautomers of adenine are investigated in DMSO and DMF solutions. To investigate the structural dependence of the coupling constants and to understand how polarization propagates in the system, Fermi contact (FC) terms were calculated for the individual isomers and analyzed by using density functional theory (DFT), and the coupling pathways were visualized using real_space functions. The coupling electron deformation densities (CDD) of several 1H_X (X = 13C, 15N) pairs are evaluated and compared. In order to analyze the CDD in more detail, a new approach to break down the CDD into contributions from Boys or Pipek_Mezey localized molecular orbitals (LMOs) has been developed. A similar approach has been applied to split the value of the FC contribution to the J coupling into the LMO contributions.
Related projects:	Proteins in metabolism and interaction of organisms with the environment Biomolecular centre