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

0348924 - ÚOCHB 2011 RIV US eng J - Journal Article
Marek, R. - Křístková, A. - Maliňáková, K. - Toušek, J. - Marek, J. - Hocek, Michal - Malkina, O. L. - Malkin, V. G.
Interpretation of Indirect Nuclear Spin-Spin Couplings in Isomers of Adenine: Novel Approach to Analyze Coupling Electron Deformation Density Using Localized Molecular Orbitals.
Journal of Physical Chemistry A. Roč. 114, č. 24 (2010), s. 6689-6700. ISSN 1089-5639. E-ISSN 1520-5215
Grant - others:GA MŠk(CZ) LC06030
Program: LC
Institutional research plan: CEZ:AV0Z40550506
Keywords : coupling constant
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.732, year: 2010

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.
Permanent Link: http://hdl.handle.net/11104/0006065