Density functional theory hyperfine couplings

Several recent papers have reported Density Functional Theory (DFT) calculations on the primary oxidation and reduction products observed in irradiated single crystals of the common nucleobases thymine [53], cytosine [54], guanine [55], and adenine [56]. The theoretical calculations include estimates of spin densities and isotropic and anisotropic hyperfine couplings which can be compared with experimental results (obtained from detailed EPR/ENDOR experiments). 

Naumov S, Beckert D (2002) Reply to the Comment on A Fourier transform EPR study of uracil and thymine radical anions in aqueous solution)/ by DM Close. Phys Chem Chem Phys 4 45 Naumov S, Barthel A, Reinhold J, Dietz F, Geimer J, Beckert D (2000) Calculation of spin densities of radicals of pyrimidine-type bases by density functional theory. Influence of solvent and comparison with EPR results. Phys Chem Chem Phys 2 4207-4211 Naumov S, Hildenbrand K, von Sonntag C (2001) Tautomers of the N-centered radical generated by reaction of SO4 - with N(1)substituted cytosines in aqueous solution. Calculation of isotropic hyperfine coupling constants by a density functional method. J Chem Soc Perkin Trans 2 1648-1653... 

The electronic structures and isotopic hyperfine coupling constants of a series of neutral 1,3,2-dithiazolyl radicals 1-4 were investigated by means of density functional theory (DFT) <1996MRC913>. 

ESR spectra can provide not only an unambiguous assignment of radicals, but also experimental information about their geometrical and electronic structures and reactions. CW-ESR spectroscopy combined with matrix isolation methods and ionizing radiation (y-ray, X-ray, etc.) is applied to the studies on reactive intermediate radicals including anionic and cationic species trapped in low temperature solid matrices. ESR parameters, especially hyperfine (hf) couplings, are predicted with considerable precision by recent advances in computational methods such as density functional theory (DFT), which affords a valuable bridge between experiment and theory at a most fundamental level. 

Besides a g-factor and aminoxyl nitrogen coupling constant dependent on the species trapped, the ESR spectra also showed different patterns due to hyperfine splitting characteristic of the radical scavenged. This last important feature was investigated by means of density functional theory calculations. The overall summary of the ESR characteristics of various ARs produced in nitrones has been completed [19, 72]. In these studies, the various aspects and features of application of the spin trap method in invetigations of the mechanism of chemical reactions are considered. 

The ESR hyperfine coupling is determined by triplet perturbations. Thus, in principle one should use an unrestricted wave function to describe the reference state. However, it is also possible to use a spin-restricted wave function (Fernandez et al. 1992) and take into account the triplet nature of the perturbation in the definition of the response. Within such a (e.g., SCF or MCSCF) restricted-unrestricted approach, first-order properties are given as the sum of the usual expectation value term and a response correction that takes into account the change of the wave function induced by the perturbation (of the type (0 H° 0)). This restricted-unrestricted approach has also been extended to restricted Kohn-Sham density functional theory (Rinkevicius et al. 2004). 

Arbuznikov, A. V., Vaara, J., Kaupp, M. (2004). Relativistic spin-orbit effects on hyperfine coupling tensors by density-functional theory. Journal of Chemical Physics, 120, 2127. 

Rinkevicius, Z., Telyatnyk, L., Vahtras, O., Agren, H. (2004). Density functional theory for hyperfine coupling constants with the restricted-unrestricted approach. Journal of Chemical Physics, 121, 7614. 

Basis Sets Correlation Consistent Sets Circular Dichro-ism Electronic Complete Active Space Self-consistent Field (CASSCF) Second-order Perturbation Theory (CASPT2) Configuration Interaction Density Functional Applications Density Functional Theory (DFT), Hartree-Fock (HF), and the Self-consistent Field Electronic Diabatic States Definition, Computation, and Applications ESR Hyperfine Calculations Magnetic Circular Dichroism of rt Systems Non-adiabatic Derivative Couplings Relativistic Theory and Applications Structure Determination by Computer-based Spectrum Interpretation Valence Bond Curve Crossing Models. 

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