DFT calculations of the EPR parameters for Cu(ii) DETA imidazole complexes

Literature Information

Publication Date 2009-07-01
DOI 10.1039/B905750A
Impact Factor 3.676
Authors

William M. Ames, Sarah C. Larsen


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Abstract

The electron paramagnetic resonance (EPR) parameters for Cu(II) diethylenetriamine imidazole complexes, which serve as empirical models for copper-containing proteins, were calculated using density functional theory (DFT). The orientations of three different types of imidazole ligands, imidazole, 1-methylimidazole and 4-methylimidazole, were investigated by rotating the ligand about the Cu(II) imidazole bond. The calculated EPR values indicate that the imidazole ligands studied are oriented approximately ±45° with respect to the ligand plane. EPR parameters calculated using the B3LYP density functional in conjunction with the conductor-like solvent model (COSMO) show the best agreement with the experimentally determined EPR values. Good agreement with electron spin echo envelope modulation (ESEEM) data is achieved when an explicit water molecule is located near the remote nitrogen atom of the imidazole ligand. The implications of these DFT calculations for interpreting experimental pulsed EPR data for copper proteins containing imidazole ligands are discussed.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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