Effect of Amino Acid Ligands on the Structure of Iron Porphyrins and Their Ability to Bind Oxygen

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2014-06, Vol.118 (25), p.4565-4574
• Main Authors: Berryman, Victoria E. J, Baker, Matthew G, Boyd, Russell J
• Format: Article
• Language: English
• Subjects: Amino acids; Amino Acids - chemistry; Amino Acids - metabolism; Binding energy; Density; Dispersions; Functionals; Ground state; Iron; Iron - chemistry; Iron - metabolism; Models, Chemical; Molecular Structure; Oxygen - chemistry; Oxygen - metabolism; Porphyrins; Porphyrins - chemistry; Porphyrins - metabolism; Quantum Theory; Thermodynamics
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp502541y

Density functional theory is used to study a series of model iron porphyrins in the gas phase. In the first part of this study, three range-separated hybrid density functionals developed by Chai and Head-Gordon were assessed; ωB97, ωB97X, and ωB97XD. The effects of including full Hartree–Fock exchange at long-range and dispersion corrections are reported with respect to the geometries and binding energies of oxygen to the iron porphyrin systems. The functionals all correctly predict the quintet ground state for the deoxy-iron porphyrins, where typically hybrid functionals fail and predict a triplet ground state. Including dispersion in ωB97XD is shown to give the best results for the O2 binding energy and geometrical parameters. The second part of the study employs ωB97XD to study iron porphine systems with different amino acids in the axial position. Geometrical parameters are reported and compared to experimental data, where available. Binding energies of the systems with oxygen are also reported and discussed.