Spin densities from subsystem density-functional theory: Assessment and application to a photosynthetic reaction center complex model

Journal Article · Mon May 21 00:00:00 EDT 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4709771· OSTI ID:22047210

Solovyeva, Alisa ^[1]; Pavanello, Michele ^[1]; Neugebauer, Johannes ^[2]

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1. Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands)
2. Technical University Braunschweig, Institute for Physical and Theoretical Chemistry, Hans-Sommer-Str. 10, 38106 Braunschweig (Germany)

Subsystem density-functional theory (DFT) is a powerful and efficient alternative to Kohn-Sham DFT for large systems composed of several weakly interacting subunits. Here, we provide a systematic investigation of the spin-density distributions obtained in subsystem DFT calculations for radicals in explicit environments. This includes a small radical in a solvent shell, a {pi}-stacked guanine-thymine radical cation, and a benchmark application to a model for the special pair radical cation, which is a dimer of bacteriochlorophyll pigments, from the photosynthetic reaction center of purple bacteria. We investigate the differences in the spin densities resulting from subsystem DFT and Kohn-Sham DFT calculations. In these comparisons, we focus on the problem of overdelocalization of spin densities due to the self-interaction error in DFT. It is demonstrated that subsystem DFT can reduce this problem, while it still allows to describe spin-polarization effects crossing the boundaries of the subsystems. In practical calculations of spin densities for radicals in a given environment, it may thus be a pragmatic alternative to Kohn-Sham DFT calculations. In our calculation on the special pair radical cation, we show that the coordinating histidine residues reduce the spin-density asymmetry between the two halves of this system, while inclusion of a larger binding pocket model increases this asymmetry. The unidirectional energy transfer in photosynthetic reaction centers is related to the asymmetry introduced by the protein environment.

• OSTI ID: 22047210
• Journal Information: Journal of Chemical Physics, Vol. 136, Issue 19; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
60 APPLIED LIFE SCIENCES
ASYMMETRY
BACTERIA
CATIONS
DENSITY
DENSITY FUNCTIONAL METHOD
GUANINE
HISTIDINE
PHOTOSYNTHESIS
PHOTOSYNTHETIC REACTION CENTERS
PROTEINS
RADICALS
SPIN
SPIN ORIENTATION
THYMINE