Self-consistent field convergence for proteins: a comparison of full and localized-molecular-orbital schemes
Wick C, Hennemann M, Stewart JJP, Clark T (2014)
Publication Type: Journal article
Publication year: 2014
Journal
Publisher: Springer Verlag (Germany)
Book Volume: 20
Pages Range: 2159
Volume: 20
Issue: 3
Journal Issue: 3
DOI: 10.1007/s00894-014-2159-y
Abstract
Proteins in the gas phase present an extreme (and unrealistic) challenge for self-consistent-field iteration schemes because their ionized groups are very strong electron donors or acceptors, depending on their formal charge. This means that gas-phase proteins have a very small band gap but that their frontier orbitals are localized compared to “normal” conjugated semiconductors. The frontier orbitals are thus likely to be separated in space so that they are close to, but not quite, orthogonal during the SCF iterations. We report full SCF calculations using the massively parallel EMPIRE code and linear scaling localized-molecular-orbital (LMO) calculations using Mopac2009. The LMO procedure can lead to artificially over-polarized wavefunctions in gas-phase proteins. The full SCF iteration procedure can be very slow to converge because many cycles are needed to overcome the over-polarization by inductive charge shifts. Example molecules have been constructed to demonstrate this behavior. The two approaches give identical results if solvent effects are included.
Authors with CRIS profile
Christian Wick
Computer-Chemie-Centrum
Matthias Hennemann
Computer-Chemie-Centrum
Timothy Clark
Computer-Chemie-Centrum
Additional Organisation(s)
Involved external institutions
United States (USA) (US)How to cite
APA:
Wick, C., Hennemann, M., Stewart, J.J.P., & Clark, T. (2014). Self-consistent field convergence for proteins: a comparison of full and localized-molecular-orbital schemes. Journal of Molecular Modeling, 20(3), 2159. https://dx.doi.org/10.1007/s00894-014-2159-y
MLA:
Wick, Christian, et al. "Self-consistent field convergence for proteins: a comparison of full and localized-molecular-orbital schemes." Journal of Molecular Modeling 20.3 (2014): 2159.
BibTeX: Download