Heck, Alexander and Woiczikowski, P. Benjamin and Kubar, Tomas and Welke, Kai and Niehaus, Thomas and Giese, Bernd and Skourtis, Spiros and Elstner, Marcus and Steinbrecher, Thomas B. (2014) Fragment Orbital Based Description of Charge Transfer in Peptides Including Backbone Orbitals. JOURNAL OF PHYSICAL CHEMISTRY B, 118 (16). pp. 4261-4272. ISSN 1520-6106,
Full text not available from this repository. (Request a copy)Abstract
Charge transfer in peptides and proteins can occur on different pathways, depending on the energetic landscape as well as the coupling between the involved orbitals. Since details of the mechanism and pathways are difficult to access experimentally, different modeling strategies have been successfully applied to study these processes in the past. These can be based on a simple empirical pathway model, efficient tight binding type atomic orbital Hamiltonians or ab initio and density functional calculations. An interesting strategy, which allows an efficient calculations of charge transfer parameters, is based on a fragmentation of the system into functional units. While this works well for systems like DNA, where the charge transfer pathway is naturally divided into distinct molecular fragments, this is less obvious for charge transfer along peptide and protein backbones. In this work, we develop and access a strategy for an effective fragmentation approach, which allows one to compute electronic couplings for large systems along nanosecond time scale molecular dynamics trajectories. The new methodology is applied to a solvated peptide, for which charge transfer properties have been studied recently using an empirical pathway model. As could be expected, dynamical effects turn out to be important, which emphasizes the importance of using effective quantum approaches which allow for sufficient sampling. However, the computed rates are orders of magnitude smaller than experimentally determined, which indicates the shortcomings of present modeling approaches.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ELECTRON-TRANSFER REACTIONS; DENSITY-FUNCTIONAL THEORY; MOLECULAR MECHANICAL METHODS; CYTOCHROME-C-OXIDASE; AB-INITIO; HOLE TRANSFER; STRUCTURAL FLUCTUATIONS; BIOLOGICAL MOLECULES; MATRIX-ELEMENTS; QM/MM METHODS; |
| Subjects: | 500 Science > 530 Physics |
| Divisions: | Physics > Institute of Theroretical Physics > Alumni or Retired Professors > Group Thomas Niehaus |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 13 Nov 2019 15:18 |
| Last Modified: | 13 Nov 2019 15:18 |
| URI: | https://pred.uni-regensburg.de/id/eprint/10294 |
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