Hoelzl, Christoph and Kibies, Patrick and Imoto, Sho and Frach, Roland and Suladze, Saba and Winter, Roland and Marx, Dominik and Horinek, Dominik and Kast, Stefan M. (2016) Design principles for high-pressure force fields: Aqueous TMAO solutions from ambient to kilobar pressures. JOURNAL OF CHEMICAL PHYSICS, 144 (14): 144104. ISSN 0021-9606, 1089-7690
Full text not available from this repository. (Request a copy)Abstract
Accurate force fields are one of the major pillars on which successful molecular dynamics simulations of complex biomolecular processes rest. They have been optimized for ambient conditions, whereas high-pressure simulations become increasingly important in pressure perturbation studies, using pressure as an independent thermodynamic variable. Here, we explore the design of non-polarizable force fields tailored to work well in the realm of kilobar pressures - while avoiding complete reparameterization. Our key is to first compute the pressure-induced electronic and structural response of a solute by combining an integral equation approach to include pressure effects on solvent structure with a quantum-chemical treatment of the solute within the embedded cluster reference interaction site model (EC-RISM) framework. Next, the solute's response to compression is taken into account by introducing pressure-dependence into selected parameters of a well-established force field. In our proof-of-principle study, the full machinery is applied to N,N,N-trimethylamine-N-oxide (TMAO) in water being a potent osmolyte that counteracts pressure denaturation. EC-RISM theory is shown to describe well the charge redistribution upon compression of TMAO(aq) to 10 kbar, which is then embodied in force field molecular dynamics by pressure-dependent partial charges. The performance of the high pressure force field is assessed by comparing to experimental and ab initio molecular dynamics data. Beyond its broad usefulness for designing non-polarizable force fields for extreme thermodynamic conditions, a good description of the pressure-response of solutions is highly recommended when constructing and validating polarizable force fields. (C) 2016 AIP Publishing LLC.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DENSITY-FUNCTIONAL THEORY; MOLECULAR-DYNAMICS SIMULATION; TRIMETHYLAMINE-N-OXIDE; INTERACTION SITE MODEL; INTEGRAL-EQUATION THEORY; SPACE GAUSSIAN PSEUDOPOTENTIALS; NONUNIFORM POLYATOMIC SYSTEMS; TERT-BUTYL ALCOHOL; HYDROSTATIC-PRESSURE; QUANTUM-CHEMISTRY; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 05 Apr 2019 07:25 |
| Last Modified: | 05 Apr 2019 07:25 |
| URI: | https://pred.uni-regensburg.de/id/eprint/3075 |
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