dorsal/arxiv
View SchemaAn efficient Monte Carlo method for calculating ab initio transition state theory reaction rates in solution
| Authors | Radu Iftimie, Dennis Salahub, Jeremy Schofield |
|---|---|
| Categories | |
| ArXiv ID | physics/0309124 |
| URL | https://arxiv.org/abs/physics/0309124 |
| DOI | 10.1063/1.1622653 |
Abstract
In this article, we propose an efficient method for sampling the relevant state space in condensed phase reactions. In the present method, the reaction is described by solving the electronic Schr\"{o}dinger equation for the solute atoms in the presence of explicit solvent molecules. The sampling algorithm uses a molecular mechanics guiding potential in combination with simulated tempering ideas and allows thorough exploration of the solvent state space in the context of an ab initio calculation even when the dielectric relaxation time of the solvent is long. The method is applied to the study of the double proton transfer reaction that takes place between a molecule of acetic acid and a molecule of methanol in tetrahydrofuran. It is demonstrated that calculations of rates of chemical transformations occurring in solvents of medium polarity can be performed with an increase in the cpu time of factors ranging from 4 to 15 with respect to gas-phase calculations.
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"abstract": "In this article, we propose an efficient method for sampling the relevant\nstate space in condensed phase reactions. In the present method, the reaction\nis described by solving the electronic Schr\\\"{o}dinger equation for the solute\natoms in the presence of explicit solvent molecules. The sampling algorithm\nuses a molecular mechanics guiding potential in combination with simulated\ntempering ideas and allows thorough exploration of the solvent state space in\nthe context of an ab initio calculation even when the dielectric relaxation\ntime of the solvent is long. The method is applied to the study of the double\nproton transfer reaction that takes place between a molecule of acetic acid and\na molecule of methanol in tetrahydrofuran. It is demonstrated that calculations\nof rates of chemical transformations occurring in solvents of medium polarity\ncan be performed with an increase in the cpu time of factors ranging from 4 to\n15 with respect to gas-phase calculations.",
"arxiv_id": "physics/0309124",
"authors": [
"Radu Iftimie",
"Dennis Salahub",
"Jeremy Schofield"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"doi": "10.1063/1.1622653",
"title": "An efficient Monte Carlo method for calculating ab initio transition state theory reaction rates in solution",
"url": "https://arxiv.org/abs/physics/0309124"
},
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