dorsal/arxiv
View SchemaTracing the minimum-energy path on the free-energy surface
| Authors | P. Fleurat-Lessard, T. Ziegler |
|---|---|
| Categories | |
| ArXiv ID | physics/0505205 |
| URL | https://arxiv.org/abs/physics/0505205 |
| DOI | 10.1063/1.1948367 |
Abstract
The free energy profile of a reaction can be estimated in a molecular-dynamics approach by imposing a mechanical constraint along a reaction coordinate (RC). Many recent studies have shown that the temperature can greatly influence the path followed by the reactants. Here, we propose a practical way to construct the minimum energy path directly on the free energy surface (FES) at a given temperature. First, we follow the blue-moon ensemble method to derive the expression of the free energy gradient for a given RC. These derivatives are then used to find the actual minimum energy reaction path at finite temperature, in a way similar to the Intrinsic Reaction Path of Fukui on the potential energy surface [K Fukui J. Phys. Chem. 74, 4161 (1970)]. Once the path is know, one can calculate the free energy profile using thermodynamic integration. We also show that the mass-metric correction cancels for many types of constraints, making the procedure easy to use. Finally, the minimum free energy path at 300 K for the addition of the 1,1'-dichlorocarbene to ethylene is compared with a path based on a simple one-dimensional reaction coordinate. A comparison is also given with the reaction path at 0 K.
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"abstract": "The free energy profile of a reaction can be estimated in a\nmolecular-dynamics approach by imposing a mechanical constraint along a\nreaction coordinate (RC). Many recent studies have shown that the temperature\ncan greatly influence the path followed by the reactants. Here, we propose a\npractical way to construct the minimum energy path directly on the free energy\nsurface (FES) at a given temperature. First, we follow the blue-moon ensemble\nmethod to derive the expression of the free energy gradient for a given RC.\nThese derivatives are then used to find the actual minimum energy reaction path\nat finite temperature, in a way similar to the Intrinsic Reaction Path of Fukui\non the potential energy surface [K Fukui J. Phys. Chem. 74, 4161 (1970)]. Once\nthe path is know, one can calculate the free energy profile using thermodynamic\nintegration. We also show that the mass-metric correction cancels for many\ntypes of constraints, making the procedure easy to use. Finally, the minimum\nfree energy path at 300 K for the addition of the 1,1\u0027-dichlorocarbene to\nethylene is compared with a path based on a simple one-dimensional reaction\ncoordinate. A comparison is also given with the reaction path at 0 K.",
"arxiv_id": "physics/0505205",
"authors": [
"P. Fleurat-Lessard",
"T. Ziegler"
],
"categories": [
"physics.chem-ph",
"cond-mat.stat-mech"
],
"doi": "10.1063/1.1948367",
"title": "Tracing the minimum-energy path on the free-energy surface",
"url": "https://arxiv.org/abs/physics/0505205"
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