dorsal/arxiv
View SchemaPath integral evaluation of the kinetic isotope effects based on the quantum instanton approximation
| Authors | Jiri Vanicek, William H. Miller |
|---|---|
| Categories | |
| ArXiv ID | physics/0604150 |
| URL | https://arxiv.org/abs/physics/0604150 |
| Journal | The 8th International Conference: Path Integrals from Quantum Information to Cosmology, Eds. C. Burdik, O. Navratil and S. Posta, JINR, Dubna, 2005 |
Abstract
A general method for computing kinetic isotope effects is described. The method uses the quantum-instanton approximation and is based on the thermodynamic integration with respect to the mass of the isotopes and on the path-integral Monte-Carlo evaluation of relevant thermodynamic quantities. The central ingredients of the method are the Monte-Carlo estimators for the logarithmic derivatives of the partition function and the delta-delta correlation function. Several alternative estimators for these quantities are described here and their merits are compared on the benchmark hydrogen-exchange reaction, H+H_2->H_2+H on the Truhlar-Kuppermann potential energy surface. Finally, a qualitative discussion of issues arising in many-dimensional systems is provided.
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"abstract": "A general method for computing kinetic isotope effects is described. The\nmethod uses the quantum-instanton approximation and is based on the\nthermodynamic integration with respect to the mass of the isotopes and on the\npath-integral Monte-Carlo evaluation of relevant thermodynamic quantities. The\ncentral ingredients of the method are the Monte-Carlo estimators for the\nlogarithmic derivatives of the partition function and the delta-delta\ncorrelation function. Several alternative estimators for these quantities are\ndescribed here and their merits are compared on the benchmark hydrogen-exchange\nreaction, H+H_2-\u003eH_2+H on the Truhlar-Kuppermann potential energy surface.\nFinally, a qualitative discussion of issues arising in many-dimensional systems\nis provided.",
"arxiv_id": "physics/0604150",
"authors": [
"Jiri Vanicek",
"William H. Miller"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"journal_ref": "The 8th International Conference: Path Integrals from Quantum\n Information to Cosmology, Eds. C. Burdik, O. Navratil and S. Posta, JINR,\n Dubna, 2005",
"title": "Path integral evaluation of the kinetic isotope effects based on the quantum instanton approximation",
"url": "https://arxiv.org/abs/physics/0604150"
},
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