dorsal/arxiv
View SchemaAn Anderson Impurity Model for Efficient Sampling of Adiabatic Potential Energy Surfaces of Transition Metal Complexes
| Authors | M. X. LaBute, R. G. Endres, D. L. Cox |
|---|---|
| Categories | |
| ArXiv ID | physics/0406043 |
| URL | https://arxiv.org/abs/physics/0406043 |
| DOI | 10.1063/1.1795152 |
Abstract
We present a model intended for rapid sampling of ground and excited state potential energy surfaces for first-row transition metal active sites. The method is computationally inexpensive and is suited for dynamics simulations where (1) adiabatic states are required "on-the-fly" and (2) the primary source of the electronic coupling between the diabatic states is the perturbative spin-orbit interaction among the 3d electrons. The model Hamiltonian we develop is a variant of the Anderson impurity model and achieves efficiency through a physically motivated basis set reduction based on the large value of the d-d Coulomb interaction U_{d} and a Lanczos matrix diagonalization routine to solve for eigenvalues. The model parameters are constrained by fits to the partial density of states (PDOS) obtained from ab initio density functional theory calculations. For a particular application of our model we focus on electron-transfer occuring between cobalt ions solvated by ammonium, incorporating configuration interaction between multiplet states for both metal ions. We demonstrate the capability of the method to efficiently calculate adiabatic potential energy surfaces and the electronic coupling factor we have calculated compares well to previous calculations and experiment.
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"abstract": "We present a model intended for rapid sampling of ground and excited state\npotential energy surfaces for first-row transition metal active sites. The\nmethod is computationally inexpensive and is suited for dynamics simulations\nwhere (1) adiabatic states are required \"on-the-fly\" and (2) the primary source\nof the electronic coupling between the diabatic states is the perturbative\nspin-orbit interaction among the 3d electrons. The model Hamiltonian we develop\nis a variant of the Anderson impurity model and achieves efficiency through a\nphysically motivated basis set reduction based on the large value of the d-d\nCoulomb interaction U_{d} and a Lanczos matrix diagonalization routine to solve\nfor eigenvalues. The model parameters are constrained by fits to the partial\ndensity of states (PDOS) obtained from ab initio density functional theory\ncalculations. For a particular application of our model we focus on\nelectron-transfer occuring between cobalt ions solvated by ammonium,\nincorporating configuration interaction between multiplet states for both metal\nions. We demonstrate the capability of the method to efficiently calculate\nadiabatic potential energy surfaces and the electronic coupling factor we have\ncalculated compares well to previous calculations and experiment.",
"arxiv_id": "physics/0406043",
"authors": [
"M. X. LaBute",
"R. G. Endres",
"D. L. Cox"
],
"categories": [
"physics.chem-ph",
"physics.bio-ph"
],
"doi": "10.1063/1.1795152",
"title": "An Anderson Impurity Model for Efficient Sampling of Adiabatic Potential Energy Surfaces of Transition Metal Complexes",
"url": "https://arxiv.org/abs/physics/0406043"
},
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