Most of today's molecular-dynamics simulations of materials are based on the Born-Oppenheimer approximation. There are many cases, however, in which the coupling of the electrons and nuclei is important and it is necessary to go beyond the Born-Oppenheimer approximation. In these methods, the non-adiabatic coupling vectors are fundamental since they represent the link between the classical atomic motion of the nuclei and the time evolution of the quantum electronic state. In this paper we analyze the calculation of non-adiabatic coupling vectors in a basis set of local orbitals and derive an expression to calculate them in a practical and computationally efficient way. Some examples of the application of this expression using a local-orbital density functional theory approach are presented for a few simple molecules: H3, formaldimine, and azobenzene. These results show that the approach presented here, using the Slater transition-state density, is a very promising way for the practical calculation of non-adiabatic coupling vectors for large systems.
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21 April 2013
Research Article|
April 18 2013
Calculation of non-adiabatic coupling vectors in a local-orbital basis set
Enrique Abad;
Enrique Abad
1Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC),
Universidad Autónoma de Madrid
, ES-28049 Madrid, Spain
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James P. Lewis;
James P. Lewis
2Department of Physics,
West Virginia University
, Morgantown, West Virginia 26506-6315, USA
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Vladmír Zobač;
Vladmír Zobač
3Institute of Physics,
Academy of Sciences of the Czech Republic
, Cukrovarnická 10, CZ-16200 Prague, Czech Republic
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Prokop Hapala;
Prokop Hapala
3Institute of Physics,
Academy of Sciences of the Czech Republic
, Cukrovarnická 10, CZ-16200 Prague, Czech Republic
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Pavel Jelínek;
Pavel Jelínek
3Institute of Physics,
Academy of Sciences of the Czech Republic
, Cukrovarnická 10, CZ-16200 Prague, Czech Republic
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José Ortega
José Ortega
a)
1Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC),
Universidad Autónoma de Madrid
, ES-28049 Madrid, Spain
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a)
Electronic mail: [email protected]
J. Chem. Phys. 138, 154106 (2013)
Article history
Received:
January 12 2013
Accepted:
March 26 2013
Citation
Enrique Abad, James P. Lewis, Vladmír Zobač, Prokop Hapala, Pavel Jelínek, José Ortega; Calculation of non-adiabatic coupling vectors in a local-orbital basis set. J. Chem. Phys. 21 April 2013; 138 (15): 154106. https://doi.org/10.1063/1.4801511
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