Electronic structure and optical properties of quantum crystals from first principles calculations in the Born–Oppenheimer approximation
Abstract
In this work, we develop a formalism to accurately account for the renormalization of the electronic structure due to quantum and thermal nuclear motions within the Born–Oppenheimer approximation. We focus on the fundamental energy gap obtained from electronic addition and removal energies from quantum Monte Carlo calculations in either the canonical or grand-canonical ensembles. The formalism applies as well to effective single electron theories such as those based on density functional theory. We show that the electronic (Bloch) crystal momentum can be restored by marginalizing the total electron–ion wave function with respect to the nuclear equilibrium distribution, and we describe an explicit procedure to establish the band structure of electronic excitations for quantum crystals within the Born–Oppenheimer approximation. Based on the Kubo–Greenwood equation, we discuss the effects of nuclear motion on optical conductivity. Our methodology applies to the low temperature regime where nuclear motion is quantized and, in general, differs from the semi-classical approximation. We apply our method to study the electronic structure of C2/c-24 crystalline hydrogen at 200 K and 250 GPa and discuss the optical absorption profile of hydrogen crystals at 200 K and carbon diamond at 297 K.
- Authors:
-
[4]
- Univ. Paris-Saclay, Gif-sur-Yvette (France). Centre National de la Recherche Scientifique (CNRS). Commissariat a l'Energie Atomique (CEA). Maison de la Simulation
- Univ. of Illinois at Urbana-Champaign, IL (United States). Dept. of Physics
- Univ. of Grenoble Alpes, Grenoble (France). Institut Laue Langevin. Centre National de la Recherche Scientifique (CNRS). LPMMC
- Univ. Paris-Saclay, Gif-sur-Yvette (France). Centre National de la Recherche Scientifique (CNRS). Commissariat a l'Energie Atomique (CEA). Maison de la Simulation; Univ. of L’Aquila, L’Aquila (Italy). Dept. of Physical and Chemical Sciences
- Publication Date:
- Research Org.:
- Univ. of Illinois at Urbana-Champaign, IL (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); European Union Horizon 2020
- OSTI Identifier:
- 1850286
- Grant/Contract Number:
- NA0001789; 676531
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 153; Journal Issue: 23; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 60 APPLIED LIFE SCIENCES; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Chemistry; physics; Monte Carlo methods; electronic structure; statistical thermodynamics; optical absorption; band gap; density functional theory; Born-Oppenheimer approximation
Citation Formats
Gorelov, Vitaly, Ceperley, David M., Holzmann, Markus, and Pierleoni, Carlo. Electronic structure and optical properties of quantum crystals from first principles calculations in the Born–Oppenheimer approximation. United States: N. p., 2020.
Web. doi:10.1063/5.0031843.
Gorelov, Vitaly, Ceperley, David M., Holzmann, Markus, & Pierleoni, Carlo. Electronic structure and optical properties of quantum crystals from first principles calculations in the Born–Oppenheimer approximation. United States. https://doi.org/10.1063/5.0031843
Gorelov, Vitaly, Ceperley, David M., Holzmann, Markus, and Pierleoni, Carlo. Mon .
"Electronic structure and optical properties of quantum crystals from first principles calculations in the Born–Oppenheimer approximation". United States. https://doi.org/10.1063/5.0031843. https://www.osti.gov/servlets/purl/1850286.
@article{osti_1850286,
title = {Electronic structure and optical properties of quantum crystals from first principles calculations in the Born–Oppenheimer approximation},
author = {Gorelov, Vitaly and Ceperley, David M. and Holzmann, Markus and Pierleoni, Carlo},
abstractNote = {In this work, we develop a formalism to accurately account for the renormalization of the electronic structure due to quantum and thermal nuclear motions within the Born–Oppenheimer approximation. We focus on the fundamental energy gap obtained from electronic addition and removal energies from quantum Monte Carlo calculations in either the canonical or grand-canonical ensembles. The formalism applies as well to effective single electron theories such as those based on density functional theory. We show that the electronic (Bloch) crystal momentum can be restored by marginalizing the total electron–ion wave function with respect to the nuclear equilibrium distribution, and we describe an explicit procedure to establish the band structure of electronic excitations for quantum crystals within the Born–Oppenheimer approximation. Based on the Kubo–Greenwood equation, we discuss the effects of nuclear motion on optical conductivity. Our methodology applies to the low temperature regime where nuclear motion is quantized and, in general, differs from the semi-classical approximation. We apply our method to study the electronic structure of C2/c-24 crystalline hydrogen at 200 K and 250 GPa and discuss the optical absorption profile of hydrogen crystals at 200 K and carbon diamond at 297 K.},
doi = {10.1063/5.0031843},
journal = {Journal of Chemical Physics},
number = 23,
volume = 153,
place = {United States},
year = {Mon Dec 21 00:00:00 EST 2020},
month = {Mon Dec 21 00:00:00 EST 2020}
}
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