Thermal expansion in dispersion-bound molecular crystals
Abstract
In this paper, we explore how anharmonicity, nuclear quantum effects (NQE), many-body dispersion interactions, and Pauli repulsion influence thermal properties of dispersion-bound molecular crystals. Accounting for anharmonicity with ab initio molecular dynamics yields cell parameters accurate to within 2% of experiment for a set of pyridinelike molecular crystals at finite temperatures and pressures. From the experimental thermal expansion curve, we find that pyridine-I has a Debye temperature just above its melting point, indicating sizable NQE across the entire crystalline range of stability. We find that NQE lead to a substantial volume increase in pyridine-I (≈ 40% more than classical thermal expansion at 153 K) and attribute this to intermolecular Pauli repulsion promoted by intramolecular quantum fluctuations. Finally, when predicting delicate properties such as the thermal expansivity, we show that many-body dispersion interactions and more sophisticated density functional approximations improve the accuracy of the theoretical model.
- Authors:
-
- Princeton Univ., Princeton, NJ (United States). Dept. of Chemistry
- Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology
- Princeton Univ., Princeton, NJ (United States). Dept. of Chemistry. Dept. of Physics
- Publication Date:
- Research Org.:
- Princeton Univ., NJ (United States); Cornell Univ., Ithaca, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1437639
- Alternate Identifier(s):
- OSTI ID: 1437687
- Grant/Contract Number:
- SC0008626; SC0005180; AC02-05CH11231; AC02-06CH11357; DMR-1719875
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Materials
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 5; Journal ID: ISSN 2475-9953
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 74 ATOMIC AND MOLECULAR PHYSICS; crystal structure; density functional theory; structural properties; thermal expansion; thermal properties; Van der Waals interaction
Citation Formats
Ko, Hsin -Yu, DiStasio, Robert A., Santra, Biswajit, and Car, Roberto. Thermal expansion in dispersion-bound molecular crystals. United States: N. p., 2018.
Web. doi:10.1103/PhysRevMaterials.2.055603.
Ko, Hsin -Yu, DiStasio, Robert A., Santra, Biswajit, & Car, Roberto. Thermal expansion in dispersion-bound molecular crystals. United States. https://doi.org/10.1103/PhysRevMaterials.2.055603
Ko, Hsin -Yu, DiStasio, Robert A., Santra, Biswajit, and Car, Roberto. Fri .
"Thermal expansion in dispersion-bound molecular crystals". United States. https://doi.org/10.1103/PhysRevMaterials.2.055603. https://www.osti.gov/servlets/purl/1437639.
@article{osti_1437639,
title = {Thermal expansion in dispersion-bound molecular crystals},
author = {Ko, Hsin -Yu and DiStasio, Robert A. and Santra, Biswajit and Car, Roberto},
abstractNote = {In this paper, we explore how anharmonicity, nuclear quantum effects (NQE), many-body dispersion interactions, and Pauli repulsion influence thermal properties of dispersion-bound molecular crystals. Accounting for anharmonicity with ab initio molecular dynamics yields cell parameters accurate to within 2% of experiment for a set of pyridinelike molecular crystals at finite temperatures and pressures. From the experimental thermal expansion curve, we find that pyridine-I has a Debye temperature just above its melting point, indicating sizable NQE across the entire crystalline range of stability. We find that NQE lead to a substantial volume increase in pyridine-I (≈ 40% more than classical thermal expansion at 153 K) and attribute this to intermolecular Pauli repulsion promoted by intramolecular quantum fluctuations. Finally, when predicting delicate properties such as the thermal expansivity, we show that many-body dispersion interactions and more sophisticated density functional approximations improve the accuracy of the theoretical model.},
doi = {10.1103/PhysRevMaterials.2.055603},
journal = {Physical Review Materials},
number = 5,
volume = 2,
place = {United States},
year = {2018},
month = {5}
}
Web of Science
Figures / Tables:

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Figures / Tables found in this record: