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Title: 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:
 [1];  [2];  [1];  [3]
+ Show Author Affiliations
  1. Princeton Univ., Princeton, NJ (United States). Dept. of Chemistry
  2. Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology
  3. 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) (SC-22); 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.
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Ko, Hsin -Yu, DiStasio, Robert A., Santra, Biswajit, & Car, Roberto. Thermal expansion in dispersion-bound molecular crystals. United States. doi:10.1103/PhysRevMaterials.2.055603.
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Ko, Hsin -Yu, DiStasio, Robert A., Santra, Biswajit, and Car, Roberto. Fri . "Thermal expansion in dispersion-bound molecular crystals". United States. doi:10.1103/PhysRevMaterials.2.055603. https://www.osti.gov/servlets/purl/1437639.
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@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}
}
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Journal Article:
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DOI:  10.1103/PhysRevMaterials.2.055603
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Figures / Tables:

FIG. 1 FIG. 1: Predicted cell volumes (Vpred) from VC optimizations and AIMD simulations using PBE + vdW$TS\atop{SC}$ for the PLMC set. Errors are defined with respect to experiment (Vexpt) at the indicated thermodynamic conditions as Verr = (Vpred − Vexpt)/Vexpt. Inset: Overlay of predicted (blue) and experimental (red) [40] pyridine-I structures.
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