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Title: Thermal expansion in dispersion-bound molecular crystals

Journal Article · · Physical Review Materials
 [1];  [2];  [1];  [3]
  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
+ Show Author Affiliations

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.

Research Organization:
Princeton Univ., NJ (United States); Cornell Univ., Ithaca, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0008626; SC0005180; AC02-05CH11231; AC02-06CH11357; DMR-1719875
OSTI ID:
1437639
Alternate ID(s):
OSTI ID: 1437687
Journal Information:
Physical Review Materials, Vol. 2, Issue 5; ISSN 2475-9953
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

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Cited By (7)

Time-Domain Terahertz Spectroscopy and Solid-State Density Functional Theory Analysis of p-Nitrophenol Polymorphs journal December 2019
On the importance of anharmonicities and nuclear quantum effects in modelling the structural properties and thermal expansion of MOF-5 journal March 2019
Thermal expansion in insulating solids from first principles journal November 2019
Isotope effects in liquid water via deep potential molecular dynamics journal October 2019
Elastic properties of the molecular crystals of hydrocarbons from first principles calculations journal November 2019
Isotope Effects in Liquid Water via Deep Potential Molecular Dynamics text January 2019
Thermal Expansion in Insulating Solids From First Principles text January 2019

Figures / Tables (5)

FIG. 1(p. 2)figure FIG. 1
TABLE I(p. 3)table TABLE I
FIG. 2(p. 4)figure FIG. 2
FIG. 3(p. 5)figure FIG. 3
TABLE II(p. 5)table TABLE II

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Related Subjects

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