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Title: Thermal expansion in dispersion-bound molecular crystals

Journal Article · · Physical Review Materials
 [1];  [2];  [3];  [4]
  1. Princeton Univ., Princeton, NJ (United States). Dept. of Chemistry; Princeton University
  2. Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology
  3. Princeton Univ., Princeton, NJ (United States). Dept. of Chemistry
  4. 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., Princeton, NJ (United States); Cornell Univ., Ithaca, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF) (United States)
Grant/Contract Number:
SC0008626; SC0005180; AC02-05CH11231; AC02-06CH11357
OSTI ID:
1437639
Journal Information:
Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 5 Vol. 2; ISSN 2475-9953
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
74 ATOMIC AND MOLECULAR PHYSICS
Van der Waals interaction
crystal structure
density functional theory
structural properties
thermal expansion
thermal properties