Negative Linear Compressibility of Molecular and Ionic-molecular Crystals

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-12-23 DOI:10.1039/d4cp03913k

Dmitry Vasilevich Korabel'nikov, Igor Alexandrovich Fedorov

引用次数: 0

Abstract

The compressibility of crystalline tetrabromophthalic anhydride (TBPA) and 1-ethyl-3-methylimidazolium nitrate (EMN) was studied based on density functional theory including dispersion interactions at pressures below 1 GPa. It is found for the first time that EMN demonstrate negative linear compressibility (NLC) up to ~ 0.15 GPa, whereas TBPA shows significant NLC at pressures higher than ~ 0.2 GPa. Mechanisms of the observed negative linear compressibility of TBPA and EMN have been found at the microscopic (molecular) level for the first time. It was shown that NLC correlates with baric change of spatial orientation (rotation) and linear dimensions of molecular structural units relative to crystallographic axes, as well as with baric increase of intermolecular distances along NLC direction. Quantum topological analysis of electron density was used to study intermolecular interactions. It has been established that TBPA and EMN crystals are optically transparent for visible light at pressures up to 1 GPa.

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.