Dynamic Disorder, Strain, and Sublimation of Crystalline Caged Hydrocarbons from First Principles
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F23%3A43926520" target="_blank" >RIV/60461373:22340/23:43926520 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.cgd.2c01496" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.cgd.2c01496</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.cgd.2c01496" target="_blank" >10.1021/acs.cgd.2c01496</a>
Alternative languages
Result language
angličtina
Original language name
Dynamic Disorder, Strain, and Sublimation of Crystalline Caged Hydrocarbons from First Principles
Original language description
Caged hydrocarbons exhibit diverse molecular and material properties thanks to a large variability of the threedimensional carbon backbone of such molecules. The high molecular symmetry of caged hydrocarbons predetermines these materials to pack very efficiently in crystal lattices that belong to highly symmetric space groups, as well as to easily form plastic solid phases with highly pronounced dynamic disorder in the vicinity of the melting temperature. This work aims at resolving the literature debate about the two contradictory values of experimental sublimation enthalpy for cubane, being a typical state of the art for such uncommon molecules. For this purpose, we use density functional theory (DFT)-powered quasi-harmonic protocol, further fortified with the ab initio fragment-based calculation of the cohesive energy of crystalline cubane at MP2C-F12 and CCSD(T) levels. Further, this work presents a viable first-principles treatment of dynamic disorder of molecules via their hindered rotations in the crystal lattice. A protocol for assessment of the energetic and entropic aspects of this local disorder, as well as the related anharmonic contributions to the thermodynamic properties arising from these dynamic degrees of freedom is presented and validated. Finally, the question of whether the molecular steric strain is compensated by stronger crystal cohesion is addressed.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GM23-05476M" target="_blank" >GM23-05476M: Making ab initio modelling possible for disordered molecular semi-conductive materials</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Crystal Growth & Design
ISSN
1528-7483
e-ISSN
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Volume of the periodical
23
Issue of the periodical within the volume
6
Country of publishing house
US - UNITED STATES
Number of pages
16
Pages from-to
4082-4097
UT code for WoS article
000985575600001
EID of the result in the Scopus database
2-s2.0-85159614131