Probing the Accuracy of First-Principles Modeling of Molecular Crystals: Calculation of Sublimation Pressures
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F19%3A43918042" target="_blank" >RIV/60461373:22340/19:43918042 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1021/acs.cgd.8b01374" target="_blank" >https://doi.org/10.1021/acs.cgd.8b01374</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.cgd.8b01374" target="_blank" >10.1021/acs.cgd.8b01374</a>
Alternative languages
Result language
angličtina
Original language name
Probing the Accuracy of First-Principles Modeling of Molecular Crystals: Calculation of Sublimation Pressures
Original language description
An insight into current possibilities of obtaining the sublimation pressures for molecular crystals from first principles is presented. Due to their extreme sensitivity to any computational uncertainties, sublimation pressures are the strictest possible representation of first-principles data on the cohesive properties of molecular crystals, emphasizing the significance of any computational uncertainties of cohesive energies, sublimation enthalpies, or sublimation entropies which might seem acceptable from a purely energetic point of view. The sublimation pressure was computed for 20 selected molecular crystals by combining the calculated static cohesive energy, vibrational contributions to thermodynamic properties in the crystalline phase, and ideal-gas thermodynamic properties required to obtain the sublimation enthalpy and entropy as a function of temperature. The calculated sublimation pressures were compared to reference experimentally based values developed in this work. By an analysis of the uncertainties on the basis of a comparison to experimental sublimation pressures and both enthalpic and entropic contributions, the uncertainty limits for prediction of sublimation pressure based on first-principles approaches are discussed and estimated. As the sublimation pressure depends exponentially on both enthalpic and entropic contributions, the current accuracy of first-principles calculations allows its prediction typically within a factor of 10. This can still be viewed as a success, given typical uncertainties in experimentally determined sublimation thermodynamic properties, especially when extremely low volatility compounds are considered. Copyright © 2018 American Chemical Society.
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/GA17-03875S" target="_blank" >GA17-03875S: Theoretical and experimental study of thermodynamic properties and phase behavior of molecular crystals</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2019
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
19
Issue of the periodical within the volume
2
Country of publishing house
US - UNITED STATES
Number of pages
13
Pages from-to
808-820
UT code for WoS article
000458348000035
EID of the result in the Scopus database
2-s2.0-85059752220