Probing the Accuracy of First-Principles Modeling of Molecular Crystals: Calculation of Sublimation Pressures

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Probing the Accuracy of First-Principles Modeling of Molecular Crystals: Calculation of Sublimation Pressures

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Probing the Accuracy of First-Principles Modeling of Molecular Crystals: Calculation of Sublimation Pressures

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA17-03875S" target="_blank" >GA17-03875S: Teoretická a experimentální studie termodynamických vlastností a fázového chování molekulárních krystalů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2019

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Crystal Growth &amp; Design

ISSN

1528-7483

e-ISSN

—

Svazek periodika

19

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

808-820

Kód UT WoS článku

000458348000035

EID výsledku v databázi Scopus

2-s2.0-85059752220