Ab initio thermodynamic properties and their uncertainties for crystalline alpha-methanol

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F17%3A43914314" target="_blank" >RIV/60461373:22340/17:43914314 - isvavai.cz</a>

Výsledek na webu

<a href="http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP06605H#!divAbstract" target="_blank" >http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP06605H#!divAbstract</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c7cp06605h" target="_blank" >10.1039/c7cp06605h</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Ab initio thermodynamic properties and their uncertainties for crystalline alpha-methanol

Popis výsledku v původním jazyce

To investigate the performance of quasi-harmonic electronic structure methods for modeling molecular crystals at finite temperatures and pressures, thermodynamic properties are calculated for the low-temperature alpha polymorph of crystalline methanol. Both density functional theory (DFT) and ab initio wavefunction techniques up to coupled cluster theory with singles, doubles, and perturbative triples (CCSD(T)) are combined with the quasi-harmonic approximation to predict energies, structures, and properties. The accuracy, reliability, and uncertainties of the individual quantum-chemical methods are assessed via detailed comparison of calculated and experimental data on structural properties (density) and thermodynamic properties (isobaric heat capacity). Performance of individual methods is also studied in context of the hierarchy of the quantum-chemical methods. The results indicate that while some properties such as the sublimation enthalpy and thermal expansivity can be modeled fairly well, other properties such as the molar volume and isobaric heat capacities are harder to predict reliably. The errors among the energies, structures, and phonons are closely coupled, and most accurate predictions here appear to arise from fortuitous error compensation among the different contributions. This study highlights how sensitive molecular crystal property predictions can be to the underlying model approximations and the significant challenges inherent in first-principles predictions of solid state structures and thermochemistry.

Název v anglickém jazyce

Ab initio thermodynamic properties and their uncertainties for crystalline alpha-methanol

Popis výsledku anglicky

To investigate the performance of quasi-harmonic electronic structure methods for modeling molecular crystals at finite temperatures and pressures, thermodynamic properties are calculated for the low-temperature alpha polymorph of crystalline methanol. Both density functional theory (DFT) and ab initio wavefunction techniques up to coupled cluster theory with singles, doubles, and perturbative triples (CCSD(T)) are combined with the quasi-harmonic approximation to predict energies, structures, and properties. The accuracy, reliability, and uncertainties of the individual quantum-chemical methods are assessed via detailed comparison of calculated and experimental data on structural properties (density) and thermodynamic properties (isobaric heat capacity). Performance of individual methods is also studied in context of the hierarchy of the quantum-chemical methods. The results indicate that while some properties such as the sublimation enthalpy and thermal expansivity can be modeled fairly well, other properties such as the molar volume and isobaric heat capacities are harder to predict reliably. The errors among the energies, structures, and phonons are closely coupled, and most accurate predictions here appear to arise from fortuitous error compensation among the different contributions. This study highlights how sensitive molecular crystal property predictions can be to the underlying model approximations and the significant challenges inherent in first-principles predictions of solid state structures and thermochemistry.

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

2017

Kód důvěrnosti údajů

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

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Svazek periodika

19

Číslo periodika v rámci svazku

44

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

29940-29953

Kód UT WoS článku

000415576800025

EID výsledku v databázi Scopus

2-s2.0-85034580190