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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

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)

Publication year

2017

Confidentiality

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

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Volume of the periodical

19

Issue of the periodical within the volume

44

Country of publishing house

GB - UNITED KINGDOM

Number of pages

14

Pages from-to

29940-29953

UT code for WoS article

000415576800025

EID of the result in the Scopus database

2-s2.0-85034580190