Introducing the Coupled-Cluster Theory to the Amorphous World of Liquids and Their Thermodynamic Simulations

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F25%3A43932849" target="_blank" >RIV/60461373:22340/25:43932849 - isvavai.cz</a>

Result on the web

<a href="https://pubs.acs.org/doi/10.1021/acs.jctc.5c01214" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jctc.5c01214</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.5c01214" target="_blank" >10.1021/acs.jctc.5c01214</a>

Result language

angličtina

Original language name

Introducing the Coupled-Cluster Theory to the Amorphous World of Liquids and Their Thermodynamic Simulations

Original language description

Amorphous molecular materials are ubiquitous, spanning drugs, semiconductors, or solvents. Large predictive capabilities of quantum-chemical simulations of structural and thermodynamic properties and phase transitions for such amorphous materials have remained out of reach for a long time due to the related immense computational costs. This work introduces a novel fragment-based ab initio Monte Carlo (FrAMonC) simulation technique to the amorphous realm of molecular liquids and glasses. It aims at enabling thermodynamic simulations for amorphous molecular materials based on direct ab initio sampling and at minimizing the amount of a priori required empirical inputs for such simulations. Focus on individual cohesive interactions within the bulk, and their sampling from multiple first-principles potentials with a many-body expansion scheme enables the use of very accurate electron-structure methods for the most important cohesive features within the material. Even the coupled-cluster theory, the direct use of which is unprecedented for molecular simulations of thermodynamic properties for liquids, then becomes applicable to the description of bulk amorphous materials. Its incorporation in the proposed Monte Carlo simulations promises very high computational accuracy. Bulk-phase equilibrium properties at finite temperatures and pressures, such as density and vaporization enthalpy, as well as response properties such as thermal expansivity and heat capacity that are particularly challenging to predict accurately, are the observables targeted in this work. Superior computational accuracy of the introduced FrAMonC simulations is demonstrated for most target properties (liquid-phase densities, thermal expansivities, and gas-liquid differences in the heat capacities) when compared with established classical or quantum-chemical models that are commonly used to model such properties of bulk liquids.

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

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

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)

Publication year

2025

Confidentiality

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

Name of the periodical

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

1549-9626

Volume of the periodical

21

Issue of the periodical within the volume

19

Country of publishing house

US - UNITED STATES

Number of pages

11

Pages from-to

9868-9878

UT code for WoS article

001574324800001

EID of the result in the Scopus database

2-s2.0-105018683030