Predicting Melt Curves of Energetic Materials Using Molecular Models.

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F67985858%3A_____%2F22%3A00557891" target="_blank" >RIV/67985858:_____/22:00557891 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/44555601:13440/22:43897240

Výsledek na webu

<a href="http://hdl.handle.net/11104/0331771" target="_blank" >http://hdl.handle.net/11104/0331771</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/prep.202100363" target="_blank" >10.1002/prep.202100363</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Predicting Melt Curves of Energetic Materials Using Molecular Models.

Popis výsledku v původním jazyce

In this work, the solid-liquid coexistence curves of classical fully flexible atomistic models of alpha-RDX and beta-HMX were calculated using thermodynamically rigorous methodologies that identify where the free energy difference between the phases is zero. The free energy difference between each phase at a given state point was computed using the pseudosupercritical path (PSCP) method, and Gibbs-Helmholtz integration was used to evaluate the solid-liquid free energy difference as a function of temperature. This procedure was repeated for several pressures to determine points along the coexistence curve, which were then fit to the Simon-Glatzel functional form. While effective, this method is computationally expensive. An alternative approach is to compute the melting point at a single pressure via the PSCP method, and then use the Gibbs-Duhem integration technique to trace out the coexistence curve in a more computationally economical manner. Both approaches were used to determine the coexistence curve of alpha-RDX. The Gibbs-Duhem integration method was shown to generate a melt curve that is in good agreement with the PSCP-derived melt curve, while only costing similar to 10 % of the computational resources used for the PSCP method. For alpha-RDX, the predicted melting temperature increases significantly more for a given increase in pressure when compared to available experimental data.

Název v anglickém jazyce

Predicting Melt Curves of Energetic Materials Using Molecular Models.

Popis výsledku anglicky

In this work, the solid-liquid coexistence curves of classical fully flexible atomistic models of alpha-RDX and beta-HMX were calculated using thermodynamically rigorous methodologies that identify where the free energy difference between the phases is zero. The free energy difference between each phase at a given state point was computed using the pseudosupercritical path (PSCP) method, and Gibbs-Helmholtz integration was used to evaluate the solid-liquid free energy difference as a function of temperature. This procedure was repeated for several pressures to determine points along the coexistence curve, which were then fit to the Simon-Glatzel functional form. While effective, this method is computationally expensive. An alternative approach is to compute the melting point at a single pressure via the PSCP method, and then use the Gibbs-Duhem integration technique to trace out the coexistence curve in a more computationally economical manner. Both approaches were used to determine the coexistence curve of alpha-RDX. The Gibbs-Duhem integration method was shown to generate a melt curve that is in good agreement with the PSCP-derived melt curve, while only costing similar to 10 % of the computational resources used for the PSCP method. For alpha-RDX, the predicted melting temperature increases significantly more for a given increase in pressure when compared to available experimental data.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

Propellants Explosives Pyrotechnics

ISSN

0721-3115

e-ISSN

1521-4087

Svazek periodika

47

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

12

Strana od-do

e202100363

Kód UT WoS článku

000777665900001

EID výsledku v databázi Scopus

2-s2.0-85127608078