Thermodynamics of the Stockmayer fluid in an applied field / Elfimova Ekaterina A.,Ivanov Alexey O.,Sindt Julien O.,Camp Philip J. // MOLECULAR PHYSICS. - 2015. - V. 113, l. 23. - P. 3717-3728.

ISSN/EISSN:

0026-8976 / 1362-3028

Type:

Article

Abstract:

The thermodynamic properties of the Stockmayer fluid in an applied field are studied using theory and computer simulation. Theoretical expressions for the second and third virial coefficients are obtained in terms of the dipolar coupling constant (, measuring the strength of dipolar interactions as compared to thermal energy) and dipole-field interaction energy (, being proportional to the applied field strength). These expressions are tested against numerical results obtained by Mayer sampling calculations. The expression for the second virial coefficient contains terms up to (4), and is found to be accurate over realistic ranges of dipole moment and temperature, and over the entire range of the applied field strength (from zero to infinity). The corresponding expression for the third virial coefficient is truncated at (3), and is not very accurate: higher order terms are very difficult to calculate. The virial coefficients are incorporated in to a thermodynamic theory based on a logarithmic representation of the Helmholtz free energy. This theory is designed to retain the input virial coefficients, and account for some higher order terms in the sense of a resummation. The compressibility factor is obtained from the theory and compared to results from molecular dynamics simulations with a typical value = 1. Despite the mathematical approximations of the virial coefficients, the theory captures the effects of the applied field very well. Finally, the vapour-liquid critical parameters are determined from the theory, and compared to published simulation results; the agreement between the theory and simulations is good.

Author keywords:

Stockmayer fluid; applied field; theory; simulation DIPOLAR HARD-SPHERES; EQUATION-OF-STATE; VIRIAL-COEFFICIENTS; PERTURBATION-THEORY; POLAR GASES; COMPUTER-SIMULATIONS; CRITICAL-TEMPERATURE; PHASE-BEHAVIOR; LIQUID; ORDER

DOI:

10.1080/00268976.2015.1058979

Web of Science ID:

ISI:000365645800009

Соавторы в МНС:

Другие поля

Поле	Значение
Month	DEC 2
Publisher	TAYLOR \& FRANCIS LTD
Address	4 PARK SQUARE, MILTON PARK, ABINGDON OX14 4RN, OXON, ENGLAND
Language	English
EISSN	1362-3028
Keywords-Plus	DIPOLAR HARD-SPHERES; EQUATION-OF-STATE; VIRIAL-COEFFICIENTS; PERTURBATION-THEORY; POLAR GASES; COMPUTER-SIMULATIONS; CRITICAL-TEMPERATURE; PHASE-BEHAVIOR; LIQUID; ORDER
Research-Areas	Chemistry; Physics
Web-of-Science-Categories	Chemistry, Physical; Physics, Atomic, Molecular \& Chemical
Author-Email	philip.camp@ed.ac.uk
ResearcherID-Numbers	Ivanov, Alexey/E-4442-2011 Elfimova, Ekaterina/P-5003-2016
ORCID-Numbers	Ivanov, Alexey/0000-0001-8239-4039 Elfimova, Ekaterian/0000-0002-8941-8184 Camp, Philip/0000-0002-7901-1364
Funding-Acknowledgement	Ministry of Education and Science of the Russian Federation {[}3.12.2014/K, 02.A03.21.0006]; Engineering and Physical Sciences Research Council (UK)
Funding-Text	Ekaterina A. Elfimovaand Alexey O. Ivanov gratefully acknowledge research funding from the Ministry of Education and Science of the Russian Federation {[}agreement no. 3.12.2014/K, contract no. 02.A03.21.0006]. Julien O. Sindt was supported by the Engineering and Physical Sciences Research Council (UK) through the provision of a studentship.
Number-of-Cited-References	60
Usage-Count-Last-180-days	1
Usage-Count-Since-2013	5
Journal-ISO	Mol. Phys.
Doc-Delivery-Number	CX4CM