On the decay of the pair correlation function and the line of vanishing excess isothermal compressibility in simple fluids

التفاصيل البيبلوغرافية
العنوان: On the decay of the pair correlation function and the line of vanishing excess isothermal compressibility in simple fluids
المؤلفون: Stopper, Daniel, Hansen-Goos, Hendrik, Roth, Roland, Evans, Robert
سنة النشر: 2019
المجموعة: Condensed Matter
مصطلحات موضوعية: Condensed Matter - Soft Condensed Matter, Condensed Matter - Statistical Mechanics
الوصف: We re-visit the competition between attractive and repulsive interparticle forces in simple fluids and how this governs and connects the macroscopic phase behavior and structural properties as manifest in pair correlation functions. We focus on the asymptotic decay of the total correlation function $h(r)$ which is, in turn, controlled by the form of the pair direct correlation function $c(r)$. The decay of $r h(r)$ to zero can be either exponential (monotonic) if attraction dominates repulsion and exponentially damped oscillatory otherwise. The Fisher-Widom (FW) line separates the phase diagram into two regions characterized by the two different types of asymptotic decay. We show that there is a new and physically intuitive thermodynamic criterion which approximates well the actual FW line. This new criterion defines a line where the isothermal compressibility takes its ideal gas value $\chi_T=\chi_T^\text{id}$. We test our hypothesis by considering four commonly used models for simple fluids. In all cases the new criterion yields a line in the phase diagram that is close to the actual FW line for the thermodynamic state points that are most relevant. We also investigate (Widom) lines of maximal correlation length, emphasizing the importance of distinguishing between the true and Ornstein-Zernike correlation lengths
نوع الوثيقة: Working Paper
DOI: 10.1063/1.5110044
URL الوصول: http://arxiv.org/abs/1906.02948
رقم الأكسشن: edsarx.1906.02948
قاعدة البيانات: arXiv