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¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene π orbitals.
Dimensionless Groups in Fluid Mechanics01:15

Dimensionless Groups in Fluid Mechanics

Dimensionless groups in fluid mechanics provide simplified ratios that help analyze fluid behavior without relying on specific units. The Reynolds number (Re), which represents the ratio of inertial to viscous forces, distinguishes between laminar and turbulent flows, making it essential in the design of pipelines and aerodynamic surfaces. The Froude number (Fr), the ratio of inertial to gravitational forces, is particularly useful in predicting wave formation and hydraulic jumps in...
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
The Van der Waals Equation01:26

The Van der Waals Equation

The ideal gas law is based on two simplifying assumptions: first, that there are no intermolecular attractions between gas molecules, and second, that the volume occupied by the molecules themselves is negligible compared with the volume of the container. However, these assumptions don't hold up under all conditions - specifically, at high pressures and low temperatures, as gas tends to deviate from ideal gas behavior.The van der Waals equation is an enhanced version of the ideal gas law,...
Generalized Hooke's Law01:22

Generalized Hooke's Law

The generalized Hooke's Law is a broadened version of Hooke's Law, which extends to all types of stress and in every direction. Consider an isotropic material shaped into a cube subjected to multiaxial loading. In this scenario, normal stresses are exerted along the three coordinate axes. As a result of these stresses, the cubic shape deforms into a rectangular parallelepiped. Despite this deformation, the new shape maintains equal sides, and there is a normal strain in the direction of the...
Van der Waals Equation01:10

Van der Waals Equation

The ideal gas law is an approximation that works well at high temperatures and low pressures. The van der Waals equation of state (named after the Dutch physicist Johannes van der Waals, 1837−1923) improves it by considering two factors.
First, the attractive forces between molecules, which are stronger at higher densities and reduce the pressure, are considered by adding to the pressure a term equal to the square of the molar density multiplied by a positive coefficient a. Second, the volume...

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Related Experiment Video

Updated: May 9, 2026

Mechanical Expansion of Steel Tubing as a Solution to Leaky Wellbores
09:32

Mechanical Expansion of Steel Tubing as a Solution to Leaky Wellbores

Published on: November 20, 2014

Generalized coupling parameter expansion: application to square well and Lennard-Jones fluids.

A Sai Venkata Ramana1

  • 1Theoretical Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India.

The Journal of Chemical Physics
|August 2, 2013
PubMed
Summary

This study enhances thermodynamic perturbation theory for simple fluids, accurately predicting properties like radial distribution functions and phase diagrams for Square-Well and Lennard-Jones fluids. The improved method overcomes limitations of integral equation theories, especially in coexistence regions.

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Last Updated: May 9, 2026

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Analyzing Melts and Fluids from Ab Initio Molecular Dynamics Simulations with the UMD Package

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Area of Science:

  • Thermodynamics
  • Statistical Mechanics
  • Physical Chemistry

Background:

  • Thermodynamic perturbation theory (TPT) is crucial for understanding fluid behavior.
  • Integral equation theories (IETs) have limitations, particularly in liquid-vapor coexistence regions.
  • Bridge functions play a key role in accurately describing fluid correlations.

Purpose of the Study:

  • To generalize TPT by incorporating derivatives of the bridge function with respect to the coupling parameter.
  • To apply this enhanced theory to Square-Well (SW) and Lennard-Jones (LJ) fluids.
  • To assess the accuracy and applicability of the method compared to IET and simulations.

Main Methods:

  • Generalized coupling parameter expansion in TPT, including bridge function derivatives.
  • Application of seventh-order TPT to SW and LJ fluids using the Sarkisov bridge function.
  • Comparison of results with integral equation theory and simulation data.

Main Results:

  • Accurate reproduction of radial distribution functions for SW and LJ fluids.
  • Successful prediction of liquid-vapor phase diagrams, even in regions where IETs fail.
  • Improved liquid-vapor phase diagram for SW fluids using Carnahan-Starling for the hard-sphere reference system.
  • Significant impact of bridge function derivatives on the liquid part of the phase diagram.
  • Good agreement between theoretical and simulation results for surface tension of SW fluids.
  • Consistent equation of state for LJ fluids compared to IET.

Conclusions:

  • The generalized TPT offers improved accuracy over standard IET when reference system properties are known.
  • The method provides a viable alternative for solving Ornstein-Zernkequations when reference system data is unavailable.
  • The inclusion of bridge function derivatives enhances the predictive power of TPT for fluid phase behavior.