Pressure: Difference between revisions

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*[http://dx.doi.org/10.1063/1.4948711  Ronald E. Miller, Ellad B. Tadmor, Joshua S. Gibson, Noam Bernstein and Fabio Pavia "Molecular dynamics at constant Cauchy stress", Journal of Chemical Physics '''144''' 184107 (2016)]
*[http://dx.doi.org/10.1063/1.4948711  Ronald E. Miller, Ellad B. Tadmor, Joshua S. Gibson, Noam Bernstein and Fabio Pavia "Molecular dynamics at constant Cauchy stress", Journal of Chemical Physics '''144''' 184107 (2016)]
*[http://dx.doi.org/10.1063/1.4984834 E. R. Smith, D. M. Heyes, and D. Dini "Towards the Irving-Kirkwood limit of the mechanical stress tensor", Journal of Chemical Physics '''146''' 224109 (2017)]
*[http://dx.doi.org/10.1063/1.4984834 E. R. Smith, D. M. Heyes, and D. Dini "Towards the Irving-Kirkwood limit of the mechanical stress tensor", Journal of Chemical Physics '''146''' 224109 (2017)]
 
*[https://doi.org/10.1063/1.5019424 Matthias Krüger, Alexandre Solon, Vincent Démery, Christian M. Rohwer, and David S. Dean "Stresses in non-equilibrium fluids: Exact formulation and coarse-grained theory", Journal of Chemical Physics '''148''' 084503 (2018)]





Latest revision as of 12:22, 2 March 2018

Pressure () is the force per unit area applied on a surface, in a direction perpendicular to that surface, i.e. the scalar part of the stress tensor under equilibrium/hydrostatic conditions.

Thermodynamics[edit]

In thermodynamics the pressure is given by

where is the Helmholtz energy function, is the volume, is the Boltzmann constant, is the temperature and is the canonical ensemble partition function.

Units[edit]

The SI units for pressure are Pascals (Pa), 1 Pa being 1 N/m2, or 1 J/m3. Other frequently encountered units are bars and millibars (mbar); 1 mbar = 100 Pa = 1 hPa, 1 hectopascal. 1 bar is 105 Pa by definition. This is very close to the standard atmosphere (atm), approximately equal to typical air pressure at earth mean sea level: atm, standard atmosphere = 101325 Pa = 101.325 kPa = 1013.25 hPa = 1.01325 bar

Stress[edit]

The stress is given by

where is the force, is the area, and is the stress tensor, given by

where where , , and are normal stresses, and , , , , , and are shear stresess.

Virial pressure[edit]

The virial pressure is commonly used to obtain the pressure from a general simulation. It is particularly well suited to molecular dynamics, since forces are evaluated and readily available. For pair interactions, one has (Eq. 2 in [1]):

where is the pressure, is the temperature, is the volume and is the Boltzmann constant. In this equation one can recognize an ideal gas contribution, and a second term due to the virial. The overline is an average, which would be a time average in molecular dynamics, or an ensemble average in Monte Carlo; is the dimension of the system (3 in the "real" world). is the force on particle exerted by particle , and is the vector going from to : .

This relationship is readily obtained by writing the partition function in "reduced coordinates", i.e. , etc, then considering a "blow-up" of the system by changing the value of . This would apply to a simple cubic system, but the same ideas can also be applied to obtain expressions for the stress tensor and the surface tension, and are also used in constant-pressure Monte Carlo.

If the interaction is central, the force is given by

where the force corresponding to the intermolecular potential :

For example, for the Lennard-Jones potential, . Hence, the expression reduces to

Notice that most realistic potentials are attractive at long ranges; hence the first correction to the ideal pressure will be a negative contribution: the second virial coefficient. On the other hand, contributions from purely repulsive potentials, such as hard spheres, are always positive.

Pressure equation[edit]

For particles acting through two-body central forces alone one may use the thermodynamic relation

Using this relation, along with the Helmholtz energy function and the canonical partition function, one arrives at the so-called pressure equation (also known as the virial equation):

where , is a central potential and is the pair distribution function.

See also[edit]

References[edit]

Related reading