# Difference between revisions of "Virial pressure"

m |
(Punctuation correction) |
||

Line 17: | Line 17: | ||

:<math> p = \frac{ k_B T N}{V} + \frac{ 1 }{ d V } \overline{ \sum_{i<j} f(r_{ij}) r_{ij} }. </math> | :<math> p = \frac{ k_B T N}{V} + \frac{ 1 }{ d V } \overline{ \sum_{i<j} f(r_{ij}) r_{ij} }. </math> | ||

− | Notice that most [[Realistic models |realistic potentials]] are attractive at long ranges | + | Notice that most [[Realistic models |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 sphere model | hard spheres]], are always positive. |

==See also== | ==See also== | ||

*[[Test volume method]] | *[[Test volume method]] | ||

[[category: statistical mechanics]] | [[category: statistical mechanics]] |

## Revision as of 09:57, 7 October 2010

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:

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.