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In statistical mechanics, the '''cluster expansion''' (also called the '''high temperature expansion''' or '''hopping expansion''') is a power series expansion of the [[Partition function (statistical mechanics)|partition function]] of a statistical field theory around a model that is a union of non-interacting 0-dimensional field theories. Cluster expansions originated in the work of {{harvtxt|Mayer|Montroll|1941}}. Unlike the usual perturbation expansion, it converges in some non-trivial regions, in particular when the interaction is small.
 
==Classical case==
===General theory===
In statistical mechanics, the properties of a system of noninteracting particles are described using the
partition function. For N noninteracting particles, the system is described by the Hamiltonian
:<math> \big. H_0=\sum_i^N \frac{p_i^2}{2m}</math>,
and the partition function can be calculated (for the classical case) as
:<math>\big. Z_0 =\frac{1}{N!h^{3N}}\int \prod_i d\vec{p}_i\;d\vec{r}_i \exp\left\{ -\beta H_0(\{r_i,p_i\})\right\}
=\frac{V^N}{N!h^{3N}}\left(  \frac{2\pi m}{\beta} \right)^{\frac{3N}{2}}.
</math>
From the partition function, one can calculate the [[Helmholtz free energy]] <math>\big. F_0=-k_BT\ln Z_0 </math> and, from  that, all the thermodynamic properties of the system, like the [[entropy]], the internal energy, the [[chemical potential]] etc.
 
When the particles of the system interact, an exact calculation of the partition function is usually not possible. For low density, the interactions can be approximated with
a sum of two-particle potentials:
:<math>\big.
U\left( \{r_i\} \right) = \sum_{i=1, i<j}^N u_2(|\vec{r}_i-\vec{r}_j|) =
\sum_{i=1, i<j}^N u_2(r_{ij}).
</math>
For this interaction potential, the partition function can be written as
 
:<math>\big. Z =Z_0 \ Q</math> ,
and the free energy is
:<math>F=F_0 - k_BT\!\ln\left( Q \right)</math> ,
where Q is the [[configuration integral]]:
:<math> Q=\frac{1}{V^N}\int \prod_i d\vec{r}_i\exp\left\{
-\beta  \sum_{i=1, i<j}^N u_2(r_{ij})
\right\}.</math>
 
===Calculation of the configuration integral===
The configuration integral <math>Q</math> cannot  be calculated analytically for a general pair potential
<math>u_2(r)</math>. One way to calculate the potential approximately is to use the Mayer cluster expansion. This expansion is based on the observation that the exponential in the equation for <math>Q</math> can be written as a product of the form
:<math>
\exp\left\{
-\beta  \sum_{i=1, i<j}^N u_2(r_{ij})
\right\}=\prod_{i=1, i<j}^N\exp\left\{ -\beta u_2(r_{ij}) \right\}
</math>.
Next, define the [[Mayer function]] <math>f_{ij}</math> by <math>\exp\left\{ -\beta u_2(r_{ij}) \right\}=1+f_{ij}</math>. After substitution, the equation for the configuration integral becomes:
 
:<math>\big.  
Q=\frac{1}{V^N}\int \prod_i d\vec{r}_i
\prod_{i=1, i<j}^N \left(1+f_{ij}\right)
</math>
The calculation of the product in the above equation leads into a series of terms; the first is equal to one, the second term is equal to the sum over i and j of the terms <math>f_{ij}</math>, and the process continues until all the higher order terms are calculated.  
 
:<math>  
\prod_{i=1, i<j}^N \left(1+f_{ij}\right)=
1+ \sum_{i=1, i<j}^N\; f_{ij} + \sum_{i=1,i<j, \atop k=1,k<l}^N \;f_{ij}\;f_{kl}+\cdots
</math>
 
With this expansion it is possible to find terms of different order, in terms of the number of particles that are involved. The first term is the single-particle term, the second term corresponds to the two-particle interactions, the third to the three-particle interactions, and so on. This physical interpretation is the reason this expansion is called the cluster expansion: each term represents the interactions within clusters of a certain number of particles.
 
Substituting the expansion of the product back into the expression for the configuration integral results in a series expansion for <math>Q</math>:
 
:<math>\big.
Q=1+\frac{N}{V}\alpha_1 + \frac{N\;(N-1)}{2\;V^2}\alpha_2+\cdots.
</math>
Substituting in the equation for the free energy, it is possible to derive
the [[equation of state]] for the system of interacting particles. The equation will have the form
:<math>
PV=Nk_BT\left( 1 + \frac{N}{V}B_2(T) + \frac{N^2}{V^2}B_3(T) + \frac{N^3}{V^3}B_4(T)+ \cdots \right)
</math>,
which is known as the [[Virial equation]], and the components <math>B_i(T)</math> are the [[Virial coefficients]].
Each of the virial coefficients corresponds to one term from the cluster expansion (<math>B_2(T)</math> is the two-particle interaction term, <math>B_3(T)</math> is the three-particle interaction term and so on).
Keeping only the two-particle interaction term, it can be shown that the cluster expansion, with some approximations, gives the [[Van der Waals equation]].
 
This can be applied further to mixtures of gases and liquid solutions.
 
==References==
*{{Citation | author1-link=James Glimm | author2-link=Arthur Jaffe | last1=Glimm | first1=James | last2=Jaffe | first2=Arthur | title=Quantum physics | publisher=[[Springer-Verlag]] | location=Berlin, New York | edition=2nd | isbn=978-0-387-96476-8 | mr=887102 | year=1987}}
*{{Citation | last1=Itzykson | first1=Claude | last2=Drouffe | first2=Jean-Michel | title=Statistical field theory. Vol. 1 | publisher=[[Cambridge University Press]] | series=Cambridge Monographs on Mathematical Physics | isbn=978-0-521-34058-8 | mr=1175176 | year=1989}}
*{{Citation | last1=Itzykson | first1=Claude | last2=Drouffe | first2=Jean-Michel | title=Statistical field theory. Vol. 2 | publisher=[[Cambridge University Press]] | series=Cambridge Monographs on Mathematical Physics | isbn=978-0-521-37012-7 | mr=1175177 | year=1989}}
*{{citation |first1=Joseph E. |last1=Mayer |author1-link=Joseph Edward Mayer |first2=Elliott |last2=Montroll |author2-link=Elliott Montroll|title=Molecular distributions |journal=[[J. Chem. Phys.]] |volume=9 |year=1941 |pages=2–16 |doi=10.1063/1.1750822 }}
* {{Citation | first1=R. K. |last1=Pathria |authorlink = Raj Pathria |title= Statistical Mechanics |edition=Second |publisher=Butterworth-Heinemann |isbn=978-0-7506-2469-5 |year=1996}}, chapter 9.
* {{Citation |author1-link=Lev Landau |first1=Lev Davidovich |last1=Landau | title=Statistical Mechanics |edition=Third |
series=[[Course of Theoretical Physics]] |volume=5 |publisher=[[Butterworth-Heinemann]] |year=1984 |isbn=978-0-7506-3372-7}}
* {{citation |last1=Hansen |first1=J.-P. |last2=McDonald |first2=I.R. |title=Theory of Simple Liquids |year=2005 |edition=3d |publisher=[[Elsevier]] |isbn=978-0-12-370535-8}}
 
[[Category:Statistical mechanics]]

Latest revision as of 16:16, 1 June 2013

In statistical mechanics, the cluster expansion (also called the high temperature expansion or hopping expansion) is a power series expansion of the partition function of a statistical field theory around a model that is a union of non-interacting 0-dimensional field theories. Cluster expansions originated in the work of Template:Harvtxt. Unlike the usual perturbation expansion, it converges in some non-trivial regions, in particular when the interaction is small.

Classical case

General theory

In statistical mechanics, the properties of a system of noninteracting particles are described using the partition function. For N noninteracting particles, the system is described by the Hamiltonian

H0=iNpi22m,

and the partition function can be calculated (for the classical case) as

Z0=1N!h3Nidpidriexp{βH0({ri,pi})}=VNN!h3N(2πmβ)3N2.

From the partition function, one can calculate the Helmholtz free energy F0=kBTlnZ0 and, from that, all the thermodynamic properties of the system, like the entropy, the internal energy, the chemical potential etc.

When the particles of the system interact, an exact calculation of the partition function is usually not possible. For low density, the interactions can be approximated with a sum of two-particle potentials:

U({ri})=i=1,i<jNu2(|rirj|)=i=1,i<jNu2(rij).

For this interaction potential, the partition function can be written as

Z=Z0Q ,

and the free energy is

F=F0kBTln(Q) ,

where Q is the configuration integral:

Q=1VNidriexp{βi=1,i<jNu2(rij)}.

Calculation of the configuration integral

The configuration integral Q cannot be calculated analytically for a general pair potential u2(r). One way to calculate the potential approximately is to use the Mayer cluster expansion. This expansion is based on the observation that the exponential in the equation for Q can be written as a product of the form

exp{βi=1,i<jNu2(rij)}=i=1,i<jNexp{βu2(rij)}.

Next, define the Mayer function fij by exp{βu2(rij)}=1+fij. After substitution, the equation for the configuration integral becomes:

Q=1VNidrii=1,i<jN(1+fij)

The calculation of the product in the above equation leads into a series of terms; the first is equal to one, the second term is equal to the sum over i and j of the terms fij, and the process continues until all the higher order terms are calculated.

i=1,i<jN(1+fij)=1+i=1,i<jNfij+i=1,i<j,k=1,k<lNfijfkl+

With this expansion it is possible to find terms of different order, in terms of the number of particles that are involved. The first term is the single-particle term, the second term corresponds to the two-particle interactions, the third to the three-particle interactions, and so on. This physical interpretation is the reason this expansion is called the cluster expansion: each term represents the interactions within clusters of a certain number of particles.

Substituting the expansion of the product back into the expression for the configuration integral results in a series expansion for Q:

Q=1+NVα1+N(N1)2V2α2+.

Substituting in the equation for the free energy, it is possible to derive the equation of state for the system of interacting particles. The equation will have the form

PV=NkBT(1+NVB2(T)+N2V2B3(T)+N3V3B4(T)+),

which is known as the Virial equation, and the components Bi(T) are the Virial coefficients. Each of the virial coefficients corresponds to one term from the cluster expansion (B2(T) is the two-particle interaction term, B3(T) is the three-particle interaction term and so on). Keeping only the two-particle interaction term, it can be shown that the cluster expansion, with some approximations, gives the Van der Waals equation.

This can be applied further to mixtures of gases and liquid solutions.

References

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    Naturally, you will have to pay a safety deposit and that is usually one month rent for annually of the settlement. That is the place your good religion deposit will likely be taken into account and will kind part or all of your security deposit. Anticipate to have a proportionate amount deducted out of your deposit if something is discovered to be damaged if you move out. It's best to you'll want to test the inventory drawn up by the owner, which can detail all objects in the property and their condition. If you happen to fail to notice any harm not already mentioned within the inventory before transferring in, you danger having to pay for it yourself.

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    Naturally, you will have to pay a safety deposit and that is usually one month rent for annually of the settlement. That is the place your good religion deposit will likely be taken into account and will kind part or all of your security deposit. Anticipate to have a proportionate amount deducted out of your deposit if something is discovered to be damaged if you move out. It's best to you'll want to test the inventory drawn up by the owner, which can detail all objects in the property and their condition. If you happen to fail to notice any harm not already mentioned within the inventory before transferring in, you danger having to pay for it yourself.

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    Once you place down the one per cent choice price to carry down a non-public property, it's important to accept its situation as it is whenever you move in – faulty air-con, choked rest room and all. Get round this by asking your agent to incorporate a ultimate inspection clause within the possibility-to-buy letter. HDB flat patrons routinely take pleasure in this security net. "There's a ultimate inspection of the property two days before the completion of all HDB transactions. If the air-con is defective, you can request the seller to repair it," says Kelvin.

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  • Many property agents need to declare for the PIC grant in Singapore. However, not all of them know find out how to do the correct process for getting this PIC scheme from the IRAS. There are a number of steps that you need to do before your software can be approved.

    Naturally, you will have to pay a safety deposit and that is usually one month rent for annually of the settlement. That is the place your good religion deposit will likely be taken into account and will kind part or all of your security deposit. Anticipate to have a proportionate amount deducted out of your deposit if something is discovered to be damaged if you move out. It's best to you'll want to test the inventory drawn up by the owner, which can detail all objects in the property and their condition. If you happen to fail to notice any harm not already mentioned within the inventory before transferring in, you danger having to pay for it yourself.

    In case you are in search of an actual estate or Singapore property agent on-line, you simply should belief your intuition. It's because you do not know which agent is nice and which agent will not be. Carry out research on several brokers by looking out the internet. As soon as if you end up positive that a selected agent is dependable and reliable, you can choose to utilize his partnerise in finding you a home in Singapore. Most of the time, a property agent is taken into account to be good if he or she locations the contact data on his website. This may mean that the agent does not mind you calling them and asking them any questions relating to new properties in singapore in Singapore. After chatting with them you too can see them in their office after taking an appointment.

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    Once you place down the one per cent choice price to carry down a non-public property, it's important to accept its situation as it is whenever you move in – faulty air-con, choked rest room and all. Get round this by asking your agent to incorporate a ultimate inspection clause within the possibility-to-buy letter. HDB flat patrons routinely take pleasure in this security net. "There's a ultimate inspection of the property two days before the completion of all HDB transactions. If the air-con is defective, you can request the seller to repair it," says Kelvin.

    15.6.1 As the agent is an intermediary, generally, as soon as the principal and third party are introduced right into a contractual relationship, the agent drops out of the image, subject to any problems with remuneration or indemnification that he could have against the principal, and extra exceptionally, against the third occasion. Generally, agents are entitled to be indemnified for all liabilities reasonably incurred within the execution of the brokers´ authority.

    To achieve the very best outcomes, you must be always updated on market situations, including past transaction information and reliable projections. You could review and examine comparable homes that are currently available in the market, especially these which have been sold or not bought up to now six months. You'll be able to see a pattern of such report by clicking here It's essential to defend yourself in opposition to unscrupulous patrons. They are often very skilled in using highly unethical and manipulative techniques to try and lure you into a lure. That you must also protect your self, your loved ones, and personal belongings as you'll be serving many strangers in your home. Sign a listing itemizing of all of the objects provided by the proprietor, together with their situation. HSR Prime Recruiter 2010
  • Many property agents need to declare for the PIC grant in Singapore. However, not all of them know find out how to do the correct process for getting this PIC scheme from the IRAS. There are a number of steps that you need to do before your software can be approved.

    Naturally, you will have to pay a safety deposit and that is usually one month rent for annually of the settlement. That is the place your good religion deposit will likely be taken into account and will kind part or all of your security deposit. Anticipate to have a proportionate amount deducted out of your deposit if something is discovered to be damaged if you move out. It's best to you'll want to test the inventory drawn up by the owner, which can detail all objects in the property and their condition. If you happen to fail to notice any harm not already mentioned within the inventory before transferring in, you danger having to pay for it yourself.

    In case you are in search of an actual estate or Singapore property agent on-line, you simply should belief your intuition. It's because you do not know which agent is nice and which agent will not be. Carry out research on several brokers by looking out the internet. As soon as if you end up positive that a selected agent is dependable and reliable, you can choose to utilize his partnerise in finding you a home in Singapore. Most of the time, a property agent is taken into account to be good if he or she locations the contact data on his website. This may mean that the agent does not mind you calling them and asking them any questions relating to new properties in singapore in Singapore. After chatting with them you too can see them in their office after taking an appointment.

    Have handed an trade examination i.e Widespread Examination for House Brokers (CEHA) or Actual Property Agency (REA) examination, or equal; Exclusive brokers are extra keen to share listing information thus making certain the widest doable coverage inside the real estate community via Multiple Listings and Networking. Accepting a severe provide is simpler since your agent is totally conscious of all advertising activity related with your property. This reduces your having to check with a number of agents for some other offers. Price control is easily achieved. Paint work in good restore-discuss with your Property Marketing consultant if main works are still to be done. Softening in residential property prices proceed, led by 2.8 per cent decline within the index for Remainder of Central Region

    Once you place down the one per cent choice price to carry down a non-public property, it's important to accept its situation as it is whenever you move in – faulty air-con, choked rest room and all. Get round this by asking your agent to incorporate a ultimate inspection clause within the possibility-to-buy letter. HDB flat patrons routinely take pleasure in this security net. "There's a ultimate inspection of the property two days before the completion of all HDB transactions. If the air-con is defective, you can request the seller to repair it," says Kelvin.

    15.6.1 As the agent is an intermediary, generally, as soon as the principal and third party are introduced right into a contractual relationship, the agent drops out of the image, subject to any problems with remuneration or indemnification that he could have against the principal, and extra exceptionally, against the third occasion. Generally, agents are entitled to be indemnified for all liabilities reasonably incurred within the execution of the brokers´ authority.

    To achieve the very best outcomes, you must be always updated on market situations, including past transaction information and reliable projections. You could review and examine comparable homes that are currently available in the market, especially these which have been sold or not bought up to now six months. You'll be able to see a pattern of such report by clicking here It's essential to defend yourself in opposition to unscrupulous patrons. They are often very skilled in using highly unethical and manipulative techniques to try and lure you into a lure. That you must also protect your self, your loved ones, and personal belongings as you'll be serving many strangers in your home. Sign a listing itemizing of all of the objects provided by the proprietor, together with their situation. HSR Prime Recruiter 2010, chapter 9.
  • Many property agents need to declare for the PIC grant in Singapore. However, not all of them know find out how to do the correct process for getting this PIC scheme from the IRAS. There are a number of steps that you need to do before your software can be approved.

    Naturally, you will have to pay a safety deposit and that is usually one month rent for annually of the settlement. That is the place your good religion deposit will likely be taken into account and will kind part or all of your security deposit. Anticipate to have a proportionate amount deducted out of your deposit if something is discovered to be damaged if you move out. It's best to you'll want to test the inventory drawn up by the owner, which can detail all objects in the property and their condition. If you happen to fail to notice any harm not already mentioned within the inventory before transferring in, you danger having to pay for it yourself.

    In case you are in search of an actual estate or Singapore property agent on-line, you simply should belief your intuition. It's because you do not know which agent is nice and which agent will not be. Carry out research on several brokers by looking out the internet. As soon as if you end up positive that a selected agent is dependable and reliable, you can choose to utilize his partnerise in finding you a home in Singapore. Most of the time, a property agent is taken into account to be good if he or she locations the contact data on his website. This may mean that the agent does not mind you calling them and asking them any questions relating to new properties in singapore in Singapore. After chatting with them you too can see them in their office after taking an appointment.

    Have handed an trade examination i.e Widespread Examination for House Brokers (CEHA) or Actual Property Agency (REA) examination, or equal; Exclusive brokers are extra keen to share listing information thus making certain the widest doable coverage inside the real estate community via Multiple Listings and Networking. Accepting a severe provide is simpler since your agent is totally conscious of all advertising activity related with your property. This reduces your having to check with a number of agents for some other offers. Price control is easily achieved. Paint work in good restore-discuss with your Property Marketing consultant if main works are still to be done. Softening in residential property prices proceed, led by 2.8 per cent decline within the index for Remainder of Central Region

    Once you place down the one per cent choice price to carry down a non-public property, it's important to accept its situation as it is whenever you move in – faulty air-con, choked rest room and all. Get round this by asking your agent to incorporate a ultimate inspection clause within the possibility-to-buy letter. HDB flat patrons routinely take pleasure in this security net. "There's a ultimate inspection of the property two days before the completion of all HDB transactions. If the air-con is defective, you can request the seller to repair it," says Kelvin.

    15.6.1 As the agent is an intermediary, generally, as soon as the principal and third party are introduced right into a contractual relationship, the agent drops out of the image, subject to any problems with remuneration or indemnification that he could have against the principal, and extra exceptionally, against the third occasion. Generally, agents are entitled to be indemnified for all liabilities reasonably incurred within the execution of the brokers´ authority.

    To achieve the very best outcomes, you must be always updated on market situations, including past transaction information and reliable projections. You could review and examine comparable homes that are currently available in the market, especially these which have been sold or not bought up to now six months. You'll be able to see a pattern of such report by clicking here It's essential to defend yourself in opposition to unscrupulous patrons. They are often very skilled in using highly unethical and manipulative techniques to try and lure you into a lure. That you must also protect your self, your loved ones, and personal belongings as you'll be serving many strangers in your home. Sign a listing itemizing of all of the objects provided by the proprietor, together with their situation. HSR Prime Recruiter 2010
  • Many property agents need to declare for the PIC grant in Singapore. However, not all of them know find out how to do the correct process for getting this PIC scheme from the IRAS. There are a number of steps that you need to do before your software can be approved.

    Naturally, you will have to pay a safety deposit and that is usually one month rent for annually of the settlement. That is the place your good religion deposit will likely be taken into account and will kind part or all of your security deposit. Anticipate to have a proportionate amount deducted out of your deposit if something is discovered to be damaged if you move out. It's best to you'll want to test the inventory drawn up by the owner, which can detail all objects in the property and their condition. If you happen to fail to notice any harm not already mentioned within the inventory before transferring in, you danger having to pay for it yourself.

    In case you are in search of an actual estate or Singapore property agent on-line, you simply should belief your intuition. It's because you do not know which agent is nice and which agent will not be. Carry out research on several brokers by looking out the internet. As soon as if you end up positive that a selected agent is dependable and reliable, you can choose to utilize his partnerise in finding you a home in Singapore. Most of the time, a property agent is taken into account to be good if he or she locations the contact data on his website. This may mean that the agent does not mind you calling them and asking them any questions relating to new properties in singapore in Singapore. After chatting with them you too can see them in their office after taking an appointment.

    Have handed an trade examination i.e Widespread Examination for House Brokers (CEHA) or Actual Property Agency (REA) examination, or equal; Exclusive brokers are extra keen to share listing information thus making certain the widest doable coverage inside the real estate community via Multiple Listings and Networking. Accepting a severe provide is simpler since your agent is totally conscious of all advertising activity related with your property. This reduces your having to check with a number of agents for some other offers. Price control is easily achieved. Paint work in good restore-discuss with your Property Marketing consultant if main works are still to be done. Softening in residential property prices proceed, led by 2.8 per cent decline within the index for Remainder of Central Region

    Once you place down the one per cent choice price to carry down a non-public property, it's important to accept its situation as it is whenever you move in – faulty air-con, choked rest room and all. Get round this by asking your agent to incorporate a ultimate inspection clause within the possibility-to-buy letter. HDB flat patrons routinely take pleasure in this security net. "There's a ultimate inspection of the property two days before the completion of all HDB transactions. If the air-con is defective, you can request the seller to repair it," says Kelvin.

    15.6.1 As the agent is an intermediary, generally, as soon as the principal and third party are introduced right into a contractual relationship, the agent drops out of the image, subject to any problems with remuneration or indemnification that he could have against the principal, and extra exceptionally, against the third occasion. Generally, agents are entitled to be indemnified for all liabilities reasonably incurred within the execution of the brokers´ authority.

    To achieve the very best outcomes, you must be always updated on market situations, including past transaction information and reliable projections. You could review and examine comparable homes that are currently available in the market, especially these which have been sold or not bought up to now six months. You'll be able to see a pattern of such report by clicking here It's essential to defend yourself in opposition to unscrupulous patrons. They are often very skilled in using highly unethical and manipulative techniques to try and lure you into a lure. That you must also protect your self, your loved ones, and personal belongings as you'll be serving many strangers in your home. Sign a listing itemizing of all of the objects provided by the proprietor, together with their situation. HSR Prime Recruiter 2010