text:
# Pressure formulas for liquid metals and plasmas based on the density-functional theory

## 1 Introduction

In liquid metals and high density plasmas, their pressure is attributed in main to the behaviour of electrons involved in the system and the nuclear contribution is not so important. Therefore, almost pressure calculations take account of only the electron behaviour in the system; furthermore, the pressure is calculated as that of the electrons around one fixed nucleus neutralised in the volume (the Wigner-Seitz sphere). This model is called in several ways such as the ion-sphere model, the spherical shell model, the Wigner-Seitz model, or the confined atom model. In the case of plasmas, the Thomas-Fermi approximation including its extention is applied for this purpose -, and in treating metals, the pressure is calculated by solving the wave equation based on the density-functional (DF) theory -. As a consequence, the nuclear contribution to the pressure is not taken into account in almost cases. However, even in a high density plasma the nuclear contribution becomes important when its temperature is increased. In the present work, we attempt to set up formulas to determine the pressure of liquid metals (plasmas) at arbitrary temperature and density by treating them as a nucleus-electron mixture using the virial and Hellmann-Feynman theorem.

There are many investigations - to set up the equation of states (EOS) from the nucleus-electron model on the basis of the virial theorem. However, we find confusion and improper treatment in some works at the present stage. A typical and important example is the virial theorem for the electron pressure $`𝐏_\mathrm{e}`$ in the presence of fixed nuclei at the coordinate $`\{𝐑_\alpha \}`$ confined in a volume $`\mathrm{\Omega }`$ , which is described as

$$3P_\mathrm{e}\mathrm{\Omega }=2T_s[n]_\mathrm{\Omega }+E_{\mathrm{es}}(\mathrm{\Omega })_\mathrm{\Omega }n(𝐫)𝐫\frac{\delta E_{\mathrm{xc}}}{\delta n(𝐫)}d𝐫.$$
(1)
Here, $`T_s[n]_\mathrm{\Omega }`$ is the kinetic energy defined in the DF theory for the system with a density distribution $`n(𝐫)`$; $`E_{\mathrm{es}}(\mathrm{\Omega })`$ and $`E_{\mathrm{xc}}[n]`$ denote the electrostatic and exchange-correlation energies, respectively. This equation should be written correctly, as will be discussed below, in the form

$`3P_\mathrm{e}\mathrm{\Omega }`$ $`=`$ $`2T_s[n]_\mathrm{\Omega }+E_{\mathrm{es}}(\mathrm{\Omega }){\displaystyle _\mathrm{\Omega }}n(𝐫)𝐫{\displaystyle \frac{\delta E_{\mathrm{xc}}}{\delta n(𝐫)}}d𝐫`$ (2)
$`{\displaystyle \underset{\alpha }{}}𝐑_\alpha 𝐅_\alpha +{\displaystyle _S}𝐫𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐒,`$
which reveals that there are no terms representing the nuclear virial $`_\alpha 𝐑_\alpha 𝐅_\alpha `$ and a surface integral of the exchange-correlation pressure tensor $`𝐏_{\mathrm{xc}}^{\mathrm{DF}}`$ in the virial theorem given by (1). The exact equation (2) involving these terms can be rewritten as

$`3P_\mathrm{e}\mathrm{\Omega }`$ $`=`$ $`2[T_s[n]_\mathrm{\Omega }+\mathrm{\Delta }T_{\mathrm{xc}}]+[E_{\mathrm{es}}(\mathrm{\Omega })+\mathrm{\Delta }U_{\mathrm{xc}}]{\displaystyle \underset{\alpha }{}}𝐑_\alpha 𝐅_\alpha `$ (3)
$`=`$ $`2T_\mathrm{\Omega }+U_\mathrm{\Omega }{\displaystyle \underset{\alpha }{}}𝐑_\alpha 𝐅_\alpha ,`$ (4)
where $`T_\mathrm{\Omega }`$ and $`U_\mathrm{\Omega }`$ represent the true kinetic and potential energies, respectively, determined by treating the electrons as a many-electron system instead of the DF method. Here, the correction terms, $`\mathrm{\Delta }T_{\mathrm{xc}}`$ and $`\mathrm{\Delta }U_{\mathrm{xc}}`$, are related to the trace of the exchange-correlation pressure tensor $`𝐏_{\mathrm{xc}}`$ as follows

$$2\mathrm{\Delta }T_{\mathrm{xc}}+\mathrm{\Delta }U_{\mathrm{xc}}=_\mathrm{\Omega }\mathrm{tr}𝐏_{\mathrm{xc}}d𝐫.$$
(5)
On the other hand, the virial theorem (1) due to the lack of the surface integral term leads to the relation

$$2\mathrm{\Delta }T_{\mathrm{xc}}+\mathrm{\Delta }U_{\mathrm{xc}}=_\mathrm{\Omega }n(𝐫)𝐫\frac{\delta E_{\mathrm{xc}}}{\delta n(𝐫)}d𝐫,$$
(6)
which becomes zero for a uniform electron density inappropriately.

The nuclear virial term in (4) causes some confusion in the calculation of EOS, since it has an inverse sign as to be considered as the nuclear pressure of the system, or it brings a difference from a naive virial theorem. Following Slater , many investigators including works of Janak , Averill and Painter  and Ziesche, Grafenstein and Nielsen  have adopted a definition of the pressure in terms of the nuclear virial

$$3P_\mathrm{e}\mathrm{\Omega }\underset{\alpha }{}𝐑_\alpha 𝐅_\alpha =2T_\mathrm{\Omega }+U_\mathrm{\Omega }.$$
(7)
The virial theorem (1) is a result of this definition of the pressure. In the present work, we have proved that the electron pressure in the presence of nuclei fixed at $`\{𝐑_\alpha \}`$ should be given by (2) instead of (7).

On the other hand, another form of pressure definition is proposed by some authors  with use of the Maxwell pressure tensor. However, this definition provides the real pressure only when some restriction is imposed, as will be discussed in the present work. In the next section, we pick up some important equations to discuss the virial theorem for a nucleus-electron mixture. Then, these equations are used to derive the electron pressure in the presence of nuclei in Sec. 3, and the thermodynamical pressure as a whole system in Sec. 6. Some comments on other pressure formulas are made in Sec. 4 and Sec. 5. The last section is devoted to summary and discussion.

## 2 Exact relations to derive pressure formulas

For the purpose of preparing to derive pressure formulas, we describe in this section some necessary and important equations which can be proved without approximation.

(1) The DF theory:
Nuclei with the atomic number $`Z`$ fixed at positions $`\{𝐑_\alpha \}`$ causes an external potential $`U_{\mathrm{ext}}(𝐫)`$ for the electrons

$$U_{\mathrm{ext}}(𝐫)\underset{\alpha =1}{\overset{N}{}}\frac{Ze^2}{|𝐫𝐑_\alpha |}=\frac{\delta E_{\mathrm{en}}}{\delta n(𝐫)}.$$
(8)
Here, $`E_{\mathrm{en}}`$ is the electron-nucleus part of the total electrostatic energy $`E_{\mathrm{es}}[n]`$ for this system with an electron density distribution $`n(𝐫)`$

$`E_{\mathrm{es}}[n]`$ $``$ $`{\displaystyle \frac{e^2}{2}}{\displaystyle \frac{n(𝐫)n(𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫𝑑𝐫^{}}{\displaystyle \underset{\alpha =1}{\overset{N}{}}}{\displaystyle \frac{Ze^2n(𝐫^{})}{|𝐫^{}𝐑_\alpha |}𝑑𝐫^{}}+{\displaystyle \frac{1}{2}}{\displaystyle \underset{\alpha \beta }{}}{\displaystyle \frac{Z^2e^2}{|𝐑_\alpha 𝐑_\beta |}}`$ (9)
$``$ $`E_{\mathrm{ee}}+E_{\mathrm{en}}+E_{\mathrm{nn}}.`$ (10)
The DF theory provides the effective external potential $`U_{\mathrm{eff}}(𝐫)`$ in terms of the intrinsic interaction part of the free-energy $`_{\mathrm{int}}_{\mathrm{xc}}+E_{\mathrm{ee}}`$

$$U_{\mathrm{eff}}(𝐫)=U_{\mathrm{ext}}(𝐫)+\frac{\delta _{\mathrm{int}}}{\delta n(𝐫)}\mu _{\mathrm{int}}=\frac{\delta E_{\mathrm{es}}}{\delta n(𝐫)}+\frac{\delta _{\mathrm{xc}}}{\delta n(𝐫)}\mu _{\mathrm{int}}.$$
(11)
This effective external potential provides a way to calculate an exact electron density distribution $`n(𝐫)`$ by solving a wave equation for the one-electron wave function $`\phi _i(𝐫)`$

$$\left[\frac{\mathrm{}^2}{2m}^2+U_{\mathrm{eff}}(𝐫)\right]\phi _i(𝐫)=ϵ_i\phi _i(𝐫),$$
(12)
in the form

$$n(𝐫)=\underset{i}{}f(ϵ_i)|\phi _i(𝐫)|^2,$$
(13)
with use of the Fermi distribution $`f(ϵ_i)`$ for arbitrary temperature.

(2) Electrostatic energy $`E_{\mathrm{es}}[n]`$:
Since the interactions among electrons and nuclei are all Coulombic, the electrostatic energy $`E_{\mathrm{es}}[n]`$, (9), is shown to satisfy the following equation

$`E_{\mathrm{es}}`$ $`=`$ $`{\displaystyle n(𝐫)𝐫\frac{\delta E_{\mathrm{es}}}{\delta n(𝐫)}d𝐫}{\displaystyle \underset{\alpha }{}}𝐑_\alpha _\alpha E_{\mathrm{es}}`$ (14)
$`=`$ $`{\displaystyle n(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫}+{\displaystyle n(𝐫)𝐫\frac{\delta _{\mathrm{xc}}}{\delta n(𝐫)}d𝐫}{\displaystyle \underset{\alpha }{}}𝐑_\alpha _\alpha E_{\mathrm{es}}.`$ (15)
In the above, (14) is derived by noting the relation

$$𝐫v(|𝐫𝐫^{}|)+𝐫^{}^{}v(|𝐫𝐫^{}|)=|𝐫𝐫^{}|v^{}(|𝐫𝐫^{}|),$$
(16)
with $`v^{}(r)v(r)/r`$, and (15) is led by the use of (11). Equations, (14) and (15), are fundamental to derive the virial theorem for a nucleus-electron mixture.

(3) The kinetic energy in the DF theory:
In the DF theory, the kinetic energy $`T_s[n]_\mathrm{\Omega }`$ of the electrons confined in an arbitrary finite volume $`\mathrm{\Omega }`$ of the system is defined by the following equation (17) in terms of the wave functions for (12), and it can be proved that this kinetic energy is associated with the external effective potential $`U_{\mathrm{eff}}`$ given by (11) and the density distribution $`n(𝐫)`$ under this external potential in the form

$`2T_s[n]_\mathrm{\Omega }`$ $``$ $`2{\displaystyle \underset{i}{}}f(ϵ_i){\displaystyle _\mathrm{\Omega }}\phi _i^{}(𝐫){\displaystyle \frac{\mathrm{}^2}{2m}}^2\phi _i(𝐫)𝑑𝐫`$ (17)
$`=`$ $`{\displaystyle _\mathrm{\Omega }}n(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫+{\displaystyle _S}𝐀𝑑𝐒.`$ (18)
Here, the tensor $`𝐀`$ involved in the surface integral for the surface $`S`$ of the volume $`\mathrm{\Omega }`$ is defined by the following equation (19), which can be represented in other ways such as (20) and (21) in terms of the kinetic tensor $`\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}`$ defined by (21) as follows

$`𝐀`$ $``$ $`{\displaystyle \underset{i}{}}f(ϵ_i){\displaystyle \frac{\mathrm{}^2}{2m}}\{\phi _i^{}[𝐫\phi _i](𝐫\phi _i)(\phi _i^{})\}`$ (19)
$`=`$ $`{\displaystyle \underset{i}{}}f(ϵ_i){\displaystyle \frac{\mathrm{}^2}{4m}}\{\phi _i^{}[𝐫\phi _i](𝐫\phi _i)(\phi _i^{})+\mathrm{c}.\mathrm{c}.\}`$ (20)
$`=`$ $`[𝐫𝐏_\mathrm{K}^{\mathrm{DF}}]{\displaystyle \frac{\mathrm{}^2}{4m}}^2n(𝐫)[𝐫\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}],`$ (21)
with

$$P_{\mathrm{K},\mu \nu }^{\mathrm{DF}}\underset{i}{}f(ϵ_i)\frac{\mathrm{}^2}{4m}[\phi _i^{}_\mu _\nu \phi _i+\phi _i_\mu _\nu \phi _i^{}(_\mu \phi _i^{})(_\nu \phi _i)(_\mu \phi _i)(_\nu \phi _i^{})].$$
(22)
It should be noticed that these relations can be applied to a subspace $`\mathrm{\Omega }`$ chosen arbitrarily in the whole space of the system. The proof of the above relations is seen in Appendix.

(4) Pressure for a noninteracting electron gas in the external potential $`U_{\mathrm{eff}}(𝐫)`$:
The pressure tensor $`𝐏_\mathrm{e}^0`$ of a noninteracting electron gas in the external potential $`U_{\mathrm{eff}}(𝐫)`$ follows the next equation

$$𝐏_\mathrm{e}^0=n(𝐫)U_{\mathrm{eff}}(𝐫),$$
(23)
which is a result of the local momentum balance. Here, note that $`n(𝐫)`$ is the density distribution of a noninteracting electron gas in the external potential $`U_{\mathrm{eff}}(𝐫)`$.

(5) Mathematical formula:
For arbitrary tensor $`𝐏`$, the following surface integral can be written in a volume integral form

$$_\mathrm{\Omega }(𝐫𝐏)𝑑𝐫=_S𝐫𝐏𝑑𝐒=_\mathrm{\Omega }\mathrm{tr}𝐏d𝐫+_\mathrm{\Omega }𝐫𝐏𝑑𝐫.$$
(24)
## 3 Electron pressure in the presence of fixed nuclei

When the nuclei fixed at positions $`\{𝐑_\alpha \}`$ generate an inhomogeneous electron gas with the density distribution $`n(𝐫)`$, the electron pressure tensor $`𝐏_\mathrm{e}`$ of this system is defined by the following equation

$$𝐏_\mathrm{e}n(𝐫)\left[\underset{\alpha =1}{\overset{N}{}}\frac{Ze^2}{|𝐫𝐑_\alpha |}+\frac{e^2n(𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫^{}\right]=n(𝐫)\frac{\delta E_{\mathrm{es}}}{\delta n(𝐫)}.$$
(25)
On the basis of this definition for $`𝐏_\mathrm{e}`$, we can prove the virial theorem for a subspace $`\mathrm{\Omega }`$ arbitrarily chosen in the system as follows

$`{\displaystyle _S}𝐫𝐏_\mathrm{e}𝑑𝐒`$ $`=`$ $`{\displaystyle _S}𝐫(\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}})𝑑𝐒`$ (26)
$`=`$ $`2T_s[n]_\mathrm{\Omega }+E_{\mathrm{es}}(\mathrm{\Omega })+{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_{\mathrm{xc}}d𝐫{\displaystyle \underset{\alpha ϵ\mathrm{\Omega }}{}}𝐑_\alpha 𝐅_\alpha `$ (27)
$`=`$ $`2T_\mathrm{\Omega }+U_\mathrm{\Omega }{\displaystyle \underset{\alpha ϵ\mathrm{\Omega }}{}}𝐑_\alpha 𝐅_\alpha ={\displaystyle _S}𝐫\sigma _{\mathrm{Bader}}𝑑𝐒.`$ (28)
Here, $`𝐏_{\mathrm{xc}}^{\mathrm{DF}}`$ is the exchange-correlation pressure tensor defined in the DF theory as

$$𝐏_{\mathrm{xc}}^{\mathrm{DF}}n(𝐫)\frac{\delta _{\mathrm{xc}}}{\delta n(𝐫)}.$$
(29)
which gives the explicit expression for the electrons in the jellium model at zero temperature in the local-density approximation (LDA) in the form

$$P_{\mathrm{xc},\mu \nu }^{\mathrm{LDA}}=n^2\frac{dϵ_{\mathrm{xc}}}{dn}\delta _{\mu \nu },$$
(30)
with the exchange-correlation energy $`ϵ_{\mathrm{xc}}(n)`$ per particle. Also, the force $`𝐅_\alpha `$ for $`\alpha `$-nucleus is introduced on the basis of the Hellmann-Feynman theorem: $`𝐅_\alpha =_\alpha E_{\mathrm{es}}`$. In (28), the true kinetic and potential energies, $`T_\mathrm{\Omega }T_s+\mathrm{\Delta }T_{\mathrm{xc}}`$ and $`U_\mathrm{\Omega }E_{\mathrm{es}}(\mathrm{\Omega })+\mathrm{\Delta }U_{\mathrm{xc}}`$, which should be provided by treating the many-electron problem, are obtained from the correction terms, $`\mathrm{\Delta }T_{\mathrm{xc}}`$ and $`\mathrm{\Delta }U_{\mathrm{xc}}`$; these correction terms are determined to satisfy the next relations

$`2\mathrm{\Delta }T_{\mathrm{xc}}+\mathrm{\Delta }U_{\mathrm{xc}}`$ $`=`$ $`{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_{\mathrm{xc}}d𝐫`$ (31)
$`\mathrm{\Delta }T_{\mathrm{xc}}+\mathrm{\Delta }U_{\mathrm{xc}}`$ $`=`$ $`E_{\mathrm{xc}}.`$ (32)
In the LDA for the electrons in the jellium model, these correction terms are explicitly written as

$`\mathrm{\Delta }T_{\mathrm{xc}}`$ $`=`$ $`{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_{\mathrm{xc}}d𝐫E_{\mathrm{xc}}{\displaystyle _\mathrm{\Omega }}n(𝐫)\{3\mu _{\mathrm{xc}}(𝐫)4ϵ_{\mathrm{xc}}(𝐫)\}𝑑𝐫,`$ (33)
$`\mathrm{\Delta }U_{\mathrm{xc}}`$ $`=`$ $`2E_{\mathrm{xc}}{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_{\mathrm{xc}}d𝐫{\displaystyle _\mathrm{\Omega }}n(𝐫)\{5ϵ_{\mathrm{xc}}(𝐫)3\mu _{\mathrm{xc}}(𝐫)\}𝑑𝐫`$ (34)
with $`\mu _{\mathrm{xc}}=(nϵ_{\mathrm{xc}})/n`$. Furthermore, it is important to note that the virial theorem (28) can be described in terms of the true kinetic stress tensor $`\sigma _{\mathrm{Bader}}`$, which is defined by Bader  for the interacting electrons outside the framework of the DF theory; the proof of (28) is given in -. Thus, the virial theorem with several expressions, (26)-(28), provides the electron pressure either in the form of surface integral (26) or volume integral (27), if the volume is chosen so that the pressure is constant on the surface $`S`$ of $`\mathrm{\Omega }`$. At this point, it should be mentioned that the electron pressure in the fixed nuclei is represented by the volume integral form (27) correctly if the virial of the forces which hold the nuclei is subtracted, while there is no need of this subtraction for the surface integral expression (26).

In the following, we give a brief outline of the proof of (26)-(28). At first, we can prove that the pressure tensor $`𝐏_\mathrm{e}^0`$, (23), of a noninteracting electron gas is identical with the kinetic pressure $`\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}`$, (21), in the DF theory

$$𝐏_\mathrm{e}^0=\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}$$
(35)
with use of (24), (23), (18) and (21) as follows

$`{\displaystyle _S}𝐫𝐏_\mathrm{e}^0𝑑𝐒`$ $`=`$ $`{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_\mathrm{e}^0d𝐫+{\displaystyle _\mathrm{\Omega }}𝐫𝐏_\mathrm{e}^0𝑑𝐫`$ (36)
$`=`$ $`2T_s[n]_\mathrm{\Omega }{\displaystyle n(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫}`$ (37)
$`=`$ $`{\displaystyle _S}𝐫\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}𝑑𝐒.`$ (38)
Next, the electron pressure tensor $`𝐏_\mathrm{e}`$ is shown to be a sum of its kinetic pressure tensor $`\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}`$ and the exchange-correlation pressure tensor $`𝐏_{\mathrm{xc}}^{\mathrm{DF}}`$

$$𝐏_\mathrm{e}=𝐏_\mathrm{e}^0+𝐏_{\mathrm{xc}}^{\mathrm{DF}}=\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}},$$
(39)
from (23) and (25) as below

$$(𝐏_\mathrm{e}𝐏_\mathrm{e}^0)=n(𝐫)[U_{\mathrm{eff}}(𝐫)\delta E_{\mathrm{es}}/\delta n(𝐫)]=n(𝐫)[\delta _{\mathrm{xc}}/\delta n(𝐫)]=𝐏_{\mathrm{xc}}^{\mathrm{DF}}.$$
(40)
In final, with use of (37), (39), (15) and (31), an identity (41) is shown to arrive at the proof of (26)-(28) as is described in the following

$`{\displaystyle _S}𝐫𝐏_\mathrm{e}𝑑𝐒`$ $`=`$ $`{\displaystyle _S}𝐫𝐏_\mathrm{e}^0𝑑𝐒+{\displaystyle _S}𝐫[𝐏_\mathrm{e}𝐏_\mathrm{e}^0]𝑑𝐒={\displaystyle _S}𝐫(\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}})𝑑𝐒`$ (41)
$`=`$ $`2T_s[n]_\mathrm{\Omega }{\displaystyle _\mathrm{\Omega }}n(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫+{\displaystyle _S}𝐫𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐒`$ (43)
$`=`$ $`2T_s[n]_\mathrm{\Omega }+E_{\mathrm{es}}(\mathrm{\Omega }){\displaystyle _\mathrm{\Omega }}n(𝐫)𝐫{\displaystyle \frac{\delta _{\mathrm{xc}}}{\delta n(𝐫)}}d𝐫`$
$`{\displaystyle \underset{\alpha ϵ\mathrm{\Omega }}{}}𝐑_\alpha _\alpha E_{\mathrm{es}}+{\displaystyle _S}𝐫𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐒`$
$`=`$ $`2T_s[n]_\mathrm{\Omega }+E_{\mathrm{es}}(\mathrm{\Omega })+{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_{\mathrm{xc}}d𝐫{\displaystyle \underset{\alpha ϵ\mathrm{\Omega }}{}}𝐑_\alpha 𝐅_\alpha `$ (44)
$`=`$ $`2[T_s[n]_\mathrm{\Omega }+\mathrm{\Delta }T_{\mathrm{xc}}]+[E_{\mathrm{es}}(\mathrm{\Omega })+\mathrm{\Delta }U_{\mathrm{xc}}]{\displaystyle \underset{\alpha ϵ\mathrm{\Omega }}{}}𝐑_\alpha 𝐅_\alpha .`$ (45)
In the derivation of (44), Eq. (29) and the tensor relation (24) are used in the form

$$n(𝐫)𝐫\frac{\delta _{\mathrm{xc}}}{\delta n(𝐫)}d𝐫+_S𝐫𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐒=_\mathrm{\Omega }𝐫𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐫+_S𝐫𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐒=_\mathrm{\Omega }\mathrm{tr}𝐏_{\mathrm{xc}}^{\mathrm{DF}}d𝐫,$$
(46)
which is written in the LDA for the electrons in the jellium model as

$$n(𝐫)𝐫\frac{\delta _{\mathrm{xc}}}{\delta n(𝐫)}d𝐫=n(𝐫)𝐫\mu _{\mathrm{xc}}d𝐫=3n^2\frac{d}{dn}ϵ_{\mathrm{xc}}𝑑𝐫n^2\frac{d}{dn}ϵ_{\mathrm{xc}}𝐫𝑑𝐒.$$
(47)
## 4 Maxwell stress tensor and electron pressure tensor

In the previous section, we have shown that the electron pressure tensor is given by $`𝐏_e\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}`$ in the DF theory. On the other hand, Nielsen and Martin  and some other  have defined the electron pressure tensor $`𝐏_e^{\mathrm{NM}}`$ using the Maxwell pressure tensor as to be

$$𝐏_e^{\mathrm{NM}}\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}+𝐏^\mathrm{M}.$$
(48)
In this section, we inquire into the relationship between these two pressure tensors.

When the nuclei is fixed at the positions $`\{𝐑_\alpha \}`$ with a charge density distribution $`\rho _+(𝐫)_\alpha Ze\delta (𝐫𝐑_\alpha )`$, and this nuclear distribution produces an electron charge distribution $`\rho _{}(𝐫)en(𝐫)`$, an electrostatic potential $`\varphi (𝐫)`$ of this system is determined by the Poisson equation

$$^2\varphi (𝐫)=4\pi [\rho _+(𝐫)+\rho _{}(𝐫)].$$
(49)
In terms of the electric field $`𝐄(𝐫)=\varphi (𝐫)`$ determined by this Poisson equation, we can define the Maxwell stress tensor $`𝐓`$ as

$$𝐓\frac{1}{4\pi }\left(\varphi \varphi \frac{1}{2}|\varphi |^2\mathrm{𝟏}\right)=\frac{1}{4\pi }\left(𝐄𝐄\frac{1}{2}|𝐄|^2\mathrm{𝟏}\right).$$
(50)
Here, $`\varphi (𝐫)`$ is represented as a solution of (49) in the form

$$\varphi (𝐫)=\frac{[\rho _+(𝐫^{})+\rho _{}(𝐫^{})]}{|𝐫𝐫^{}|}𝑑𝐫^{}=\underset{\alpha =1}{\overset{N}{}}\frac{Ze}{|𝐫𝐑_\alpha |}\frac{en(𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫^{}\frac{\mathrm{\Phi }(𝐫)}{e}$$
(51)
with

$$\mathrm{\Phi }(𝐫)\frac{e^2n(𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫^{}\underset{\alpha =1}{\overset{N}{}}\frac{Ze^2}{|𝐫𝐑_\alpha |}=\frac{\delta E_{\mathrm{es}}}{\delta n(𝐫)}.$$
(52)
The Maxwell stress tensor is shown to satisfy the following equation

$$𝐓=[\rho _+(𝐫)+\rho _{}(𝐫)]\varphi (𝐫)=\frac{1}{e}[\rho _+(𝐫)+\rho _{}(𝐫)]\mathrm{\Phi }(𝐫).$$
(53)
With use of (52), (53) and (24), we obtain the relations between the Maxwell stress tensor $`𝐓`$ and the electrostatic energy $`E_{\mathrm{es}}`$, (9), of the system (excluding nuclear self-interactions)

$`{\displaystyle _\mathrm{\Omega }}𝐫𝐓𝑑𝐫`$ $`=`$ $`{\displaystyle _\mathrm{\Omega }}n(𝐫)𝐫{\displaystyle \frac{\delta E_{\mathrm{es}}}{\delta n(𝐫)}}d𝐫{\displaystyle \underset{\alpha ϵ\mathrm{\Omega }}{}}𝐑_\alpha _\alpha E_{\mathrm{es}}`$ (54)
$`=`$ $`E_{\mathrm{es}}(\mathrm{\Omega })={\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐓d𝐫+{\displaystyle _S}𝐫𝐓𝑑𝐒.`$ (55)
Thus, we obtain the following relation which is important to know how the Maxwell stress tensor $`𝐓`$ plays a role in the virial theorem

$`{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐓d𝐫`$ $`=`$ $`{\displaystyle \frac{1}{8\pi }}{\displaystyle _\mathrm{\Omega }}|𝐄|^2𝑑𝐫={\displaystyle _\mathrm{\Omega }}[\rho _+(𝐫)+\rho _{}(𝐫)]𝐫\varphi (𝐫)𝑑𝐫𝑑𝐫^{}{\displaystyle _S}𝐫𝐓𝑑𝐒`$ (56)
$`=`$ $`E_{\mathrm{es}}(\mathrm{\Omega }){\displaystyle _S}𝐫𝐓𝑑𝐒.`$ (57)
At this stage, we introduce the Maxwell pressure tensor $`𝐏^\mathrm{M}𝐓`$; then, we obtain the following relations from (53), (52) and (25)

$$(\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}+𝐏^\mathrm{M})=\underset{\alpha }{}𝐅_\alpha \delta (𝐫𝐑_\alpha ),$$
(58)
$$_\mathrm{\Omega }𝐫(\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}+𝐏^\mathrm{M})𝑑𝐫=\underset{\alpha ϵ\mathrm{\Omega }}{}𝐑_\alpha 𝐅_\alpha .$$
(59)
Therefore, we get an expression with use of (57)

$$_\mathrm{\Omega }\mathrm{tr}(\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}+𝐏^\mathrm{M})𝑑𝐫=2T_\mathrm{\Omega }+U_\mathrm{\Omega }+_S𝐫𝐏^\mathrm{M}𝑑𝐒,$$
(60)
for an arbitrary subspace $`\mathrm{\Omega }`$ chosen in the system. It should be mentioned that in the standard treatment the surface integral in (57) is neglected, and as a result, the surface integral of the Maxwell pressure tensor does not appear in (60); Eq. (60) without the surface integral term implies that $`𝐏_e^{\mathrm{NM}}`$ defined by (48) seems to be interpreted as the electron pressure tensor giving the virial theorem exactly . This is not the case, since the surface integral exists in (60) in general. At the same time, it should be kept in mind that we have the virial theorem for $`𝐏_e^{\mathrm{NM}}`$

$$_S𝐫(\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}+𝐏^\mathrm{M})𝑑𝐒=2T_\mathrm{\Omega }+U_\mathrm{\Omega }\underset{\alpha ϵ\mathrm{\Omega }}{}𝐑_\alpha 𝐅_\alpha .$$
(61)
only if a volume $`\mathrm{\Omega }`$ is chosen so as to fulfill the condition $`_S𝐫𝐏^\mathrm{M}𝑑𝐒=0`$ on the surface of this volume; in this case, (61) reduces to (26).

In conclusion, as a consequence of (60) and (61), the tensor $`𝐏_e^{\mathrm{NM}}`$ defined by (48) plays a role of the electron pressure tensor in the presence of the fixed nuclei only for a subspace $`\mathrm{\Omega }`$, on which surface the condition $`_S𝐫𝐏^\mathrm{M}𝑑𝐒=0`$ is satisfied.

## 5 Comparison with other electron-pressure formulas

In Sec. 3, we derived the virial theorem (26)-(28), in the surface integral and volume integral forms, for the electrons in the presence of fixed nuclei, which provides the electron pressure in condensed matter at arbitrary temperature and density. On the other hand, there have been proposed many methods to calculate the electron-pressure in the fixed nuclei. In the present section, we will make comparison of our result with some of other formulations, and give some comments.

If the electron pressure is assumed to be constant on the surface of the Wigner-Seitz sphere, Eq. (26) with (20) provides the electron pressure in the presence of the fixed nuclei in a surface integral form

$`{\displaystyle _S}𝐫𝐏_\mathrm{e}𝑑𝐒`$ $`=`$ $`3P_\mathrm{e}V={\displaystyle _S}𝐫(\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}})𝑑𝐒`$ (62)
$`=`$ $`{\displaystyle \underset{i}{}}f(ϵ_i){\displaystyle \frac{\mathrm{}^2}{4m}}{\displaystyle _S}\{\phi _i^{}[𝐫\phi _i](𝐫\phi _i)(\phi _i^{})+\mathrm{c}.\mathrm{c}.\}dS`$
$`+{\displaystyle _S}𝐫𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐒.`$
When we use the LDA expression for $`P_{\mathrm{xc},\mu \nu }^{\mathrm{DF}}n^2ϵ_{\mathrm{xc}}/n\delta _{\mu \nu }`$ in the above, (62) reduces to Liberman’s pressure formula. However, the nuclear virial term does not appear in (62) on comparison with the Liberman expression (7).

On the other hand, if we choose the volume $`\mathrm{\Omega }`$ to be the Wigner-Seitz sphere with a radius $`r_0`$, the virial theorem in the surface integral form, (26), with (22) can be rewritten as

$`P_\mathrm{e}`$ $`=`$ $`{\displaystyle \underset{i}{}}f(ϵ_i){\displaystyle _S}\phi _i^{}(r_0,\widehat{𝐫})\left[ϵ_iU_{\mathrm{eff}}{\displaystyle \frac{\widehat{\mathrm{}}^2}{2mr_0^2}}\right]\phi _i(r_0,\widehat{𝐫}){\displaystyle \frac{d\mathrm{\Omega }}{4\pi }}`$ (63)
$`+{\displaystyle \underset{i}{}}f(ϵ_i){\displaystyle \frac{\mathrm{}^2}{2m}}{\displaystyle _S}\left|{\displaystyle \frac{\phi _i}{r_0}}\right|^2\left[\left|r{\displaystyle \frac{\phi _i}{r}}/\phi _i\right|^2\mathrm{}\left\{r{\displaystyle \frac{\phi _i}{r}}/\phi _i\right\}\right]_{r_0}{\displaystyle \frac{d\mathrm{\Omega }}{4\pi }}+P_{\mathrm{xc}}^{\mathrm{DF}}(r_0)`$
with $`d\mathrm{\Omega }\mathrm{sin}\theta d\theta \varphi `$ and the definition of an operator $`\widehat{\mathrm{}}^2`$: $`\widehat{\mathrm{}}^2Y_{\mathrm{}}^m(\theta ,\varphi )=\mathrm{}(\mathrm{}+1)\mathrm{}^2Y_{\mathrm{}}^m(\theta ,\varphi )`$.
Equation (63) becomes the pressure formula given by Nieminen-Hodge  and Pettifor . Furthermore, when the volume is chosen to be the Wigner-Seitz cell with the muffin-tin approximation, and the exchange-correlation effect is described by a generalized gradient approximation, Eq. (63) leads to the pressure formula given by Legrand and Perrot  by taking account of the discontinuity in the electron density distribution.

Nielsen and Martin  with other investigators  have defined the pressure in terms of the Maxwell pressure tensor in the form

$$𝐏_e^{\mathrm{NM}}\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}+𝐏^\mathrm{M}.$$
(64)
As was discussed in details in Sec. 4, this tensor $`𝐏_e^{\mathrm{NM}}`$ cannot be interpreted as the electron pressure except the case when we treat the pressure in a restricted subspace $`\mathrm{\Omega }`$ chosen to satisfy the condition $`_S𝐫𝐏^\mathrm{M}𝑑𝐒=0`$ on its surface (e.g. Wigner-Seitz cell). When this condition is fulfilled, we obtain virial expressions such as

$`{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_e^{\mathrm{NM}}𝑑𝐫`$ $`=`$ $`2T_\mathrm{\Omega }+U_\mathrm{\Omega },`$ (65)
$`{\displaystyle _S}𝐫𝐏_e^{\mathrm{NM}}𝑑𝐒`$ $`=`$ $`2T_\mathrm{\Omega }+U_\mathrm{\Omega }{\displaystyle \underset{\alpha ϵ\mathrm{\Omega }}{}}𝐑_\alpha 𝐅_\alpha .`$ (66)
In addition, Ziesche, Gräfenstein and Nielsen  have defined the pressure in terms of $`_\alpha 𝐑_\alpha 𝐅_\alpha `$ considering a solid as an isolated system \[that is, $`_S𝐫𝐏^{\mathrm{NM}}𝑑𝐒=0`$\] by

$$3P_\mathrm{e}\mathrm{\Omega }\underset{\alpha }{}𝐑_\alpha 𝐅_\alpha =2T_\mathrm{\Omega }+U_\mathrm{\Omega },$$
(67)
as was defined by Slater . However, the electron pressure in the fixed nuclei should be defined by (28), where the virial of the forces that hold the nuclei fixed is subtracted here to be added later in the thermodynamic pressure formula (86) as will be discussed in the next section.

Janak  derived the pressure formula starting from the virial theorem of the volume integral form which is written in our version as

$$3PV=2T_s[n]+E_{\mathrm{es}}+_V\mathrm{tr}𝐏_{\mathrm{xc}}𝑑𝐫.$$
(68)
In this equation, he replaced $`E_{\mathrm{es}}`$ in a volume $`V`$ containing $`N`$ nuclei by an approximate expression (71)

$`Nu_{\mathrm{es}}`$ $``$ $`E_{\mathrm{es}}`$ (69)
$`=`$ $`{\displaystyle _V}n(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫+{\displaystyle _V}n(𝐫)𝐫{\displaystyle \frac{\delta E_{\mathrm{xc}}}{\delta n(𝐫)}}d𝐫{\displaystyle \underset{\alpha }{}}𝐑_\alpha _\alpha E_{\mathrm{es}}`$ (70)
$``$ $`N\left[{\displaystyle _{\mathrm{\Omega }_0}}n(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫+{\displaystyle _{\mathrm{\Omega }_0}}n(𝐫)𝐫{\displaystyle \frac{\delta E_{\mathrm{xc}}}{\delta n(𝐫)}}d𝐫{\displaystyle \frac{1}{4}}C{\displaystyle \frac{Z_{\mathrm{out}}^2}{a}}\right],`$ (71)
as was written in his equation (18) for the unit cell $`\mathrm{\Omega }_0`$. Thus, the Ewald term $`\frac{1}{4}C\frac{Z_{\mathrm{out}}^2}{a}`$ can be taken as the nuclear virial in this approximation. With this replacement, Eq. (68) is rewritten as the next equation (72), which leads to a simplified expression of his pressure formula \[his (24)\] as (73)

$`3PV`$ $`=`$ $`{\displaystyle _S}𝐫𝐏_\mathrm{e}𝑑𝐒+{\displaystyle \underset{\alpha }{}}𝐑_\alpha 𝐅_\alpha `$ (72)
$``$ $`3N\left[{\displaystyle \frac{2}{5}}ϵ_\mathrm{F}^0+n{\displaystyle \frac{dϵ_{\mathrm{xc}}}{dn}}\right]_{n=n_0^{\mathrm{}}}N{\displaystyle \frac{1}{4}}C{\displaystyle \frac{Z_{\mathrm{out}}^2}{a}}`$ (73)
with $`ϵ_\mathrm{F}^0`$ being the Fermi energy of a noninteracting electron gas, if the muffin-tin approximation is not introduced. In the derivation of (73), the electron density $`n`$ is assumed to be constant $`n_0^\mathrm{e}`$ at the surface of the unit cell $`\mathrm{\Omega }_0`$ and we used the following relations

$$T_s[n]_{\mathrm{\Omega }_0}T_s[n_0^\mathrm{e}]_{\mathrm{\Omega }_0}=\frac{1}{2}_{\mathrm{\Omega }_0}n(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫,$$
(74)
and

$$T_s[n_\mathrm{b}]_{\mathrm{\Omega }_0}=\frac{1}{2}_{\mathrm{\Omega }_0}n_\mathrm{b}(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫,$$
(75)
for the bound-electron density $`n_\mathrm{b}(𝐫)`$. Equation (73) indicates an essential structure of his pressure formula, although simplified. For the same reason, his formula \[his (25)\] for the total energy becomes

$$E=\frac{N}{2}_{\mathrm{\Omega }_0}n(𝐫)𝐫U_{\mathrm{eff}}(𝐫)𝑑𝐫+E[n_0^\mathrm{e}]\{\mathrm{\Delta }T_{\mathrm{xc}}[n(𝐫)]\mathrm{\Delta }T_{\mathrm{xc}}[n_0^\mathrm{e}]\}N\frac{1}{4}C\frac{Z_{\mathrm{out}}^2}{a},$$
(76)
where $`\mathrm{\Delta }T_{\mathrm{xc}}[n(𝐫)]`$ in the LDA is given by (33).

## 6 Pressure in liquid metals and plasmas

In Sec. 3, we have derived pressure formulas for the electrons in the fixed nuclei. However, the thermodynamical pressure of liquid metals and plasmas must be determined as a nucleus-electron mixture as a whole; the electron pressure $`P_e`$ is only a part of the whole pressure $`P`$, although $`P_e`$ is nearly equal to the total pressure in metals.

In general, the thermodynamic pressure is defined by $`P=F/\mathrm{\Omega }|_{N,T}`$ using the free-energy of the system: $`F=k_\mathrm{B}T\mathrm{ln}Z_N`$ with the partition function $`Z_N=\mathrm{Tr}\mathrm{exp}(\beta \widehat{H})`$ of a nucleus-electron mixture. Here, its Hamiltonian $`\widehat{H}\widehat{H}_{\mathrm{ee}}+\widehat{H}_{\mathrm{en}}+\widehat{H}_{\mathrm{nn}}`$ consists of the electron and nucleus Hamiltonians $`\widehat{H}_{\mathrm{ee}}`$ and $`\widehat{H}_{\mathrm{nn}}`$, in conjunction with the electron-nucleus interaction Hamiltonian $`\widehat{H}_{\mathrm{en}}`$. When the nuclei can be treated as classical particles $`[𝐏_\alpha ,𝐑_\alpha ]=0`$, the partition function is written in the form (see  for details)

$$Z_N=\frac{1}{N!h^{3N}}𝑑𝐑^N𝑑𝐏^N\mathrm{exp}[\beta H_{\mathrm{eff}}]$$
(77)
with

$$H_{\mathrm{eff}}=\underset{\alpha }{}\frac{𝐏_\alpha ^2}{2M}+\mathrm{\Phi }(\{𝐑_\alpha \};n),$$
(78)
$$\mathrm{\Phi }(\{𝐑_\alpha \};n)_0+E_{\mathrm{es}}[\widehat{n}_\mathrm{I},n]+_{\mathrm{xc}}[\widehat{n}_\mathrm{I},n]=_\mathrm{e}[\{𝐑_\alpha \};n].$$
(79)
Here, $`\widehat{n}_\mathrm{I}(𝐫)=_\alpha \delta (𝐫𝐑_\alpha )`$ denotes the microscopic nuclear density distribution. Also, it is important to realise that $`\mathrm{\Phi }(\{𝐑_\alpha \};n)`$ plays a role of a many-body interaction among the nuclei, and $`_\mathrm{e}[\{𝐑_\alpha \};n]=\mathrm{\Phi }(\{𝐑_\alpha \};n)`$ represents at the same time the free energy of the electrons under the external potential caused by the fixed nuclei at the positions $`\{𝐑_\alpha \}`$ in the DF theory with reference to $`_0`$, the free-energy of noninteracting electron gas.

A volume change of the free energy can be calculated by introducing a new variable $`\lambda `$ defined by $`\mathrm{\Omega }(\lambda )=\lambda ^3\mathrm{\Omega }`$ in the following way

$$\mathrm{\Omega }\frac{F}{\mathrm{\Omega }}=\mathrm{\Omega }(\lambda )\frac{F(\lambda )}{\lambda }\frac{\lambda }{\mathrm{\Omega }(\lambda )}|_{\lambda =1}=\frac{\lambda }{3}\frac{F}{\lambda }|_{\lambda =1}.$$
(80)
Here, $`F(\lambda )k_\mathrm{B}T\mathrm{ln}Z_N(\lambda )`$ is defined by

$`Z_N(\mathrm{\Omega })`$ $`=`$ $`{\displaystyle \frac{1}{N!h^{3N}}}{\displaystyle _\mathrm{\Omega }}𝑑𝐑^N{\displaystyle 𝑑𝐏^N\mathrm{exp}[\beta H_{\mathrm{eff}}(𝐑,𝐏)]}`$ (81)
$`=`$ $`{\displaystyle \frac{\mathrm{\Omega }(\lambda )^N}{N!h^{3N}}}{\displaystyle _0^1}𝑑\overline{𝐑}^N{\displaystyle 𝑑𝐏^N\mathrm{exp}[\beta H_{\mathrm{eff}}(\eta \overline{𝐑},𝐏)]}Z_N(\lambda )`$ (82)
with $`\overline{𝐑}=𝐑/\eta (\lambda )`$ and $`\eta ^3(\lambda )\mathrm{\Omega }(\lambda )`$. Then, the $`\lambda `$-derivative of $`F`$ is easily performed as follows

$`{\displaystyle \frac{F(\lambda )}{\lambda }}`$ $`=`$ $`{\displaystyle \frac{Nk_\mathrm{B}T}{\mathrm{\Omega }}}{\displaystyle \frac{\mathrm{\Omega }}{\lambda }}`$ (83)
$`+{\displaystyle \frac{\mathrm{\Omega }(\lambda )^N}{Z_N(\lambda )}}{\displaystyle _0^1}𝑑\overline{𝐑}^N{\displaystyle 𝑑𝐏^N\mathrm{exp}[\beta H_{\mathrm{eff}}(\eta \overline{𝐑},𝐏)]\frac{H_{\mathrm{eff}}}{\lambda }}`$
with

$`{\displaystyle \frac{H_{\mathrm{eff}}}{\lambda }}|_{\lambda =1}`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Phi }(\eta \overline{𝐑},\mathrm{\Omega }(\lambda ))}{\lambda }}|_{\lambda =1}={\displaystyle \underset{\alpha }{}}𝐑_\alpha _\alpha \mathrm{\Phi }+3\mathrm{\Omega }{\displaystyle \frac{\mathrm{\Phi }}{\mathrm{\Omega }}}.`$ (84)
Finally as a consequence of the above equation, the thermodynamical pressure of liquid (solid) metals and plasmas is established as a mixture of nuclei and electrons in the form

$`3P\mathrm{\Omega }`$ $`=`$ $`3\mathrm{\Omega }{\displaystyle \frac{F}{\mathrm{\Omega }}}=\lambda {\displaystyle \frac{F}{\lambda }}|_{\lambda =1}`$ (85)
$`=`$ $`3Nk_\mathrm{B}T+{\displaystyle \frac{1}{\mathrm{\Xi }}}{\displaystyle 𝑑𝐑^N\mathrm{exp}[\beta \mathrm{\Phi }]\left\{3\mathrm{\Omega }\frac{\mathrm{\Phi }}{\mathrm{\Omega }}+\underset{\alpha }{}𝐑_\alpha 𝐅_\alpha \right\}}`$ (86)
$`=`$ $`3Nk_\mathrm{B}T+3\mathrm{\Omega }{\displaystyle \frac{\mathrm{\Phi }}{\mathrm{\Omega }}}+{\displaystyle \underset{\alpha }{}}𝐑_\alpha 𝐅_\alpha `$ (87)
with

$$\mathrm{\Xi }\frac{1}{N!\mathrm{\Lambda }^{3N}}𝑑𝐑^N\mathrm{exp}[\beta \mathrm{\Phi }(\{𝐑_\alpha \})],$$
(88)
and $`\mathrm{\Lambda }`$ being the de Broglie thermal wavelength of the nuclei. Here, $`\mathrm{\Omega }\mathrm{\Phi }/\mathrm{\Omega }=P_\mathrm{e}\mathrm{\Omega }`$ is the electron-pressure in the fixed nuclei, which can be determined by (26) or (27) within the framework of the DF theory, since $`\mathrm{\Phi }=_\mathrm{e}[\{𝐑_\alpha \}]`$ is the free energy of electrons in the presence of nuclei fixed at $`\{𝐑_\alpha \}`$. At this stage, an important remark should be made concerning (86). It has long been recognised  that the virial theorem for a liquid (or solid) metal is written in the form

$$3P_\mathrm{e}\mathrm{\Omega }\underset{\alpha }{}𝐑_\alpha 𝐅_\alpha =2T_\mathrm{\Omega }+U_\mathrm{\Omega }.$$
(89)
as was done by Slater . However, Eq. (86) indicates that the electron pressure under the external potential caused by fixed nuclei should be given by

$$3P_e\mathrm{\Omega }=3\mathrm{\Omega }\frac{\mathrm{\Phi }}{\mathrm{\Omega }}=2T_\mathrm{\Omega }+U_\mathrm{\Omega }\underset{\alpha ϵ\mathrm{\Omega }}{}𝐑_\alpha 𝐅_\alpha ,$$
(90)
as was shown in (28), and that the thermodynamical pressure $`P`$ of a liquid (solid) metal should be defined by (86) as a nucleus-electron mixture, where the nuclear virial term in (90) disappears by cancellation.

Thus, the EOS of the nucleus-electron mixture is determined by two types of the formulas using a surface integral and a volume integral in the final form

$`3P\mathrm{\Omega }`$ $`=`$ $`3Nk_\mathrm{B}T+{\displaystyle _S}𝐫\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐒+{\displaystyle \underset{\alpha }{}}𝐑_\alpha 𝐅_\alpha `$ (91)
$`=`$ $`3Nk_\mathrm{B}T+2T_s[n]+E_{\mathrm{es}}+{\displaystyle \mathrm{tr}𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐫},`$ (92)
with combined use of (86), (26) and (27). It is worth pointing out that the volume integral form (92) of the virial theorem contains the nuclear virial contribution, although it does not appear explicitly comparing with the surface integral form (91). In addition, it should be kept in mind here that the term $`𝐏_{\mathrm{xc}}^{\mathrm{DF}}(\widehat{n}_\mathrm{I},n)`$ depends on the ion-configuration $`\widehat{n}_\mathrm{I}(𝐫)`$, and therefore it is not that of the jellium model in a strict sense. In the jellium model with use of the LDA, the exchange-correlation pressure is given by $`P_{\mathrm{xc},\mu \nu }^{\mathrm{DF}}=n^2dϵ_{\mathrm{xc}}/dn\delta _{\mu \nu }`$. In this approximation, we obtain the following expressions

$$_\mathrm{\Omega }\mathrm{tr}𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐫3_\mathrm{\Omega }n^2\frac{dϵ_{\mathrm{xc}}}{dn}𝑑𝐫$$
(93)
$$_S𝐫\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}𝑑𝐒3\mathrm{\Omega }\left[n\frac{2}{5}ϵ_\mathrm{F}^0+n^2\frac{dϵ_{\mathrm{xc}}}{dn}\right]_{n=n_0^e},$$
(94)
where the electron density is assumed to be constant $`n_0^e`$ on the surface of the volume $`\mathrm{\Omega }`$.

On the other hand, in liquid metals and plasmas where their effective interactions among ions with uniform density $`n_0^\mathrm{I}`$ can be described by a pair interaction $`v_{\mathrm{II}}^{\mathrm{eff}}(r)`$, the average of the nuclear virial is given by

$$\underset{\alpha }{}𝐑_\alpha 𝐅_\alpha =\frac{1}{2}Nn_0^\mathrm{I}g_{\mathrm{II}}(r)𝐫v_{\mathrm{II}}^{\mathrm{eff}}(r)𝑑𝐫.$$
(95)
Therefore, the EOS of liquid metals and plasmas is described in this approximation by a formula

$`P`$ $`=`$ $`n_0^\mathrm{I}k_\mathrm{B}T+{\displaystyle \frac{2}{3}}{\displaystyle \frac{T_\mathrm{\Omega }}{\mathrm{\Omega }}}`$ (96)
$`+{\displaystyle \frac{1}{6}}n_0^\mathrm{I}{\displaystyle g_{\mathrm{ee}}^0(r)v_{\mathrm{ee}}(r)𝑑𝐫}{\displaystyle \frac{1}{6}}(n_0^\mathrm{I})^2{\displaystyle g_{\mathrm{II}}(r)𝐫v_{\mathrm{II}}^{\mathrm{eff}}(r)𝑑𝐫}`$
$`=`$ $`n_0^\mathrm{I}k_\mathrm{B}T+n^2{\displaystyle \frac{d}{dn}}\left({\displaystyle \frac{3}{5}}ϵ_\mathrm{F}^0+ϵ_{\mathrm{xc}}\right)|_{n_0^e}{\displaystyle \frac{1}{6}}(n_0^\mathrm{I})^2{\displaystyle g_{\mathrm{II}}(r)𝐫v_{\mathrm{II}}^{\mathrm{eff}}(r)𝑑𝐫}.`$ (97)
Here, $`g_{ee}^0(r)`$ is a free electron part of the electron-electron radial distribution function  defined by

$`1+n_0^e_Q[g_{ee}^0(r)1]{\displaystyle \frac{1}{\pi }}{\displaystyle _{\mathrm{}}^{\mathrm{}}}𝑑\omega {\displaystyle \frac{\mathrm{}\beta }{1\mathrm{exp}(\beta \mathrm{}\omega )}}\mathrm{}{\displaystyle \frac{\chi _Q^0[\omega ]}{1+n_0^e\beta v_{\mathrm{ee}}(Q)[1G(Q,\omega )]\chi _Q^0[\omega ]}},`$ (98)
in terms of the dynamical local-field correction $`G(Q,\omega )`$ in the electron-ion mixture. In the jellium approximation, we obtain expressions, $`G(Q,\omega )G^{\mathrm{jell}}(Q,\omega )`$ and

$$\left(\frac{T_\mathrm{\Omega }}{\mathrm{\Omega }}\right)_{\mathrm{jell}}=n\left(\frac{3}{5}ϵ_\mathrm{F}^0+3n\frac{dϵ_{\mathrm{xc}}}{dn}ϵ_{\mathrm{xc}}\right)|_{n_0^e}=n\left(\frac{3}{5}ϵ_\mathrm{F}^0+3\mu _{\mathrm{xc}}4ϵ_{\mathrm{xc}}\right)|_{n_0^e}$$
(99)
to be used in (96) leading to (97). At this point, it should be noted that when we approximate $`\mathrm{\Phi }(\{𝐑_\alpha \})`$ at earlier stage to be

$$\mathrm{\Phi }(\{𝐑_\alpha \})U_0(\mathrm{\Omega })+\frac{1}{2}\underset{\alpha \beta }{}v_{\mathrm{II}}^{\mathrm{eff}}(|𝐑_\alpha 𝐑_\beta |),$$
(100)
we obtain another EOS

$$\frac{\beta P}{n_0^\mathrm{I}}=1+n_0^\mathrm{I}\frac{dU_0}{dn_0^\mathrm{I}}\frac{1}{6}\beta n_0^\mathrm{I}g_{\mathrm{II}}(r)\left[𝐫3n_0^\mathrm{I}\frac{}{n_0^\mathrm{I}}\right]v_{\mathrm{II}}^{\mathrm{eff}}(r)𝑑𝐫,$$
(101)
which is used as a standard virial formula for a liquid metal . The difference between (97) and (101) comes from the electron-pressure term in (87). This term with an approximate expression to $`\mathrm{\Phi }`$ (100) leads to (101), while this term with use of the exact expression (26) yields a more accurate and simpler pressure-formula (97).

## 7 Summary and discussion

As a first step, we have derived pressure formulas, (26) and (27), for the electrons under the external potential produced by fixed nuclei on the basis of the DF theory; one is a surface integral form and the other, a volume integral form showing the exact virial theorem (28). The electron pressure tensor is represented by a sum of the kinetic tensor and exchange-correlation pressure tensor, $`𝐏_\mathrm{e}=\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}`$, in the DF theory.

As a second step, the thermodynamical pressure $`P`$ is defined by the volume derivative of the free energy for a nucleus-electron mixture (liquid metals or plasmas) on the assumption that the nuclei behave as classical particles. This procedure leads to the EOS formula given by (86), which contains the electron-pressure in the presence of fixed nuclei and the nuclear virial. In final, we obtain pressure formulas, (91) and (92), for liquid metals and plasmas in the surface integral and volume integral forms, respectively. In this respect, it is important to recognise that the exchange-correlation pressure tensor $`𝐏_{\mathrm{xc}}^{\mathrm{DF}}(\widehat{n}_\mathrm{I},n)`$ is that of the electron-ion mixture, which is approximated by that of the jellium model in the standard treatment.

For a liquid metal, when we can approximate a many-body interaction $`\mathrm{\Phi }(\{𝐑_\alpha \};n)`$ (79) among the nuclei to be represented by the sum of a binary interaction $`v_{\mathrm{II}}^{\mathrm{eff}}(r)`$, Eq. (91) is reduced to a virial pressure formula (96). Furthermore, when the electrons in the mixture can be treated by the jellium model, (that is, the electron is weakly coupled with the ions in the electron-ion mixture), we obtain a virial pressure formula (97), which is simpler and more accurate than the standard virial formula (101) for a liquid metal .

Also, our formulation for the pressure have clarified confusion and improper expressions found in the previous works, as was addressed in the introduction. The electron pressure in the presence of fixed nuclei should be determined by (90) instead of (89), as was discussed in Sec. 6. Also, a tensor, $`𝐏_e^{\mathrm{NM}}\stackrel{~}{𝐏}_\mathrm{K}^{\mathrm{DF}}+𝐏_{\mathrm{xc}}^{\mathrm{DF}}+𝐏^\mathrm{M}`$ with the Maxwell pressure tensor $`𝐏^\mathrm{M}`$, can be interpreted as a pressure tensor only when we treat a subspace $`\mathrm{\Omega }`$ of the system fulfilling the condition $`_S𝐫𝐏^\mathrm{M}𝑑𝐒=0`$ on its surface. Therefore, there is no need to introduce a correction term due to the Maxwell pressure tensor in the Liberman pressure expression , in spite of the suggestion by Follland  and Nielsen and Martin .

There is a fundamental problem whether we can choose arbitrarily any subspace in the system for the virial theorem to be applicable. Srebrenik and Bader  have answered to this question by giving the zero-flux surface condition to a subspace; a subspace has a close surface through which the flux of $`n(𝐫)`$ is everywhere zero, that is,

$$n(𝐫)𝐞(𝐫)=0,$$
(102)
for any point $`𝐫`$ in a close surface with a normal vector $`𝐞(𝐫)`$. In a local virial theorem constructed on this condition, there is no ambiguity in the definition of kinetic energy $`T_s`$ and the kinetic tensor $`𝐏_\mathrm{K}^{\mathrm{DF}}`$, as will be discussed in Appendix.

## Appendix. Proof of (18)

In the DF theory, the wave function is determined by the Schrödinger equation with a self-consistent external potential $`U_{\mathrm{eff}}(𝐫)`$

$$\left[\frac{\mathrm{}^2}{2m}^2+U_{\mathrm{eff}}(𝐫)ϵ_i\right]\phi _i(𝐫)=0.$$
(103)
By multiplying (103) by $`\phi _i^{}𝐫`$, there results

$`\phi _i^{}𝐫\left[{\displaystyle \frac{\mathrm{}^2}{2m}}^2+U_{\mathrm{eff}}(𝐫)ϵ_i\right]\phi _i(𝐫)`$ $`=`$ $`{\displaystyle \frac{\mathrm{}^2}{2m}}\phi _i^{}𝐫^2\phi _i+\phi _i^{}𝐫U_{\mathrm{eff}}\phi _i`$ (104)
$`+[U_{\mathrm{eff}}ϵ_i]\phi _i^{}𝐫\phi _i=0.`$
Therefore, from the above equation , we obtain

$`\phi _i^{}\phi _i𝐫U_{\mathrm{eff}}`$ $`=`$ $`{\displaystyle \frac{\mathrm{}^2}{2m}}[\phi _i^{}𝐫^2\phi _i(^2\phi _i^{})(\mathrm{r}\phi _i)]`$ (105)
$`=`$ $`{\displaystyle \frac{\mathrm{}^2}{2m}}\left[2\phi _i^{}^2\phi _i\{(\phi _i^{})^2(𝐫\phi _i/\phi _i^{})\}\right].`$
This equation is rewritten in the form

$`2\phi _i^{}{\displaystyle \frac{\mathrm{}^2}{2m}}^2\phi _i=\phi _i^{}\phi _i𝐫U_{\mathrm{eff}}+A`$ (106)
with

$`A`$ $`=`$ $`{\displaystyle \frac{\mathrm{}^2}{2m}}\{\phi _i^{}[𝐫\phi _i](𝐫\phi _i)(\phi _i^{})\}`$ (107)
$`=`$ $`{\displaystyle \frac{\mathrm{}^2}{4m}}\{\phi _i^{}[𝐫\phi _i](𝐫\phi _i)(\phi _i^{})+\mathrm{c}.\mathrm{c}.\}`$ (108)
$`=`$ $`{\displaystyle \frac{\mathrm{}^2}{4m}}\{(\phi _i^{}\phi _i)+(𝐫)(\phi _i^{}\phi _i)2[(𝐫\phi _i)(\phi _i^{})+(𝐫\phi _i^{})(\phi _i)]\}`$ (110)
$`=`$ $`{\displaystyle \frac{\mathrm{}^2}{4m}}\{(\phi _i^{}\phi _i)+\phi _i^{}(𝐫)\phi _i+\phi _i(𝐫)\phi _i^{}`$
$`(𝐫\phi _i)(\phi _i^{})(𝐫\phi _i^{})(\phi _i)\},`$
which leads to (18) with (19)-(21).

On the other hand, (18) can be proved in a direct way by following Pauli . Pauli have proved that the probability current

$$𝐢\frac{1}{2}\left[(\phi \frac{\widehat{𝐩}}{m}\phi ^{})+(\phi \frac{\widehat{𝐩}}{m}\phi ^{})^{}\right]$$
(111)
for a wave function of a single electron moving under the external potential $`U_{\mathrm{eff}}(𝐫)`$ obeys the following continuity equation

$$m\frac{}{t}𝐢=𝐒(\phi \phi ^{})U_{\mathrm{eff}}(𝐫)$$
(112)
with a tensor defined by

$$S_{\mu \nu }(\phi )\frac{\mathrm{}^2}{4m}\left[\phi _\mu _\nu \phi ^{}+\phi ^{}_\mu _\nu \phi _\mu \phi _\nu \phi ^{}_\mu \phi ^{}_\nu \phi \right].$$
(113)
This provides the following equation for the static case

$$m𝐫\frac{}{t}𝐢=𝐫𝐒(\phi \phi ^{})𝐫U_{\mathrm{eff}}(𝐫)=0.$$
(114)
When we interpret $`𝐏_\mathrm{K}^{\mathrm{DF}}`$ defined by

$$𝐏_\mathrm{K}^{\mathrm{DF}}\underset{i}{}f(ϵ_i)𝐒(\phi _i)$$
(115)
as a kinetic tensor in the DF theory, (114 ) is changed into the form

$`{\displaystyle _\mathrm{\Omega }}𝐫𝐏_\mathrm{K}^{\mathrm{DF}}𝑑𝐫`$ $`=`$ $`{\displaystyle _\mathrm{\Omega }}n(𝐫)U_{\mathrm{eff}}(𝐫)𝑑𝐫`$ (116)
$`=`$ $`{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_\mathrm{K}^{\mathrm{DF}}𝑑𝐫{\displaystyle _S}𝐫𝐏_\mathrm{K}^{\mathrm{DF}}𝑑𝐒,`$
with use of a tensor relation (24). By noting the relation

$`\mathrm{tr}𝐒`$ $`=`$ $`{\displaystyle \underset{\mu }{}}S_{\mu \mu }={\displaystyle \frac{\mathrm{}^2}{4m}}\left[\phi ^{}^2\phi \phi ^2\phi ^{}+2\phi ^{}\phi \right]`$ (117)
$`=`$ $`\left[(\phi ^{}{\displaystyle \frac{\mathrm{}^2}{2m}}^2\phi )+(\phi ^{}{\displaystyle \frac{\mathrm{}^2}{2m}}^2\phi )^{}\right]+{\displaystyle \frac{\mathrm{}^2}{4m}}^2(\phi ^{}\phi )`$ (118)
$`=`$ $`2{\displaystyle \frac{1}{2m}}\left|{\displaystyle \frac{\mathrm{}}{i}}\phi \right|^2{\displaystyle \frac{\mathrm{}^2}{4m}}^2(\phi ^{}\phi )`$ (119)
$`=`$ $`{\displaystyle \frac{1}{2}}\left[(\phi ^{}{\displaystyle \frac{\mathrm{}^2}{2m}}^2\phi )+(\phi ^{}{\displaystyle \frac{\mathrm{}^2}{2m}}^2\phi )^{}\right]+{\displaystyle \frac{1}{2m}}\left|{\displaystyle \frac{\mathrm{}}{i}}\phi \right|^2,`$ (120)
we can represent the trace of $`𝐏_\mathrm{K}^{\mathrm{DF}}`$ in the form

$$_\mathrm{\Omega }\mathrm{tr}𝐏_\mathrm{K}^{\mathrm{DF}}𝑑𝐫=2T_s[n]_\mathrm{\Omega }+\frac{\mathrm{}^2}{4m}_Sn(𝐫)𝑑𝐒.$$
(121)
From (116) and (121), we obtain in final

$`2T_s[n]_\mathrm{\Omega }`$ $`=`$ $`{\displaystyle _\mathrm{\Omega }}n(𝐫)U_{\mathrm{eff}}(𝐫)𝑑𝐫`$ (122)
$`+{\displaystyle _S}𝐫𝐏_\mathrm{K}^{\mathrm{DF}}𝑑𝐒{\displaystyle \frac{\mathrm{}^2}{4m}}{\displaystyle _S}n(𝐫)𝑑𝐒,`$
which is identical with (18) with (21). In this respect, it is interesting to note that we have arbitrariness to define the kinetic-energy functional in another form

$`2T_s[n]_\mathrm{\Omega }`$ $``$ $`{\displaystyle _\mathrm{\Omega }}\mathrm{tr}𝐏_\mathrm{K}^{\mathrm{DF}}𝑑𝐫`$ (124)
$`=`$ $`{\displaystyle \underset{i}{}}f(ϵ_i){\displaystyle _\mathrm{\Omega }}\left[(\phi _i^{}{\displaystyle \frac{\mathrm{}^2}{2m}}^2\phi _i)+(\phi _i^{}{\displaystyle \frac{\mathrm{}^2}{2m}}^2\phi _i)^{}\right]𝑑𝐫`$
$`+{\displaystyle \frac{\mathrm{}^2}{4m}}{\displaystyle _\mathrm{\Omega }}^2n(𝐫)𝑑𝐫,`$
involving the last term of (122) here.

## References


format: text

text:
# Varying Cosmological Constant and the Machian Solution in the Generalized Scalar-Tensor Theory

## Abstract

The cosmological constant $`(1/2)\lambda _1\varphi _{,\mu }\varphi ^{,\mu }/\varphi ^2`$ is introduced to the generalized scalar-tensor theory of gravitation with the coupling function $`\omega (\varphi )=\eta /(\xi 2)`$ and the Machian cosmological solution satisfying $`\varphi =O(\rho /\omega )`$ is discussed for the homogeneous and isotropic universe with a perfect fluid (with negative pressure). We require the closed model and the negative coupling function for the attractive gravitational force. The constraint $`\omega (\varphi )<3/2`$ for $`0\xi <2`$ leads to $`\eta >3`$. If $`\lambda _1<0`$ and $`0\eta /\lambda _1<2`$, the universe shows the slowly accelerating expansion. The coupling function diverges to $`\mathrm{}`$ and the scalar field $`\varphi `$ converges to $`G_{\mathrm{}}^1`$ when $`\xi 2`$ ($`t+\mathrm{}`$). The cosmological constant decays in proportion to $`t^2`$. Thus the Machian cosmological model approaches to the Friedmann universe in general relativity with $`\ddot{a}=0`$, $`\lambda =0`$, and $`p=\rho /3`$ as $`t+\mathrm{}`$. General relativity is locally valid enough at present.
PACS numbers: 04.50.+h, 98.80.-k

Since the generalized scalar-tensor theory of gravitation - was proposed, many attempts to determine the arbitrary coupling function $`\omega (\varphi )`$ have been made (see, for example, - and references therein). Recently we discussed a new aspect of the coupling function in the Machian point of view and proposed $`\omega (\varphi )=\eta /(\xi 2)`$ . This coupling function does not include explicitly the scalar field $`\varphi `$ but depends on the parameter $`\xi `$, and varies in time very slowly owing to the physical revolution of matter in the universe ($`0\xi (t)<2`$). As the parameter $`\xi `$ approaches to $`2`$ (negative pressure $`\gamma =1/3`$), the coupling function diverges to the minus infinity. If we assume $`ϵ2\xi 10^3`$ at present, we obtain $`\omega 10^3`$ which is compatible with the recent observations .

For this coupling function, the generalized scalar-tensor theory of gravitation has a simple cosmological solution satisfying $`\varphi =O(\rho /\omega )`$ (Machian solution) for the homogeneous and isotropic universe with a perfect fluid with pressure. The scalar field in this closed model converges to a finite constant $`G_{\mathrm{}}^1>0`$ (, which does not differ much from the present gravitational constant $`G_0^1`$) when $`\xi 2`$ (probably, $`t+\mathrm{}`$). So the Machian cosmological solution realize dynamically the almost constant gravitational ”constant” as the result of the evolution of the universe.

However, this cosmological model shows the extremely slowly decelerating expansion when $`\xi 2`$, which is not compatible with the recent measurements  of the distances to type Ia supernovae. In the present paper, we discuss the Machian cosmological solution in the (modified) generalized scalar-tensor theory of gravitation with the varying cosmological constant to realize the slowly accelerating expansion of the universe.

Let us start with the following action -

$$S=d^4x\sqrt{g}\left\{\varphi \left[R+\lambda (\varphi ,\varphi _{,\mu }\varphi ^{,\mu })\right]+16\pi L_m\frac{\omega (\varphi )}{\varphi }g^{\mu \nu }\varphi _{,\mu }\varphi _{,\nu }\right\},$$
(1)
where $`R`$ is the scalar curvature of the metric $`g_{\mu \nu }`$, $`\varphi (x)`$ is the Brans-Dicke scalar field, $`\omega (\varphi )`$ is an arbitrary coupling function, and $`L_m`$ represents the Lagrangian for the matter fields. The term $`\lambda (\varphi ,\varphi _{,\mu }\varphi ^{,\mu })`$ represents the cosmological constant, which is modified from $`\lambda (\varphi )`$, a function of only $`\varphi `$. It should be noted that the term $`\varphi _{,\mu }\varphi ^{,\mu }`$ is a scalar. The ordinary cosmological constant must be positive ($`\lambda >0`$) for the cosmological repulsion. We assume a particular form of the cosmological constant in the Machian point of view (in order to realize a solution satisfying $`\varphi =O(\rho /\omega )`$):

$$\lambda (\varphi ,\varphi _{,\mu }\varphi ^{,\mu })\frac{1}{2}\lambda _1\varphi _{,\mu }\varphi ^{,\mu }/\varphi ^2,$$
(2)
where $`\lambda _1`$ is a constant (later, we require $`\lambda _1<0`$). For this particular cosmological constant, we obtain from the action Eq.(1)

$$S=d^4x\sqrt{g}\left\{\varphi R+16\pi L_m\frac{\left[\omega (\varphi )+\lambda _1\right]}{\varphi }g^{\mu \nu }\varphi _{,\mu }\varphi _{,\nu }\right\}.$$
(3)
We can regard that the present cosmological constant is a constant-part of the coupling function of $`\varphi `$. The variation of Eq.(3) with respect to $`g_{\mu \nu }`$ and $`\varphi `$ leads to the field equations

$`R_{\mu \nu }{\displaystyle \frac{1}{2}}Rg_{\mu \nu }`$ $`=`$ $`{\displaystyle \frac{8\pi }{\varphi }}T_{\mu \nu }{\displaystyle \frac{\left[\omega (\varphi )+\lambda _1\right]}{\varphi ^2}}\left(\varphi _{,\mu }\varphi _{,\nu }{\displaystyle \frac{1}{2}}g_{\mu \nu }\varphi _{,\lambda }\varphi ^{,\lambda }\right)`$ (4)
$`{\displaystyle \frac{1}{\varphi }}(\varphi _{,\mu ;\nu }g_{\mu \nu }\mathrm{}\varphi ),`$
$$\mathrm{}\varphi =\frac{1}{3+2\left[\omega (\varphi )+\lambda _1\right]}\left[8\pi T+\frac{d\omega (\varphi )}{d\varphi }\varphi _{,\lambda }\varphi ^{,\lambda }\right],$$
(5)
which satisfy the conservation law of the energy-momentum $`T_{\mu \nu }`$

$$T_{;\nu }^{\mu \nu }=0.$$
(6)
The line element for the Friedmann-Robertson-Walker metric is

$$ds^2=dt^2+a^2(t)[d\chi ^2+\sigma ^2(\chi )(d\theta ^2+\mathrm{sin}^2\theta d\phi ^2)],$$
(7)
where $`\sigma (\chi )`$ is $`\mathrm{sin}\chi `$, $`\chi `$, and $`\mathrm{sinh}\chi `$ for closed ($`k=+1`$), flat ($`k=0`$), and open ($`k=1`$) spaces, respectively. The energy-momentum tensor for the perfect fluid with pressure $`p`$ and the mass density $`\rho `$ is given as

$$T_{\mu \nu }=pg_{\mu \nu }(\rho +p)u_\mu u_\nu .$$
(8)
The nonvanishing components are $`T_{00}=\rho `$, $`T_{ii}=pg_{ii}`$ ($`i0`$), and its trace is $`T=\rho 3p`$ for the homogeneous and isotropic universe.

The energy conservation Eq.(6) leads to the equation of continuity

$$\dot{\rho }+3\frac{\dot{a}}{a}\left(\rho +p\right)=0,$$
(9)
which gives, with the barotropic equation of state

$$p(t)=\gamma \rho (t),1\gamma 1/3,$$
(10)
$$\rho (t)a^n(t)=const,$$
(11)
where $`n=3(\gamma +1)`$.

The nonvanishing components of the field equation (4) are

$`2a\ddot{a}+\dot{a}^2+k`$ $`=`$ $`{\displaystyle \frac{\left[\omega (\varphi )+\lambda _1\right]}{2}}a^2\left({\displaystyle \frac{\dot{\varphi }}{\varphi }}\right)^2+a\dot{a}\left({\displaystyle \frac{\dot{\varphi }}{\varphi }}\right)`$ (12)
$`{\displaystyle \frac{8\pi a^2p}{\varphi }}{\displaystyle \frac{8\pi a^2\left(\rho 3p\right)}{3+2\left[\omega (\varphi )+\lambda _1\right]}}{\displaystyle \frac{1}{\varphi }},`$
and

$$\frac{3}{a^2}\left(\dot{a}^2+k\right)=\frac{\left[\omega (\varphi )+\lambda _1\right]}{2}\left(\frac{\dot{\varphi }}{\varphi }\right)^2+\frac{\ddot{\varphi }}{\varphi }+\frac{8\pi \rho }{\varphi }\frac{8\pi \left(\rho 3p\right)}{3+2\left[\omega (\varphi )+\lambda _1\right]}\frac{1}{\varphi }.$$
(13)
The field equation (5) gives

$$\ddot{\varphi }+3\frac{\dot{a}}{a}\dot{\varphi }=\frac{1}{3+2\left[\omega (\varphi )+\lambda _1\right]}\left[8\pi \left(\rho 3p\right)\frac{d\omega (\varphi )}{d\varphi }\dot{\varphi }^2\right].$$
(14)
We adopt as usual Eqs.(13), (14), and (11) as the independent equations to solve simultaneously.

Let us require as the coupling function

$$\omega (\varphi )\frac{\eta }{\xi 2},$$
(15)
which is necessarily derived from the condition for the reasonable Machian solution . The parameter $`\xi =13\gamma `$ varies in time very slowly as a quasi-static process and so we may regard that the parameter $`\xi `$ is constant when we execute the derivative with respect to $`t`$. We introduce another scalar function $`\mathrm{\Phi }(t)`$ by

$$\varphi (t)=\frac{8\pi }{3+2\left[\omega (\varphi )+\lambda _1\right]}\mathrm{\Phi }(t)$$
(16)
for the Machian solution satisfying $`\varphi =O(\rho /\omega )`$. Taking Eq.(16) and $`d\omega /d\varphi =0`$ into account, we obtain from Eq.(14)

$$\ddot{\mathrm{\Phi }}+3\frac{\dot{a}}{a}\dot{\mathrm{\Phi }}=\xi \rho ,$$
(17)
which means that the ratio $`\dot{a}/a`$ does not include $`\omega `$, and so we find for the expansion parameter

$$a(t)A(\omega )\alpha (t),$$
(18)
where $`A`$ and $`\alpha `$ are arbitrary functions of only $`\omega `$ and $`t`$ respectively.

After eliminating $`\ddot{\varphi }`$ by Eq.(14), we get from Eq.(13)

$`{\displaystyle \frac{\omega }{2}}\left[\left({\displaystyle \frac{\dot{\mathrm{\Phi }}}{\mathrm{\Phi }}}\right)^2+{\displaystyle \frac{4\rho }{\mathrm{\Phi }}}\right]{\displaystyle \frac{3k}{A^2(\omega )\alpha ^2}}`$ (19)
$`=`$ $`3\left({\displaystyle \frac{\dot{\alpha }}{\alpha }}\right)^2+3\left({\displaystyle \frac{\dot{\alpha }}{\alpha }}\right)\left({\displaystyle \frac{\dot{\mathrm{\Phi }}}{\mathrm{\Phi }}}\right){\displaystyle \frac{\lambda _1}{2}}\left({\displaystyle \frac{\dot{\varphi }}{\varphi }}\right)^2{\displaystyle \frac{\left(3+2\lambda _1\right)\rho }{\mathrm{\Phi }}}.`$
For the closed and the open spaces ($`k=\pm 1`$), if we require that Eq.(19) is identically satisfied for all arbitrary values of $`\omega `$, we find that the coefficient $`A(\omega )`$ must have the following form

$$\frac{3}{A^2(\omega )}=\left|\frac{\omega (\varphi )}{2}+B\right|,$$
(20)
where $`B`$ is a constant with no dependence of $`\omega `$ and furthermore we obtain

$$\left(\frac{\dot{\mathrm{\Phi }}}{\mathrm{\Phi }}\right)^2+\frac{4\rho }{\mathrm{\Phi }}kj\frac{1}{\alpha ^2}$$
(21)
and

$$3\left(\frac{\dot{\alpha }}{\alpha }\right)^2+3\left(\frac{\dot{\alpha }}{\alpha }\right)\left(\frac{\dot{\mathrm{\Phi }}}{\mathrm{\Phi }}\right)\frac{\lambda _1}{2}\left(\frac{\dot{\varphi }}{\varphi }\right)^2\frac{\left(3+2\lambda _1\right)\rho }{\mathrm{\Phi }}kj\frac{B}{\alpha ^2}$$
(22)
using a notation $`j=1`$ for $`\omega /2+B<0`$ and $`j=+1`$ for $`\omega /2+B>0`$.

Thus we find the similar Machian cosmological solution in the generalized scalar-tensor theory of gravitation with the varying cosmological constant,

$$\mathrm{\Phi }(t)=\zeta \rho (t)t^2$$
(23)
and

$$\alpha (t)=bt$$
(24)
with

$$\zeta =1/(\xi 2),$$
(25)
$$b=\{\begin{array}{c}(4\xi ^2)^{1/2},forkj=1and\mathrm{\hspace{0.33em}0}\xi <2\hfill \\ (\xi ^24)^{1/2},forkj=+1and\mathrm{\hspace{0.33em}2}<\xi 4,\hfill \end{array}$$
(26)
and

$$B=\frac{\lambda _1}{2}\frac{3}{(\xi 2)(\xi +2)}.$$
(27)
There is a discontinuity at $`\xi =2`$ and we restrict to the range $`0\xi <2`$ owing to the evolutionary continuity from $`\xi =0`$ (the radiation era) and $`\xi =1`$ (the mater-dominated era with $`p=0`$). So we require the closed model ($`k=+1`$, $`j=1`$) for the attractive gravitational force ($`G>0`$). Both the coupling function $`\omega (\varphi )=\eta /(\xi 2)`$ for $`0\xi <2`$ and the constraint

$$\frac{\omega (\varphi )}{2}+B<0$$
(28)
lead necessarily to $`\eta >0`$ and $`\omega <0`$. We require $`\eta >3`$ to avoid the singularity ($`\omega <3/2`$). We get $`\omega (\varphi )=\eta /2`$ and $`B=\lambda _1/2+3/4`$ when $`\xi =0`$, and so the constraint Eq.(28) gives $`\eta 3>2\lambda _1`$. Experimentally, if we find $`\left|\omega \right|10^3`$ , we obtain $`2\xi ϵ10^3`$ (assuming $`\eta 3`$). Though the constants $`\zeta `$ and $`b`$ diverge at $`\xi =2`$, the scalar field $`\varphi `$ and the expansion parameter $`a(t)`$ themselves do not diverge at $`\xi =2`$. The crucial point at $`\xi =2`$ is that the sign of the coupling function $`\omega (\varphi )`$ reverses there ($`j=1j=+1`$ for $`k=+1`$).

The expansion parameter is finally expressed as

$$a(t)A(\omega )bt=\left[6/f(\xi )\right]^{1/2}t,$$
(29)
where

$$f(\xi )\lambda _1(\xi 2)(\xi +2)+\eta (\xi +2)6.$$
(30)
When $`\xi 2`$, we get the finite expansion parameter

$$a(t)=\sqrt{3/(2\eta 3)}t.$$
(31)
For the enough expansion at present, we need require that the constant $`\eta `$ is not so much. The value $`\eta =3`$ gives the expansion parameter$`a(t)=t`$ (light velocity). If $`\eta >3`$ and $`\lambda _1<0`$, the quadratic function $`f(\xi )`$ is always positive for the variable $`\xi `$ ($`0\xi <2`$) and satisfies Eq.(28). The function $`f(\xi )`$ becomes a maximum at $`\xi _{\mathrm{max}}=\eta /\lambda _1`$. In the case $`\xi _{\mathrm{max}}2`$, $`f(\xi )`$ gives a monotonous increasing function for $`0\xi <2`$, and in the case $`0<\xi _{\mathrm{max}}<2`$, gives a monotonous decreasing function for $`\xi _{\mathrm{max}}\xi <2`$. If $`\eta >3`$ and $`\lambda _1>0`$, the quadratic function $`f(\xi )`$ is positive for $`0\xi <2`$ when $`\eta 3>2\lambda _1`$, and gives always a monotonous increasing function for $`0\xi <2`$. If $`\lambda _1=0`$, then the function $`f(\xi )`$ becomes a linear function and shows a monotonous increase for $`\eta >0`$. Therefore, if $`\lambda _1<0`$, and $`0\eta /\lambda _1<2`$, the universe shows the slowly accelerating expansion for the period $`\eta /\lambda _1\xi <2`$.

The scalar field $`\varphi `$ for the coupling function $`\omega (\varphi )=\eta /(\xi 2)`$ is given as the following and we obtain when $`\xi 2`$

$$\varphi (t)=\frac{8\pi \rho (t)t^2}{\left(3+\lambda _1\right)(\xi 2)+2\eta }\frac{4\pi \rho (t)t^2}{\eta }const,$$
(32)
which converges to a definite and finite constant in the limit. The asymptotic behavior ($`\xi 2`$) of the scalar field is the same as that of the case without the cosmological constant. It should be remarked that the gravitational constant $`G`$ is determined by the mass density and the age of the universe if we adopt $`\eta 3`$ as the coupling function is large enough. If $`t_0=1.5\times 10^{10}yr`$, we obtain $`\rho _0=1.6\times 10^{29}g.cm^3`$, which is very near to the critical density $`\rho _c10^{29}g.cm^3`$. As the parameter $`\xi 2`$, the coupling function $`\omega (\varphi )`$ diverges to the minus infinity and the gravitational constant approaches dynamically to the constant $`G_{\mathrm{}}`$

The cosmological constant $`\lambda (t)`$ decreases rapidly in proportion to $`t^2`$ as the universe expands and converges to zero when $`\xi 2`$ ($`t+\mathrm{}`$):

$$\lambda (t)=\frac{\lambda _1}{2}\left(\frac{\dot{\varphi }}{\varphi }\right)^2\frac{(\xi 2)^2}{t^2}0.$$
(33)
The effective cosmological constant $`\mathrm{\Lambda }(t)`$ introduced in the previous paper  also decreases rapidly and converges to zero when $`\xi 2`$ ($`t+\mathrm{}`$):

$$\mathrm{\Lambda }(t)\frac{\omega (\varphi )}{2}\left(\frac{\dot{\varphi }}{\varphi }\right)^2\frac{\xi 2}{t^2}0.$$
(34)
It should be noted that the sign of the cosmological term $`\lambda (t)<0`$ is opposite to that of the usual cosmological term in the $`(i,i)`$ components of the field equations, and inversely the effective cosmological term $`\mathrm{\Lambda }(t)>0`$ is opposite in the $`(0,0)`$ component.

We can estimate the order of each terms appeared in Eqs.(12) and (13) by means of the present Machian cosmological solution when $`\omega (\varphi )=\eta /(\xi 2)\mathrm{}`$, for example,

$$\frac{8\pi }{3+2\left[\omega (\varphi )+\lambda _1\right]}\frac{a^2\xi \rho }{\varphi }\xi 20,$$
(35)
$$\frac{8\pi a^2\rho }{\varphi }\frac{6\eta }{2\eta 3}O(1),$$
(36)
$$\frac{8\pi a^2p}{\varphi }\frac{2\eta }{2\eta 3}O(1),$$
(37)
$$\frac{\omega (\varphi )}{2}a^2\left(\frac{\dot{\varphi }}{\varphi }\right)^2\xi 20,$$
(38)
$$\frac{\lambda _1}{2}a^2\left(\frac{\dot{\varphi }}{\varphi }\right)^2(\xi 2)^20,$$
(39)
$$a\dot{a}\left(\frac{\dot{\varphi }}{\varphi }\right)\xi 20,$$
(40)
and

$$a^2\frac{\ddot{\varphi }}{\varphi }\xi 20.$$
(41)
The crucial difference from the correspondences  in the Brans-Dicke theory  is that even the term Eq.(38) converges to zero when $`\omega (\varphi )\mathrm{}`$. This means that the abnormal term vanishes and the generalized scalar-tensor theory of gravitation reproduces the correspondent solution of general relativity with the same energy-momentum tensor completely when $`\xi 2`$ ($`t+\mathrm{}`$).

In the Brans-Dicke theory, the coupling parameter $`\omega `$ is arbitrary, and so we realize that the Machian solution does not reduce to that of general relativity for the fixed finite time $`t`$ when $`\left|\omega \right|+\mathrm{}`$. However, we cannot determine, for example, the limit of the term $`\mathrm{\Lambda }(t)\omega /t^2`$ when $`\left|\omega \right|+\mathrm{}`$ and $`t+\mathrm{}`$ in the Brans-Dicke theory. If we regard the coupling function $`\omega (\varphi )`$ as an arbitrary parameter in the generalized scalar-tensor theory, we obtain the similar correspondences (for example, $`\omega (\varphi )a^2\left(\dot{\varphi }/\varphi \right)^2O(1)`$) in the Brans-Dicke theory for the same Machian cosmological solution for the fixed finite time $`t`$. In this case, the generalized scalar-tensor theory does not reduce to general relativity when $`\left|\omega \right|+\mathrm{}`$ and $`\omega ^3d\omega /d\varphi 0`$. We find that the scalar field $`\varphi `$ converges to zero when $`\left|\omega \right|+\mathrm{}`$ according to the postulate $`\varphi =O(\rho /\omega )`$. For the present Machian cosmological solution in the generalized scalar-tensor theory, we know the behavior of the coupling function $`\omega (\varphi )`$ when $`t+\mathrm{}`$ and so we can estimate definitely the limit of the solution when $`t+\mathrm{}`$. Thus the generalized scalar-tensor theory of gravitation approaches dynamically to general relativity in the result of the evolution of the universe when $`t+\mathrm{}`$.

Let us remember the Friedmann equations with the cosmological term for the homogeneous and isotropic universe in general relativity:

$$2a\ddot{a}+\dot{a}^2+k\lambda a^2=\kappa pa^2,$$
(42)
$$\frac{3}{a^2}\left(\dot{a}^2+k\right)\lambda =\kappa \rho ,$$
(43)
where $`\kappa `$ is Einstein’s gravitational constant. We get from Eq.(42) when $`\ddot{a}=0`$ and $`p=\rho /3`$

$$\frac{3}{a^2}\left(\dot{a}^2+k\right)3\lambda =\kappa \rho ,$$
(44)
and find $`\lambda =0`$. If we require $`\ddot{a}(t)=0`$ and $`\lambda (t)0`$ ($`t+\mathrm{}`$), we obtain $`p\rho /3`$. This fact supports that the final state of the Machian cosmological solution with the decaying cosmological constant is the negative pressure $`\gamma =1/3`$ ($`\xi =2`$). Taking Eqs.(31) and (35)-(41) ($`k=+1`$), and $`\kappa 8\pi G_{\mathrm{}}`$ into account, we observe that Eqs.(12) and (13) reduce to Eqs.(42) and (43) respectively when $`\omega (\varphi )\mathrm{}`$ ($`t+\mathrm{}`$). The constant $`\eta `$ still remains indefinite. It is interesting that the Machian cosmological solution in the Brans-Dicke theory, of which the coupling parameter is constant and arbitrary, is correspondent to the static Einstein universe ($`\dot{a}0`$ when $`\omega \mathrm{}`$).

The cosmological constant $`\lambda (\varphi )`$ is not consistent with the Machian cosmological solution satisfying $`\varphi =O(\rho /\omega )`$ for the variable parameter $`\xi `$. Only the present form of the cosmological constant $`(1/2)\lambda _1\varphi _{,\mu }\varphi ^{,\mu }/\varphi ^2`$ admits the Machian solution in the generalized scalar-tensor theory of gravitation. The constraint $`\omega (\varphi )<3/2`$ leads to $`\eta >3`$. If $`\lambda _1<0`$ and $`0\eta /\lambda _1<2`$, the universe surely shows the slowly accelerating expansion for the later period from $`\xi =\eta /\lambda _1`$, though the expansion parameter is explicitly a linear function of $`t`$. For example, if we adopt $`\eta =3`$ and $`\lambda _1=3`$, the universe exhibits the slowly decelerating expansion before the matter-dominated era $`\xi =1`$ (for the positive pressure), the slowly accelerating expansion after the matter-dominated era (for the negative pressure) respectively.

In the generalized scalar-tensor theory of gravitation, not only the gravitational constant but also the variation of the coupling function is derived from the evolution of the universe. The remaining problem is to determine the time-variation of the parameter $`\xi (t)`$ by the physical evolution of matter in the universe. Our conjecture is that the universe passed the radiation era ($`\xi =0`$) and the matter-dominated era with negligible pressure ($`\xi =1`$) rapidly in the early stage, and has been staying the negative pressure era ($`1<\xi <2`$, maybe almost near $`\xi =2`$) for the almost all period of $`10^{10}yr`$. Finally, the universe will approach to the state of $`\xi =2`$ ($`\gamma =1/3`$) as it expands for ever.
Acknowledgment

The author is grateful to Professor Carl Brans for helpful discussions and his hospitality at Loyola University (New Orleans) where this work was done. He would also like to thank the Nagasaki Prefectural Government for financial support.