Chemical Physics Letters 658 (2016) 224–229

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Chemical Physics Letters

journal homepage: www.elsevier.com/locate/cplett

Research paper

Accuracy of temperature-derivative of radial distribution function

calculated under approximations in Ornstein-Zernike theory for one-
component Lennard-Jones fluid
Tatsuhiko Miyata ⇑, Sanae Miyazaki
Department of Physics, Ehime University, 2-5 Bunkyo-Cho, Matsuyama, Ehime 790-8577, Japan

a r t i c l e i n f o a b s t r a c t

Article history: The accuracy of the temperature derivative of radial distribution function obtained under hypernetted
Received 7 May 2016 chain (HNC), Kovalenko-Hirata (KH), Percus-Yevick (PY) and Verlet-modified (VM) closure approxima-
In final form 18 June 2016 tions is examined for one-component Lennard-Jones fluid. As relevant thermodynamic quantities,
Available online 21 June 2016
constant-volume heat capacity and thermal pressure coefficient are investigated in terms of their accu-
racy under the above four approximations. It is found that HNC and KH closures overestimate these quan-
Keywords: tities, whereas PY closure tends to underestimate them. VM closure predicts rather accurately the
Temperature derivative of radial
quantities. A significant cancellation is observed along the integration for the above quantities under
distribution function
Ornstein-Zernike integral equation theory
HNC and KH closures, especially at high density state.
Constant-volume heat capacity Ó 2016 Elsevier B.V. All rights reserved.
Thermal pressure coefficient
Lennard-Jones system

1. Introduction involves a temperature derivative of the distribution functions

Recently, attention has been paid to the Ornstein-Zernike (OZ)
theory [1–3] in terms of the accuracy of the relevant solvation free
energy (SFE) [4–6]. Related to this topic, the accuracy of excess inter-
nal energy, virial pressure and excess chemical potential have also
been examined for one-component Lennard-Jones (LJ) fluids [7,8],
where hypernetted chain (HNC) [1–3], Kovalenko-Hirata (KH)
[3,9], Percus-Yevick (PY) [1,2], and Verlet modified (VM) [10] closure
approximations have been considered. As far as the above men-
tioned thermodynamic quantities are concerned, the most impor-
tant point for the correction in terms of the radial distribution
function (RDF) is the position of the first rising (FR) region of the first
peak: namely, under assuming that the position of FR region of RDF
is precise enough, the above thermodynamic quantities are quite
accurate even if some error is still remained in the farther region
than the first peak of the RDF [6–8]. The importance of the FR region
of RDF arises from the fact that the region corresponds to a repulsive
region of the analogs of potential (or that of potential itself).
A decomposition of the SFE into energy term and entropy term
is often utilized in the analysis of solvation thermodynamics (For
example, see Ref. [11]). Since the solvation entropy is calculated
from the temperature derivative of the SFE, its rigorous calculation
⇑ Corresponding author.
E-mail address: miyata.tatsuhiko.mf@ehime-u.ac.jp (T. Miyata).
[12]. Although a numerical calculation for the temperature deriva-
tive of the distribution functions has been reported to date [12–
14], there seems to be no systematic study upon its accuracy. This
article examines the accuracy of the temperature derivative of the
RDF.
When studying the accuracy of, e.g., SFE, excess internal energy
and virial pressure, the result of molecular dynamics (MD) simula-
tion has been employed as a standard (or reference) data [6–8],
where an analysis of the error in the integrand for these thermody-
namic quantities, especially focusing on the RDF, has successfully
been executed. On the other hand, it is difficult to calculate directly
the temperature derivative of the RDF based on the MD method.
This study employs the finite difference approximation to calculate
it numerically using MD simulation. In order to utilize the result of
MD simulation as a standard data for the accuracy test of OZ theory
in this context, it is necessary to check the quantitative validity of
the temperature derivative of the RDF that is obtained on the basis
of the finite difference approximation. Since the RDF evaluated by
MD simulation involves the statistical error, attention must be paid
also to the sampling number. While the solvation entropy is usu-
ally considered in a two-component solute-solvent system at the
infinite dilution limit for the solute, it is also worth considering
the temperature derivative of the RDF for one-component system
from the viewpoint of verifying the accuracy of MD simulation.
Increasing the sampling number for the pair distribution function

http://dx.doi.org/10.1016/j.cplett.2016.06.049
0009-2614/Ó 2016 Elsevier B.V. All rights reserved.
 T. Miyata, S. Miyazaki / Chemical Physics Letters 658 (2016) 224–229 225

(or relevant quantity) for one-component system is relatively easy In Eq. (8), s(r) is defined by
thanks to the identity of the particles, compared to the solute-
sðrÞ ¼ hðrÞ  cðrÞ  bu2 ðrÞ; ð9Þ
solvent pair distribution function (or similar quantity) in a two-
component system at infinite dilution. We shall also point out that where
when attempting to examine the accuracy of the temperature
r6  3
1
r6qr
derivative of RDF, it would be effective to check the consistency u2 ðrÞ ¼ 4e exp  3 ; ð10Þ
of the relevant thermodynamic quantities. r qr r
This article deals with the temperature derivative of the RDF for and aVM is given by
one-component LJ fluid. The main objective of this study is to inves-
tigate the influence of HNC, KH, PY and VM approximations in OZ aVM ¼ 1:0175  0:275  qr3 : ð11Þ
theory upon the temperature derivative of the RDF. We consider The OZ equation, Eq. (2), is coupled with one of the closure approx-
the constant-volume heat capacity and the thermal pressure coeffi- imations stated above, to obtain the correlation functions. The RDF
cient as examples of the relevant thermodynamic quantities. Prior to gðrÞ is related to hðrÞ as
examining the accuracy of approximated OZ theory, we check the
validity of the temperature derivative of RDF obtained from MD sim- gðrÞ ¼ hðrÞ þ 1: ð12Þ
ulation that is based on the finite difference approximation. In this
validity check, we focus on the consistency between the constant-
2.2. Equations for temperature-derivative of RDF
volume heat capacity evaluated through the temperature derivative
of RDF and that through the fluctuation of relevant quantities. Sim-
This section describes the equations to be solved numerically
ilar consistency in the thermal pressure coefficient is also examined.
for the temperature-derivative of RDF. The method described here
Finally, the influence of approximations in OZ theory upon these
is based on the analysis by Yu et al. [12]. First, Eq. (2) is Fourier
thermodynamic quantities is reported.
transformed, followed by a differentiation with respect to T. After
2. Theory and computational methods a simple algebraic manipulation, we get
^
@ hðkÞ ^
@ ^cðkÞ 1 þ qhðkÞ
We restrict ourselves only to a one-component LJ fluid through- ¼ ; ð13Þ
@T @T 1  q^cðkÞ
out this study. The LJ potential is written as

12
6 
r r where k is the wave number, and the hat denotes the Fourier trans-
uðrÞ ¼ 4e  : ð1Þ form. The temperature derivatives of closure equations (Eqs. (4)–
r r
(7)) are as follows:
(A) HNC closure approximation:
2.1. Ornstein-Zernike theory  
@cðrÞ 1 @hðrÞ @cðrÞ
¼ gðrÞ buðrÞ þ hðrÞ  : ð14Þ
@T T @T @T
This section describes a brief outline of OZ theory. The OZ equa-
tion reads [1–3] (B) KH closure approximation:
8 h i
hðrÞ ¼ cðrÞ þ qc  hðrÞ; ð2Þ
@cðrÞ < gðrÞ 1T buðrÞ þ hðrÞ @T  @T
@hðrÞ @cðrÞ
for dðrÞ 6 0
¼ ð15Þ
where hðrÞ and cðrÞ represent the total and direct correlation func- @T : 1 buðrÞ for dðrÞ > 0:
tions, respectively. q is the fluid density, and ⁄ stands for the convo- T

lution integral. In this study, we employ the following four closure (C) PY closure approximation:
approximations to complement OZ theory, where uðrÞ and b are the  
interaction potential energy and 1=kB T, respectively (kB denotes the @cðrÞ 1 @hðrÞ @cðrÞ
¼ gðrÞ buðrÞ þ ðexp½buðrÞ  1Þ  : ð16Þ
Boltzmann constant, and T the temperature). First, we define dðrÞ as @T T @T @T
dðrÞ ¼ buðrÞ þ hðrÞ  cðrÞ: ð3Þ (D) VM closure approximation:
Then, the closure equations we consider herein are as follows.
 
@cðrÞ 1 @hðrÞ @cðrÞ @bðrÞ
¼ gðrÞ buðrÞ þ hðrÞ  þ gðrÞ ; ð17Þ
@T T @T @T @T
(A) HNC closure approximation [1–3]:
where
1 þ hðrÞ ¼ exp½dðrÞ: ð4Þ ( 2þaVM sðrÞ @sðrÞ
@bðrÞ  2f1þaVM sðrÞg sðrÞ @T for sðrÞ P 0
(B) KH closure approximation [3,9]: ¼ ð18Þ
 @T sðrÞ @sðrÞ for sðrÞ < 0:
@T
exp½dðrÞ for dðrÞ 6 0
1 þ hðrÞ ¼ ð5Þ
1 þ dðrÞ for dðrÞ > 0: @sðrÞ=@T in Eq. (18) is given by

(C) PY closure approximation [1,2]: @sðrÞ @hðrÞ @cðrÞ 1

¼  þ bu2 ðrÞ: ð19Þ
@T @T @T T
1 þ hðrÞ ¼ exp½buðrÞf1 þ hðrÞ  cðrÞg: ð6Þ
For HNC approximation, Eqs. (13) and (14) are solved simulta-
(D) VM closure approximation [10]: neously for @hðrÞ=@T and @cðrÞ=@T. @hðrÞ=@T and @cðrÞ=@T for KH
1 þ hðrÞ ¼ exp½dðrÞ þ bðrÞ; ð7Þ approximation are obtained from Eqs. (13) and (15) simultane-
ously. Similarly, PY or VM approximation solves Eqs. (13) and
where (16) or Eqs. (13) and (17), respectively, for @hðrÞ=@T and @cðrÞ=@T.
8 Notice that @gðrÞ=@T is equivalent to @hðrÞ=@T (see Eq. (12)). We
< sðrÞ2
for sðrÞ P 0
2f1þaVM sðrÞg shall also note that it is necessary to obtain the numerical solution
bðrÞ ¼ ð8Þ
:  1 sðrÞ2 for sðrÞ < 0: of OZ equation (Eq. (2)) and closure equation (One of Eqs. (4)–(7))
2
prior to solving the equations for @hðrÞ=@T and @cðrÞ=@T.
226 T. Miyata, S. Miyazaki / Chemical Physics Letters 658 (2016) 224–229

2.3. Constant-volume heat capacity and thermal pressure coefficient state (I), whereas kB T=e ¼ 3:2; 3:4; 3:8; and 4:0 regarding the states
(II) and (III). The timestep of 5 fs is adopted for all the states rele-
We treat the constant-volume heat capacity, C V ¼ ð@E=@TÞq , and vant to (II) and (III), whereas 10 fs is applied to all the states rele-
the thermal pressure coefficient, cV ¼ ð@p=@TÞq , where E and p rep- vant to (I). The cutoff length of the LJ potential is set at 7r. As a
resent the internal energy and the pressure, respectively. Let us thermostat, we employ the Nose-Hoover chain. After equilibrating
consider the energy equation and the virial equation [1]. Then, the system by 1 ns simulation, the production run of 2 ns in length
C V and cV are given by is performed to evaluate the RDF, C V and cV .
Z 1
CV 3 2 @gðrÞ
¼ k B þ 2p q drr uðrÞ ð20Þ
N 2 0 @T 3. Results and discussion
and
First, we examine the precision of @gðrÞ=@T obtained from MD
Z 1
2 duðrÞ @gðrÞ
3 simulation using the finite difference approximation. Examples of
cV ¼ qkB  pq2 drr ; ð21Þ
gðrÞ and @gðrÞ=@T from MD simulation are shown in Fig. 1, regard-
3 0 dr @T
ing the thermodynamic state (III) (see Supplementary Content for
respectively, where N represents the number of molecules. For OZ the data at the other thermodynamic states). Fig. 1(a) shows gðrÞ
theory, we use Eqs. (20) or (21) to calculate C V or cV . C V and cV
at ðqr3 ; kB T=eÞ ¼ ð0:9; 3:4Þ and ðqr3 ; kB T=eÞ ¼ ð0:9; 3:8Þ. The differ-
are also written as [15]
ence in the temperature, kB T=e, is 0.4 in the case of Fig. 1(a), which
 
3 is hereafter denoted by kB DT=e ¼ 0:4. Subtracting gðrÞ at
hdU 2 i ¼ kB T 2 C V  NkB ð22Þ
2 ðqr3 ; kB T=eÞ ¼ ð0:9; 3:4Þ from that at ðqr3 ; kB T=eÞ ¼ ð0:9; 3:8Þ, fol-
lowed by being divided by kB DT=e ¼ 0:4, yields the dimensionless
and @gðrÞ=@T at the thermodynamic state (III) based on the finite differ-
hdUdpi ¼ kB T 2 ðcV  qkB Þ; ð23Þ ence approximation. Thus determined @gðrÞ=@T is drawn in Fig. 1
(b), which corresponds to the left axis of ordinate. The curve of
respectively, where h  i denotes the ensemble average in a canon- @gðrÞ=@T using the temperature difference of kB DT=e ¼ 0:8 is also
ical (NVT) ensemble. dU in Eqs. (22) and (23) is the deviation of indicated in Fig. 1(b). The difference between the two curves of
potential energy from its ensemble average, and dp in Eq. (23) is @gðrÞ=@T in Fig. 1(b) is practically invisible with the scale of left
pressure correspondence. We employ Eqs. (20)–(23) for canonical axis of ordinate. Nevertheless, we plot the difference between
ensemble MD simulation to evaluate C V and cV . Regarding MD sim- these curves also in Fig. 1(b) (right axis of ordinate), which
ulation, @gðrÞ=@T in Eqs. (20) and (21) is obtained from the finite dif- indicates that the magnitude of the difference is at most a few
ference approximation.

2.4. Computational details 2.5

(a) kBT/ε = 3.4
We set r ¼ 3:405 Å and e ¼ 0:2380 kcal/mol throughout this 2.0 kBT/ε = 3.8
study. We consider the following three thermodynamic states in
this article: the state (I) ðqr3 ; kB T=eÞ ¼ ð0:7; 2:4Þ, the state (II) 1.5
g(r) [-]

ðqr3 ; kB T=eÞ ¼ ð0:7; 3:6Þ, and the state (III) ðqr3 ; kB T=eÞ ¼ ð0:9; 3:6Þ.
As for OZ theory, we set the grid separation and the number of 1.0
grids as 0.01 Å and 16,384, respectively. MDIIS method [16] is used
for numerical convergence of the equations regarding hðrÞ and cðrÞ, 0.5
whereas Picard method is used for obtaining @hðrÞ=@T and
@cðrÞ=@T. The outline of the Picard method we used is as follows. 0.0
We shall consider HNC approximation as an example for explana- 0.0 0.5 1.0 1.5 2.0 2.5
tion. First, Eqs. (2) and (4) should be solved, the solution of which r/σ [-]
are used in solving Eqs. (13) and (14). Then, the initial guesses for
@hðrÞ=@T and @cðrÞ=@T, which may be set as zero in the current sys- 0.4 0.03
tem, are substituted into the right hand side of Eq. (14) to renew (b) kBΔT/ε = 0.4
@cðrÞ=@T. After applying the Fourier transform to @cðrÞ=@T, kBΔT/ε = 0.8
dg(r)/dT×(ε/kB) [-]

0.2
^
@ hðkÞ=@T is evaluated through Eq. (13), followed by an inverse difference 0.02
difference [-]

Fourier transform to obtain @hðrÞ=@T. This cycle is repeated until

@hðrÞ=@T is converged. Similar algorithm is applied also to other 0.0
0.01
approximations. The numerical tolerance for convergence is set
at 108 for the states of (I) and (II), whereas 109 for the state of -0.2
(III). The offset of gðrÞ less than 2  106 inside the repulsive core 0.00
observed after the numerical convergence is cut off.
-0.4
In the MD calculation, we perform an NVT ensemble MD simu- 0 1 2 3 4 5
lation to calculate the RDF, C V and cV . 5324 LJ particles are placed
r/σ [-]
in a cubic cell under the periodic boundary condition so that the
fluid number density becomes a prescribed value. In order to Fig. 1. (a) Examples of gðrÞ obtained from MD simulation concerning the thermo-
obtain the temperature-derivative of RDF by a finite difference dynamic state (III). (b) Examples of @gðrÞ=@T obtained from MD simulation at the
approximation, we perform additional MD simulations both at thermodynamic state (III), which correspond to the left axis of ordinate. The data of
@gðrÞ=@T in the panel (b) is based on the finite difference approximation. The
slightly raised temperature and at slightly lowered temperature
difference of @gðrÞ=@T between the finite difference approximation with
at a given density in comparison with the states (I), (II) and (III): kB DT=e ¼ 0:4 and that with kB DT=e ¼ 0:8 is also shown in the panel (b), which
namely, we consider kB T=e ¼ 2:0; 2:2; 2:6; and 2:8 regarding the corresponds to the right axis of ordinate.
 T. Miyata, S. Miyazaki / Chemical Physics Letters 658 (2016) 224–229 227

percentage compared to the magnitude of the oscillation in Table 2

@gðrÞ=@T. A systematic error is observed in the vicinity of The values of cV r3 =kB obtained from MD simulation through Eqs. (21) and (23). In a
numerical integration of Eq. (21), @gðrÞ=@T evaluated from a finite difference
r=r ¼ 1:0. Probably, this systematic error is due to the employment approximation is used, where two temperature differences are considered: one is
of finite difference approximation. We summarize the data of kB DT=e ¼ 0:4, whereas the other is kB DT=e ¼ 0:8. The corresponding results of
C V =ðNkB Þ and cV r3 =kB obtained from MD simulation in Tables 1 cV r3 =kB are indicated in the rows of kB DT=e ¼ 0:4 and kB DT=e ¼ 0:8, respectively.
and 2, respectively. Table 1 shows C V =ðNkB Þ through the integra- State qr3 kB T=e kB DT=e ¼ 0:4 kB DT=e ¼ 0:8 Eq. (23)
tion of Eq. (20) using the finite difference approximation with
(I) 0.7 2.4 2.65 2.65 2.62 ± 0.04
kB DT=e ¼ 0:4, and those with kB DT=e ¼ 0:8, together with the (II) 0.7 3.6 2.37 2.38 2.41 ± 0.03
results of Eq. (22). Table 2 shows the correspondence of cV r3 =kB (III) 0.9 3.6 4.25 4.27 4.25 ± 0.07
related to Eqs. (21) and (23). The numerical integration of Eqs.
(20) and (21) is performed in the range of 0 < r=r < 7:0, and the
farther integration than r=r ¼ 7:0 is cut off. At each thermody- 0.4
namic state, the results of C V =ðNkB Þ obtained from Eqs. (20) both (a) MD
with kB DT=e ¼ 0:4 and kB DT=e ¼ 0:8 coincide excellently with each HNC
KH
other. Furthermore, C V =ðNkB Þ through Eq. (20) agrees with that

dg(r)/dT×(ε/kB) [-]
PY
through Eq. (22) roughly within the statistical error. Similar ten- 0.2 VM

dency is observed also for cV r3 =kB in Table 2. Therefore, we may

conclude that the difference between the MD results of @gðrÞ=@T
with the finite difference approximation of kB DT=e ¼ 0:4 and those 0.0
of kB DT=e ¼ 0:8 is insignificant, as far as C V and cV are concerned. It
is also found that we can apply the finite difference approximation
to obtain @gðrÞ=@T from the MD simulation with the considerable
-0.2
accuracy. In particular, it is possible to use thus obtained 0.0 1.0 2.0 3.0
@gðrÞ=@T as a standard (or reference) data in the error analysis of
r/σ [-]
the integrand in Eqs. (20) and (21).
We turn to the error involved in the approximations of OZ the-
0.4
ory. In Fig. 2, @gðrÞ=@T obtained from OZ theory at thermodynamic
state (III) is shown (see Supplementary Content for the data at the (b) MD
HNC
other thermodynamic states). The corresponding result of @gðrÞ=@T dg(r)/dT×(ε/kB) [-]
KH
PY
from MD simulation with finite difference approximation of 0.2 VM
kB DT=e ¼ 0:4 is also shown in Fig. 2. Fig. 2(a) exhibits an overall
view of @gðrÞ=@T curves, whereas Fig. 2(b) focuses on their first
peak. The overall oscillatory behavior in @gðrÞ=@T is qualitatively
0.0
captured by the approximations considered herein (i.e. HNC, KH,
PY and VM), which is seen in Fig. 2(a). As seen in the enlarged
curves of Fig. 2(b), on the other hand, the deviations from the
MD result is significant in some approximations concerning the -0.2
0.8 0.9 1.0 1.1
first peak: in particular, a leftward shift of the first peak is remark-
able in HNC and KH approximations. PY approximation gives a r/σ [-]
slightly rightward shift concerning the left half of the first peak
Fig. 2. (a) Examples of @gðrÞ=@T from OZ theory together with that from MD
of @gðrÞ=@T. VM approximation predicts the first peak of @gðrÞ=@T
simulation at the thermodynamic state (III). The MD result is obtained from the
rather accurately. The latter result for VM closure concerning the finite difference approximation with kB DT=e ¼ 0:4. (b) Enlarged curves of @gðrÞ=@T
accuracy of @gðrÞ=@T may be expected from the fact that VM clo- shown in the panel (a) focusing on their first peak.
sure provides rather accurate gðrÞ in wide range of thermodynamic
states [7,10]. For the thermodynamic states (I) and (II), we have
confirmed that qualitatively similar results are obtained to the Table 3
Comparison of C V =ðNkB Þ between MD simulation and OZ theory. The data of MD
state (III) regarding the HNC, KH and VM approximations, as seen
simulation indicated in this table is obtained through Eq. (22).
in Supplementary Content. Under PY approximation at the state
(I), a slightly leftward shift is observed in the right half of the first State qr3 kB T=e MD HNC KH PY VM
peak of @gðrÞ=@T. (I) 0.7 2.4 2.01 ± 0.01 2.06 2.07 1.98 2.00
The values of C V and cV obtained from OZ theory are summa- (II) 0.7 3.6 1.96 ± 0.01 2.00 2.00 1.93 1.95
rized in Tables 3 and 4, respectively. The results of MD simulation (III) 0.9 3.6 2.24 ± 0.01 2.33 2.35 2.18 2.22

using Eqs. (22) and (23) are also included in Tables 3 and 4, respec-
tively. HNC closure tends to overestimate both C V and cV . KH clo-
Table 4
Comparison of cV r3 =kB between MD simulation and OZ theory. The data of MD
simulation indicated in this table is obtained through Eq. (23).
Table 1
The values of C V =ðNkB Þ obtained from MD simulation through Eqs. (20) and (22). In a State qr3 kB T=e MD HNC KH PY VM
numerical integration of Eq. (20), @gðrÞ=@T evaluated from a finite difference
approximation is used, where two temperature differences are considered: one is (I) 0.7 2.4 2.62 ± 0.04 2.79 2.82 2.43 2.60
kB DT=e ¼ 0:4, whereas the other is kB DT=e ¼ 0:8. The corresponding results of (II) 0.7 3.6 2.41 ± 0.03 2.49 2.51 2.24 2.34
C V =ðNkB Þ are indicated in the rows of kB DT=e ¼ 0:4 and kB DT=e ¼ 0:8, respectively. (III) 0.9 3.6 4.25 ± 0.07 4.56 4.62 3.92 4.14

State qr3 kB T=e kB DT=e ¼ 0:4 kB DT=e ¼ 0:8 Eq. (22)

(I) 0.7 2.4 2.01 2.01 2.01 ± 0.01

(II) 0.7 3.6 1.96 1.96 1.96 ± 0.01 sure exhibits the overestimation slightly more than HNC closure.
(III) 0.9 3.6 2.25 2.25 2.24 ± 0.01
It is found that PY closure exhibits a tendency to underestimate
228 T. Miyata, S. Miyazaki / Chemical Physics Letters 658 (2016) 224–229

these quantities. VM closure provides relatively accurate values

dg(r)/dT×(ε/kB) [-] or – (1/ε)×du(r)/dr [Å ]

0.8 2.8

–1
difference in IγV(r)
both for C V and cV at the thermodynamic states considered here. (a) 2.4
dg(r)/dT×(ε/kB) from MD
In what follows, we analyze the integrands of Eqs. (20) and (21) dg(r)/dT×(ε/kB) from HNC
2.0
to examine the source of error in C V and cV obtained from approx- 0.4 – (1/ε)×du(r)/dr

difference in IγV(r) [-]

imated OZ theories. Let us define ICV ðrÞ and IcV ðrÞ for this purpose 1.6
as 1.2
Z 0
0.0
2pq r
0 @gðr Þ 0.8
ICV ðrÞ ¼ dr r 02 uðr 0 Þ ð24Þ
kB 0 @T 0.4
-0.4 0.0
and
Z -0.4
2pq2 r3 r
0 duðr 0 Þ @gðr 0 Þ 0.8 1.0 1.2 1.4
IcV ðrÞ ¼  dr r 03 0 ; ð25Þ
3kB 0 dr @T r/σ [-]

respectively. In Fig. 3, examples of ‘‘differences in ICV ðrÞ” between

dg(r)/dT×(ε/kB) [-] or – (1/ε)×du(r)/dr [Å ]

0.8 2.8

–1
MD simulation and OZ theory at the thermodynamic state (III) are difference in IγV(r)
shown, which correspond to the right axes of ordinate. Fig. 3
(b) dg(r)/dT×(ε/kB) from MD 2.4
(a) and (b) indicates the ‘‘difference in ICV ðrÞ” of HNC and KH clo- dg(r)/dT×(ε/kB) from KH
2.0
0.4 – (1/ε)×du(r)/dr

difference in IγV(r) [-]

sure, respectively, in comparison with MD result (see Supplemen-
1.6
tary Content for the other data). The region where the curve of
‘‘difference in ICV ðrÞ” is right-upward indicates the overestimation 1.2
0.0
of the integrand in Eq. (20), and vice versa. In Fig. 3, the correspond- 0.8
ing curves of @gðrÞ=@T and uðrÞ=e are also shown, which correspond 0.4
to the left axes of ordinate. Similarly, examples of ‘‘differences in
-0.4 0.0
IcV ðrÞ” between MD and OZ theory are exhibited in Fig. 4, which cor-
respond to the right axes of ordinate. Fig. 4(a) and (b) deals with -0.4
0.8 1.0 1.2 1.4
HNC and KH approximations, respectively (The other data can be
found in Supplementary Content). The overestimation of the inte-
r/σ [-]
grand in Eq. (21) is indicated by the right-upward region in the Fig. 4. The differences in IcV ðrÞ, which correspond to the right axes of ordinate.
curve of ‘‘difference in IcV ðrÞ”. The curves of @gðrÞ=@T and @gðrÞ=@T and ð1=eÞ  duðrÞ=dr are also shown, which correspond to the left axes of
ð1=eÞ  duðrÞ=dr are also shown in Fig. 4, which correspond to ordinate. The results presented are obtained at the thermodynamic state (III).
‘‘Difference in IcV ðrÞ” written in the panels indicates the one between MD
the left axes of ordinate. It is found that the first peak of @gðrÞ=@T
simulation and the following approximations: (a) HNC approximation, and (b) KH
approximation.

0.8 1.0
difference in ICV(r)
(a) dg(r)/dT×(ε/kB) from MD
dg(r)/dT×(ε/kB) [-] or u(r)/ε [-]

dg(r)/dT×(ε/kB) from HNC

0.8 is located in the repulsive region of uðrÞ (Fig. 3). Therefore, the error
0.4 in the first peak of @gðrÞ=@T can result in a significant deviation from
difference in ICV(r) [-]

u(r)/ε
0.6 the precise value of C V through the integral of Eq. (20). The first
minimum of @gðrÞ=@T, on the other hand, corresponds roughly to
0.4
0.0 the well of uðrÞ. The error in @gðrÞ=@T at this region (up to
r=r  1:4) also affects the precision of C V significantly. From com-
0.2
parison between Figs. 3 and 4, the first peak of @gðrÞ=@T is located
-0.4 more deeply inside the repulsive region of duðrÞ=dr than those
0.0
of uðrÞ: hence, the error in @gðrÞ=@T at this region can have stronger
0.8 1.0 1.2 1.4 influence upon cV than C V . Moreover, cV is hardly affected by the
r/σ [-] error in @gðrÞ=@T in the farther region than its first peak (e.g.
Fig. 4), which is somewhat similar to the cases of the virial pressure,
0.8 1.0 SFE and so forth [6–8].
difference in ICV(r)
(b) dg(r)/dT×(ε/kB) from MD
Under HNC closure (Figs. 3(a) and 4(a)), the first peak of
dg(r)/dT×(ε/kB) [-] or u(r)/ε [-]

dg(r)/dT×(ε/kB) from KH
0.8 @gðrÞ=@T is shifted to the left compared to MD result, as mentioned
0.4 before. In the case of excess internal energy, only the error in the
difference in ICV(r) [-]

0.0
-0.4
0.8
Fig. 3. The differences in ICV ðrÞ, which correspond to the right axes of ordinate.
@gðrÞ=@T and uðrÞ=e are also shown, which correspond to the left axes of ordinate.
The results presented are obtained at the thermodynamic state (III). ‘‘Difference in
ICV ðrÞ” written in the panels indicates the one between MD simulation and the
following approximations: (a) HNC approximation, and (b) KH approximation.
u(r)/ε
0.6 first peak in gðrÞ was important [7]. When we consider C V , how-
ever, both the first peak and the first minimum in @gðrÞ=@T can
0.4
affect the accuracy of C V significantly. Although only the error in
the left half of the first peak (or the FR region) in gðrÞ was impor-
0.2
tant for virial pressure [7,8], the entire first peak in @gðrÞ=@T
becomes important for cV . Leftward shift of the left half of first
0.0
peak in @gðrÞ=@T leads to the overestimation of C V or cV , whereas
1.0 1.2 1.4 leftward shift of the right half of it results in a tendency of under-
r/σ [-] estimating them. This competition can be seen in both the curves
of ‘‘difference in ICV ðrÞ” in Fig. 3(a) and of ‘‘difference in IcV ðrÞ” in
Fig. 4(a): that is, the overestimation of the integrand of Eqs. (20)
and/or (21) is first accumulated as r increases, followed by a signif-
icant underestimation. For example, the curve of ‘‘difference in
IcV ðrÞ” once reaches the value of 0.66 in the vicinity of r=r ¼ 0:9.
 T. Miyata, S. Miyazaki / Chemical Physics Letters 658 (2016) 224–229
In the region of r=r > 1:0 in Fig. 4(a), on the other hand, the curve
of ‘‘difference in IcV ðrÞ” exhibits almost a plateau with the value at
around 0.3, which agrees excellently with the difference in cV r3 =kB
between MD simulation and HNC approximation at the thermody-
namic state (III) indicated in Table 4. Hence, the difference in
cV r3 =kB between MD and HNC comes almost solely from the error
in the first peak of @gðrÞ=@T. Similarly, the value of ‘‘difference in
ICV ðrÞ” at r=r ¼ 1:4 in Fig. 3(a), within the statistical error, agrees
with the corresponding difference in C V =ðNkB Þ indicated in Table 3.
The results of KH closure (Figs. 3(b) and 4(b)) are qualitatively
similar to the case of HNC closure. The first peak of @gðrÞ=@T under
KH approximation is located in the left compared to MD result.
Therefore, significant underestimation follows the overestimation
regarding the integrands both in Eqs. (20) and (21), when r
increases. When r=r > 1:3, the ‘‘difference in ICV ðrÞ” arrives at
around 0.1, as seen in Fig. 3(b). This value almost coincides with
the corresponding difference in C V =ðNkB Þ shown in Table 3. Simi-
larly, the ‘‘difference in IcV ðrÞ” in the region of r=r > 1:1 roughly
matches with the corresponding difference in cV r3 =kB indicated
in Table 4. It would be striking that the maximum value in the
curve of ‘‘difference in IcV ðrÞ” under KH approximation (Fig. 4(b))
exceeds even 1.2, though the difference in cV r3 =kB between MD
and KH is at most 0.37 as indicated in Table 4.
The figures concerning the error analysis in the integrands
under PY and VM closures are indicated in Supplementary Content.
Under PY closure, both the ‘‘difference in ICV ðrÞ” and ‘‘difference in
IcV ðrÞ” exhibit almost only a decreasing behavior with increasing r
in the vicinity of the first peak in @gðrÞ=@T. The VM closure is the
most accurate among the approximations considered in this study
in terms of the first peak of @gðrÞ=@T, though slight underestima-
tion is observed in the integrands of Eqs. (20) and (21). The values
of ‘‘difference in ICV ðrÞ” or ‘‘difference in IcV ðrÞ” at r=r ¼ 1:4 under
both PY and VM approximations are roughly in agreement with the
corresponding differences in C V =ðNkB Þ or cV r3 =kB indicated in
Tables 3 and 4.
The deviations in C V and cV of OZ theory from MD results seem
to be larger at thermodynamic state (III) than at the states (I) and
(II). Since the integrals in Eqs. (20) and (21) have a factor of q, the
deviations in C V and/or cV may increase with q, provided that the
error in @gðrÞ=@T does not change remarkably by varying thermo-
dynamic states. The relatively large deviation in C V and cV at the
state (III) may be elucidated by the above viewpoint.
Finally, we shall mention some future aspects. This article has
treated only one-component LJ fluid. Extension of this study to
two-component, say solute-solvent, system would lead to, for
example, a check of accuracy of solvation entropy. The calculation
of the solvation entropy involves the differentiation of the Kirk-
wood charging formula with respect to temperature (see, for
example, Eq. (7) in Ref. [6] for the Kirkwood charging formula).
This differentiation produces @gðr; kÞ=@T that depends upon the
coupling parameter k. Although we have to be careful about the
sampling number in MD simulation for the solute-solvent pair dis-
tribution function as pointed out in the Introduction, a similar
error analysis to the current study may be applied to solute-
solvent @gðr; kÞ=@T and the relevant integration by r at each value
of k. In this extension, one would practically consider a
temperature-derivative under constant pressure rather than under
constant solvent-density (note that the analysis described in this
article is exclusively an isochoric one). This will be advantageous
since experiments are usually performed at a fixed pressure. Fur-
ther, the extension of the current analysis to polyatomic molecules
is in principle straightforward, though the computational cost for
MD simulation would become much more expensive than the
monatomic molecular system. The analysis for systems of poly-
atomic molecules may be done with multi-dimensional distribu-
229
tion functions as well as the partial radial distribution functions.
Based on the results presented in this article, extension of VM clo-
sure to multicomponent and/or polyatomic molecular system
would also be interesting.
4. Conclusion
Firstly, we have examined the precision of @gðrÞ=@T obtained
from MD simulation on the basis of the finite difference approxi-
mation. The finite difference approximation is found to be accurate
enough to provide rather consistent results regarding C V and cV .
Then, the accuracy of @gðrÞ=@T obtained from OZ theory for one-
component LJ fluid has been studied. The closure approximations
investigated in this article are HNC, KH, PY and VM closures. The
precision of C V and cV under these approximations has also been
examined. The first peak of @gðrÞ=@T estimated from HNC approx-
imation shifts to the left compared with the corresponding MD
data, which results in the overestimation of C V and cV . It is to be
noted that the remarkable overestimation of the integrands both
for C V and cV (Eqs. (20) and (21)) is largely canceled out by the fol-
lowing underestimation along the integration by r, especially at
high density state: hence, C V and cV under HNC approximation
should be understood as a result of this cancellation. KH closure
exhibits qualitatively similar behavior to HNC closure regarding
C V and cV and the relevant integrands. The cancellation behavior
under KH closure is more than HNC closure. The first peak in
@gðrÞ=@T under PY closure slightly deviates from MD result to
underestimate both C V and cV . VM closure is found to be the most
accurate among the four closure approximations tested here in
terms of @gðrÞ=@T, C V and cV .
Acknowledgment
This work was supported by Grant-in-Aid for Scientific
Research (16K05659) from MEXT, Japan. One of the authors (T.
M.) thanks Professor Fumio Hirata for fruitful discussions. The
computations were performed using Research Center for Computa-
tional Science, Okazaki, Japan.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cplett.2016.06.
049.
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