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46 Ansichten10 SeitenCoordination Number in Liquid Argon

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Coordination Number in Liquid Argon

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C O O R D I N A T I O N N U M B E R IN L I Q U I D A R G O N

W. BROSTOW and Y. SICOTTE

J~Iontr6al, Qudbec H3C 3V1, Canada

Received 26 February 1975

Structure of liquids is discussed in terms of Voronoi figures and Delaunay polyhedra. Equations of the respective models and precise experimental data recently available for argon lead

to calculated values of the coordination number z and the geometric parameter #. The relation

betweent z and # is thus found empirically. Further, calculated values of coordination numbers

are compared with those coming from thermal-neutron and X-ray scattering data. A selection

among the existing methods of obtaining z from the radial distribution function g(R) is made.

The method chosen enables one to find z [g(R)] corresponding to the Voronoi structure.

1. Introduction

C o o r d i n a t i o n n u m b e r s z are c o n v e n i e n t for characterizing structures o f dense

fluid phases, b o t h f r o m theoretical a n d f r o m e x p e r i m e n t a l points o f view. They also

serve in p r e d i c t i n g m a c r o s c o p i c p r o p e r t i e s o f industrial i m p o r t a n c e , as e.g. in the

study o f G o t o h 1) o f the surface tension o f liquids. The p r o b l e m o f e v a l u a t i n g z f r o m

the b i n a r y r a d i a l d i s t r i b u t i o n function g(R) has been c o n s i d e r e d by Pings 2) a n d by

M i k o l a j a n d Pingsa); they have discussed in detail no less t h a n f o u r distinct m e t h ods o f calculating z f r o m a given g(R) curve a n d they have m a d e some n u m e r i c a l

c o m p a r i s o n s for liquid argon. It t u r n e d out, t h a t different m e t h o d s p r o d u c e d different n u m e r i c a l values. M i k o l a j a n d Pings have n o t given preference to any o f the

m e t h o d s ; they only insisted t h a t in each case the m e t h o d used s h o u l d be clearly

defined.

L a r s s o n , D a h l b o r g a n d Sk61d 4) in their review o f scattering o f slow n e u t r o n s by

liquids find also t h a t the n u m b e r o f nearest n e i g h b o r s o b t a i n e d d e p e n d s on extrap o l a t i o n with increasing distance R f r o m the first p e a k in 47~RZg (R). S c h m i d t a n d

T o m p s o n 5) reviewing X - r a y scattering by fluids also discuss difficulties in determining: c o o r d i n a t i o n n u m b e r s ; they stress t h a t n o t only ambiguities in assigning

areas u n d e r curves b u t also sensitivity o f the f o r m o f g(R) to e x p e r i m e n t a l errors

affects values o f z o b t a i n e d .

513

514

In a model of the liquid state based on spacial distribution of molecules 6) coordination numbers represent input parameters, along with geometric parameters/~

and with intermolecular potentials u(R). Quantities such as the configurational

energy U ~ and volume Vcan be then calculated for a given temperature T. In vie~

of the problem outlined above, we could have hardly followed the usual route of

calculating macroscopic properties from a set of microscopic parameters, the latter

in our case including the coordination number. We have, therefore, inverted the

use of equations and calculated parameters z and # from known macroscopic

equilibrium properties. The results obtained are compared with z values resulting

from experimental g(R) curves. A choice between different methods of calculating

coordination numbers t'rom neutron or X-ray scattering data is then made. Moreover, a relation between coordination number and the geometric parameter ,u is

found empirically; such a relation has been sought in vain in the existing mathematics of the subject.

2. Basic relations

In the model of liquids discussed in ref. 6 the geometry of the system is exactly

defined. Neighboring molecules are joined by lines, and the links formed represent

impenetrable barriers for other molecules. The entire space is thus divided into

Delaunay polyhedra: molecules and links become respectively vertices and edges of

polyhedra. Taking each link and producing a face perpendicular to it and passing

through the point equidistant from terminal molecules results in dividing space

into an alternative assembly o f V o r o n o i polyhedra. There exists a dual relationship

between the two assembliesV'S). No limitations are imposed upon the structure, so

that links outgoing from a given atom may be of any length and the coordination

number may vary t0m one molecule to another. Thus, when calculating macroscopic properties, summation over atoms with different coordination numbers has

to be made6). In the simplest version of the theory, however, an average value oF

coordination number z for the entire phase may be used6'9). The configurational

energy of the system is then

N*

(I)

number NA ; ~0(R) dR is the probability that a link length is between R and R + dR,

the distribution given by

R2

Q

~t'(R) = - -

exp

zu(R)

2kT

l~PR 3)

kT

(2)

515

where

R*

(3)

k is the Boltzmann constant, T thermodynamic temperature, P macroscopic pressure. The geometric parameter # is the proportionality factor in the volume equation:

R*

(a)

Formulating such a relation belongs to the theory of packing and covering, based

essentially on geometry and topology. The theory in question, however, supplies us

with proofs that a three-dimensional space may be completely divided into a set of

Delaunay or, alternatively, Voronoi figuresT), but goes very little beyond that.

To define the upper integration limit R* in eqs. (1), (3) and (4), let us introduce

some terminology. We start From the location of a chosen central molecule (intermolecular distance R = 0) and we move in the positive direction along the R axis.

We encounter first the border of the Voronoi figure of the central molecule, to be

labelled R~m~,. We then reach the border of the Delaunay figure, to be labelled

Rlm.~x; our symbols are related to the respective maxima and minima of the radial

distribution function. Further, we arrive at the border of the Voronoi figure of the

second molecule. Consistently with our model, this is the upper integration limit:

continuing to label characteristic points in the same way, we thus have Ru ..... = R*.

3. Calculations

As the most extensive and accurate experimental studies have been made for

argon, we have chosen it as the object of calculations. To define the liquid-state

range, we have accepted the triple-point temperature as Tt = 83.81 K. This is the

value chosen by Pollack1), while Chen, Aziz and Lim a t), after a careful analysis

of literature data and their own vapor-pressure results in the vicinity of Tt arrive

at 83.806 + 0.001 K. As the critical point we take Tc = 150.70 K. Grigor and

Steele 12) have obtained from

measurements 150.6 ___ 0.1 K, Pings and

Teague 13) from refractive-index measurements 150.704 __ 0.015 K, the latter value

reiterated by Teague and Pingsl~).

Analysis of the equilibrium vapor-pressure data for argon has been made by

Garside and Smith ~5) and also by Verbeke16). Using no less than 180 experimental

points of 9 different authors, Verbeke has found considerable scattering of data

P-V-T

516

from different sources. In each of the two papers 15'16 a number of different P ( T )

functions was tested. We have eventually decided to use the 7-parameter formula

of Garside and Smith.

For liquid density or molar volume Vthere was also a choice of recent data and

equations 1T-19). Comparing data for T = 100.00 K, we have found V/cm 3 tool-1

= 30.65 from the corresponding-states formula of Agraval and Thodos tT). Gladun Is) gives an experimental value of 30.40 for 100.23 K, while using the Goldman

and Scrase ~9) formula one obtains 30.45. Gladun, who has not represcnted his

results by an equation, stresses good agreement of his data with those of Goldman

and Scrase. In our calculations we have thus used the equation given in ref. 19.

In view of our approach, reliability of the configurational energy U c values is

important. U c was calculated by Barker, Fisher and Watts 2) after a careful analysis

of available experimental data. Similar analysis has been more recently made by

Streett21), based on the ensemble of literature P V T data and on sound-velocity

data o f T h o e n , Vangeel and Van Dae122), and of Streett and CostaminoZ3). The

values of Streett 2~) agree within about l ,o with those of Barker et al.2). We, ourselves, have also made calculations of U c following the procedure described in detail by McGlashan 2~) and using the same data that he has used : the results obtained

are generally in agreement with the two sets mentioned. Further, there exist U

values compiled by RowlinsonZS); while his values for 87.29 K and 9 0 K are slightly higher than those in ref. 20, Rowlinson's value for T, falls exactly on extrapolation of the U ~ (T) curve drawn through the points of Barker et al. [the latter do not

give U~(T0]. We have described the data tabulated in ref. 20 plus the triple-point

value of Rowlinson by a formula:

UC/N;,k -- 11 984.9 - 479.012 T + 6.65010 T 2

(5)

The coefficients in eq. (5) have been found using a computer by a least-squares

procedure. Barker et al. do not give values of configurational energy for T > 140 K.

Eq. (5) gives at the critical point U~/NAk (150.70 K) = - 2 8 7 . Rowlinson's respective value for T = 150.86 K (what he presumes to be the critical point) is - 289, an

entirely satisfactory agreement. Thus, our formula (5) covers the entire liquid-state

range.

Another choice to be made is that of the interatomic potential u(R). Studying

the equation of state of crystals Madan 26) has used 3 different potentials. He has

found that results depend considerably on the choice of the potential. There is

little doubt that the same statement would apply to the problem at hand. Direct

experimental determination of potential parameters by molecular beams produces

interval of values within a contour rather than a single value. Consequently, as discussed by Brooks, Kalos and Grosser27), choosing between potentials on the basis

of such data is very difficult. We have decided to use two potential functions : that

51 7

of Bae 28'a9) and of Barker et al.2). The Bae potential with two adjustable parameters gives results comparable to three-parameter formulas28); the minimum for

Ar is at 3.50 A29). The Barker et al. potential 2) represents a superposition of two

earlier rather complicated equations; it has minimum at 3.76 A. Most potentials

proposed for argon, as discussed in another paper3), have minima located between

these two values.

Finally, we have found the upper integration limit R* from experimental g(R)

data. Yarnell and his colleagues 31) have determined the radial distribution function of Ar at 85 K by slow neutron scattering; these are presumably the most accurate such data presently available. F r o m their tabulated values of g(R) we have

found that the second minimum of the function 47~R2Ng (R)/V is a t R l l m i n = R*

= 5.03 A. It has been observed by Mikolaj and Pings 32) that the extrema of this

function move slightly with the temperature. They have studied a number of Ar

states for various temperatures and densities. A m o n g the measurements described

in ref. 32 however, there is only one (the run no. 31) corresponding to a liquid in

equilibrium with its vapor. As Mikolaj and Pings give positions of maxima only.

we have calculated for their run no. 31 R* = 0.5 (Ri~ox + RH~,,x) = 5.64 ~ at

148.14 K. There was little point in taking other data into consideration, as earlier

data are considered to be distinctly less accurate. Moreover, e.g., the results of

Henshaw 33) are for 84 K, i.e., almost the same temperature as these of Yarnell

et al. Given the value of R* from Yarnell data for a temperature close to the triple

point, and R* from Mikolaj and Pings data for a temperature close to the critical

point, we have simply assumed linear dependence R*(T) along the entire existence

line of liquid Ar saturated with its vapor.

The parameters so obtained plus a pair of trial values of z and/z were substituted

in eqs. (2) and (3). The lower integration limit was taken as 3.180 A. Then, using a

value of U c from eq. (5), a new value of z was calculated from eq. (1). This was

followed by obtaining a new value of # from eq. (4) and from the G o l d m a n and

Scrase volume formula19). The second computer cycle started with the second pair

of z and # values substituted into eq. (2). After several such cycles (three to six,

usually) values of/z and z which ceased to change within five significant figures were

accepted as final.

The results obtained are collected in table ~I. B F W refers to the potential of Barker, Fisher and Watts2). Our choice of linear dependence of the upper integration

limit on temperature was, as explained in the previous section, due to accessibility

of two sufficiently accurate values only. To find out, to what extent the assumed

R*(T) might affect the results, we have also made calculations taking other values

of R*. At T = 85 K, for example, using the BFW potential, we have found

518

TABLE 1

Properties of liquid Ar in equilibrium with its vapor between the triple point

and the critical point

T

(K)

P

V

-- U~

(Jcm-3) (cn.lamol i) Nak

R*

(/~)

Potential

II

Bae

BFW

Bae

BFW

Bae

BFW

Bac

BFW

Bae

BFW

Bae

BFW

Bae

B FW

Bae

BFW

Bae

BF\V

Bae

BFW

Bae

BF'W

Bae

BFW

Bae

BFW

Bae

BFW

Bae

BFW

Bae

BFW

1.0204

0.8158

1.0240

0.8187

1.0381

0.8299

1.0511

0.8407

1.0630

0.8511

.0869

0.873'0

.1173

0.9044

.1466

0.9339

.1617

0.9491

.1779

0.9660

.2228

1.0151

.2469

.0434

.2685

.0687

.3330

.1376

.4526

.2515

.7266

1.4903

83.81

0.072

28.25

707

5.017

85.00

0.083

28.40

707

5.030

90,00

O. 139

29.02

696

5.083

95.00

0.222

29.70

677

5.137

100.00

0.337

30.45

653

5.190

110.00

0.692

32.18

606

5.297

120.00

1.259

34.40

567

5.404

127.00

1.815

36.41

54[

5.479

130,00

2.100

37.45

528

5,511

133.00

2.414

38.64

512

5.543

140.00

3.279

42.38

458

5.618

143.00

3.712

44.72

423

5.650

145.00

4.024

46.79

395

5.672

148.15

4.558

51.93

341

5.705

150.00

4.899

58.54

302

5.725

150.70

5.034

70.47

287

5.733

z -

in z = 10.737 a n d / z

Zcalc '

8.777

10.715

8.789

10.729

8.720

t0.638

8.565

10.441

8.359

10.178

7.976

9.677

7.969

9.294

7.520

9.046

7.424

8.915

7.297

8.741

6.815

8.[00

6.473

7.653

6.191

7.283

5.611

6.536

5.!59

5.962

4.950

5.711

-exp.

11.4

6.9

6.0

6, 150 fi,, r e s u h e d

= 0.81 18. C o m p a r i n g t h e s e d a t a a m o n g t h e m s e l v e s a n d a l s o

w i t h t h e r e s p e c t i v e v a l u e s in t a b l e 1, o n e f i n d s o u t t h a t t h e p a r t i c u l a r c h o i c e s o f R*

m a d e h a v e n o t a f f e c t e d t h e r e s u l t s in a n y s i g n i f i c a n t w a y . T h e s a m e c o n c l u s i o n is

r e a c h e d v a r y i n g R * a t o t h e r t e m p e r a t u r e s , a n d a l s o w h e n u s i n g t h e Bae p o t e n t i a l .

I n s p e c t i n g t h e r e s u l t s , c o n s i d e r first t h e p r o b l e m o f / ~ ( z ) d e p e n d e n c e . O n e f i n d s

t h a t / , i n c r e a s e s w i t h d e c r e a s i n g z; this is, q u a l i t a t i v e l y , i n d e p e n d e n t o f t h e p o t e n -

519

system. Both Voronoi and Delaunay figures now become polygons, and tetrahedra

turn into triangles, while ,u becomes proportional to the surface area. A Yoronoi

polygon of a given molecule contains z triangles. Label nearest neighbors of the

central molecule consecutively as 1, 2, 3, etc., and label in the same way corresponding triangles in the Voronoi polygon of the central molecule. Remove now one of

the neighbors, say 2. Surface areas of triangles 1 and 3 increase now in such a way,

that they absorb completely among them the former triangle 2. Moreover, due to

perpendicularity of Voronoi borders with respect to intermolecular links, triangles

1 and 3 gain also some additional area beyond the former triangle 2. The net result

is thus an increase in the surface area of the Voronoi polygon. Thus decrease in the

coordination number is bound to increase the geometric parameter/~. The same

kind of argument holds for a three-dimensional system also, what explains the/z(z)

behavior found in table I.

While we thus understand qualitatively the interrelation between the geometric

parameter and the coordination number, a quantitative formula is clearly desirable.

As discussed in section 2, the theory of packing and covering appears far from supplying us with such a result. We have, therefore, represented the/z values in the

table by a series in descending powers of the coordination number. There was a

choice between two sets of #(z) values, depending on the u(R) potential chosen.

We have decided on the set obtained using the B F W potential, and this for at least

two reasons : a) it is from the same paper 2) that values of configurational energy

for our eq. (5) were taken; b) Barker and his colleagues claim that their interaction

potential 'gives excellent agreement with thermodynamic properties of solid, liquid

and gaseous argon". We have described the z and ,u values found with the BFW

potential by the formula

u = 0.7576

2.4142

34.706

- + - Z

(6)

Z2

Numerical values of the coefficients in eq. (6) have been found by a computer leastsquares procedure.

Return now to the problem of determining the average coordination number.

Among the methods discussed by Pings 2) and Mikolaj and Pings3), the first three

bear no relation to the geometric scheme outlined in section 2. Accordingly, we are

not going to consider them; they are in any case treated in detail by Mikolaj and

Pings. We are going to deal with the approach labeled by Mikolaj and Pings

"method D". We write

112

:: = .[ 4~,RZ ( N / V ) g(R) d R

Rt

(7)

520

W. BROSTOW A N D Y. SICOTTE

R1 = 0,

R1 = R i .... R1 = Rimi.,

Rz = R . .... = R*,

l,

R 2 = R i .... q- A ,

R,

= R~i+l~,o,.

(7a)

(7b)

(7c)

By, say, eq. (7a) we shall mean eq. (7) with the integration limits specified by (a).

Eq. (7a) represents the method D of Mikolaj and Pings. They have limited their

treatment to the first coordination shell. Eq. (7b) is used by Kaplow and his colleagues 34'35) for calculating coordination numbers in liquids and also amorphous

and crystalline solids. It is applicable for any ith coordination shell. Finally,

eq. (7c) corresponds exactly to the geometrical model as discussed in section 2:

integration limits correspond to borders of the Voronoi figure of any ith neighbor

of the central molecule. Now eq. (7a) represents the special case of eq. (7c) with

f - - 1 ; it should be remembered, that the interval 0 <= R < RI,,,~, does not contribute anything to the integral (7). Eq. (7b) of Kaplow et al. may be considered also

as a special case of (7c), namely with Ri ..... - R~.... = R ~ + 1~.... - R i .... = [ .

The fact that eq. (7c) corresponds exactly to representing a phase of matter as an

assembly of Voronoi polyhedra (also called Wigner-Seitz cells) is clearly independent of any experimental information. But we are now going to consider available,

admittedly scarce, experimental evidence. Taking g ( R ) values for 85 K tabulated

by Yarnell et al. 31) we have performed integration according to eq. (7c). The result

is given in the last column of table I. The difference between the experimental coordination number and the one obtained using the Bae potential is rather large. By

contrast, the BFW potential produces a coordination number fairly close to the

experimental value. We have mentioned above reasons for ascribing more weight

to the potential of Barker et al. Other available experimental z values are those calculated by Mikolaj and Pings3), using their own X-ray data32). As already mentioned, among states studied by Mikolaj and Pings there is only one located on the

liquid-vapor coexistence line on the liquid side. There is, however, one more point

(run no. 22), at 143 K, located fairly close to the saturation line, and we have included the corresponding result in table I also. Both values of z of Mikolaj and

Pings quoted here result, of course, from their method D ; their methods A, B and

C give values consistently lower. Comparing the results of Mikolaj and Pings with

calculations, we find that each experimental value is between the two alternative

calculated coordination numbers. This only stresses the importance of having an

accurate intermolecular potential u ( R ) .

Coordination numbers are essential for many other approaches to the liquid

state, apart of the geometric model characterized in section 2; the quasilattice theory of Guggenheim3,) cell theories 37-39) and the theory of simple liquids of Franchetti 4) at least ought to be mentioned here. Analysis of experimental methods of

52l

determining z in refs. 2 and 3 has caused some repercussions and also some extrapolations. For instance, Hildebrand et al. 4~) have somehow deduced from the

work of Mikolaj and Pings 3) that the coordination number is "misleading as a

parameter". We would like to stress that there is no ambiguity in calculating the

coordination number from experimentally measurable quantities according to

eq. (7c); the only problem involved is that of accuracy of determinations, in order

to be able to well locate the function minima. As for our procedure of inverting

eq. (i) so as to calculate coordination numbers, we find that the results obtained

are comparable to experimental ones. Thus, when experimental data for performing the integration (7c) are lacking, eq. (1) can be used to find the coordination

number. The problem with eq. (1) is also one of accessibility of reliable input data,

the intermolecular potential included.

Finally, we would like to comment on the values of coordination numbers found

by our calculations. From the early data of Eisenstein and Gingrich 42) it follows

that the coordination number of argon changes from 12 in the solid close to the

triple point to 2 in vapor around the critical point. Our data show that liquid atoms

with coordination number as high as eleven exist at the triple point, while coordinations as low as five have to exist at the critical point.

Acknowledgements

Discussions of various aspects of this work, with Dr. E. Braun of the Institute of

Physics, the National University, Mexico City, Dr. U. Dahlborg of the Institute of

Reactor Physics, Royal Institute of Technology, Stockholm, Professor C.J.Pings

of California Institute of Technology, Pasadena, and Professor N.S. Snider of

Queen's University, Kingston, Ontario are gratefully acknowledged.

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