Fluid Phase Equilibria,

37 (1987) 305-325 Elsevier Science Publishers B.V., Amsterdam -

305 Printed in The Netherlands

A Computer

Simulation

Study

of

Fluid

Ammonia

K.A.

Hansour

And

S.

Hurad

Department University Chicago,

of of

Chemical Illinois

Engineering at Chicago USA.

Illinois

60680,

ABSTRACT We
i

report ntermol are ecu1

results ar

of potential point effective

computer model dipoles, many from include

simulation consists quadrupoles body dilute dimer. of

studies a and central also

for

fluid Cennard-Jones

ammonia. part, The The

The to latmodel

which ter

added

polarizability. interactions.

introduces were

intermolecular gas liquid The and and

parameters Properties transport pared wide with range

obtained

crystal solid

lattice structure results of

properties. and have the energy, been comfor

calculated and

thermodynamic data over

properties. to a demonstrate wide range

simulation the of state adequacy

experimental of properties

model

conditions.

INTRODUCT Computer potentials, its ate ways. which simulations because no studies statistical because theory. are useful

ION for investigating approximations unique can serve theories be as status useful intermolecular are as in an involved intermeditwo general against equations in

mechanical of their

implementation. between In experiment their first

Horeover,
and role, such

simulations can

simulations as perturbation

experiments and integral

theoretical

methods

0378-3&312/87/$03.50

1987

Elsevier Science Publishers B.V.

306
can be tested for model can fluids. be

Since

a wide using

range

of

both

thermodynamic model

and can data dynam-

transport be tested

properties and

obtained a

simulations, of the available

a potential

compared In

against this a paper, potential of of

wide we

range used for

experimental of molecular

using ics

simuiations. (MO) to investigate the model point Polar chemical valuable dipole fluids and

have

method

model

ammonia. study of (LJ) well as fluid ammonia. The with

We report potential added ity. Cal, provide properties. Computer ics (both

results consists and such

a computer a central

simulation

Lennard-Jones as interest In of

interaction, dipole of polarizabiltheir a

quadrupole as ammonia

interactions, are of

because addition,

biologistudy can

engineering insight into

significance. the nature

such

several

orientation-dependent

simulations equi 1 ibrium properties, Wherever data.

were and

carried nonequi structure, the

out 1 ibrium)

using .

the The

method properties

of

molecular studied and compared general a wide

dynaminclude shear with quite range make

thermodynamic viscosity. experimental good. of such

self-diffusion simulation with of the results

coefficient, have data model data been is used is in for available

possible The the which

agreement adequacy sufficient

experimental potential quality

demonstrating for

properties, comparisons

good

to

meaningful.

INTERfiOlECUlAR
Ammonia was mode led using a potential of

POTENTIAL
the form:

(:.W,*~s)=

U( :l2)

=4,(12)

+ly2)

+Uclp(12) +UQQt

+u

ind(121+

pol

(12)

(1)

where is the

is

the

vector of

joining molecule

the i,

centers Uo(12)

of is

mass the

of

molecules LJ

1 and

2,

and

wi

orientation

central

potential,

307

U,(r,,)

4c

C(u/r,1) 2

(o/rJ

(2)

and

UCrQ'

UQQ

Uind,

Upo1,

are and

the

dipole-dipole, contributions to polarizability,

dipole-quadrupole, respectively. and dipole. which 1984; at the This are polarmodcalcu1984). mol-

quadrupole-quadrupole. The ization el induction energy energy is explicitly a self-consistent the electric the is

induction the

polarization due in creating

contribution expended the

work for

the

induced effects,

accounts using

multi-body technique

induction (Gray and the j

lated We

Gubbins, molecules

flurad, the COH of

calculate i by:

fields

due

to

all

ecule
-P

E=

2 i #j

fi.. J

(2)
ij 3

i+j

: T (3)
j ij

(3)

where

T (4)
ij

iTq(

l/

ij

The

induced-dipole

for

molecule

is

then

given

by:

+
P
II

induced,

(4)

where ability the

is

the

polarizability by, in given by, a = ammonia

tensor. (113) is Cnxx small.

In +

this nyy The +

study nzz

we

used since

a scalar the

polarizof cal-

represented polarirability is

1I

anisotropy used in

total

dipole

moment

culations

+
c1
sz

-t
total,i
fi

+
perm. i
+

induced,

(5)

since

equations

(3)

and

(4) 2

are

coupled.

an
were

iterative
sufficient

Solution
for the

is

necessary

to of

solve the

them. fields,

We found
with a

that

iterations of less

convergence

tolerance

than

10-4

308

Our

potential

model obtained

has from

two

adjustable gas adjustment see the given the model in

parameters and crystal was made

(the

two LJ

parameters). as cor-

These
explained rect

were

dilute final (atso of are

lattice in of as r/k to liquid

properties obtain the

later.

A slight densities The parameters ich, 1971)

saturation

discussion as table well 1.

thermodynamic con-

properties). stants used

other

experimental

(Kukol

Table

I:

Intermolecular

potential

parameters

for

ammonia.

c/k (K)
o (A) (esu-cm)

220.6

3.400 1.47 x 10-18 x lo-26

P Q CY

(esu-cm ) (cm21

- 3.307
22.6 x

10-25

5 IAULATION AII the

properties MD in using 1984: the reported were obtained

WETHODS
using the usual for mo lecular shear viscosity dynamics which Evans we of the

technique, was and used the obtained Harris, a

microcanonical nonequilibrium

ensemble, mo 1 ecular

except dynamics,

NEHD types 1971) for

(Evans, of for the

1983;

Haile

and

tupta,

983).
method fourth-order free

For

both

simulations, the solution of and

fifth-order

Predictor-Corrector motion, The and a

(Gear, method

translational motion.

solution (Evans

rotational

singularity

quaternion

algorithm

Hurad.

309

1977) were

was started

used

for using

solving the up final the

the

rotational positions and

equations. orientations process. of We

Most of

of a

the similar

simulations previous 1200 on longer

simulation steps, the runs. The with profile after tion during NEfiD yo (c/H) to At* shear = and state

to the point

speed

equilibration run consisted state

typically time steps

rejected depending

production studied.

6000-~000

Denser

conditions

generally

required

NEMO

technique shear on

used for the

time-varying couette system was flow, during

non-orthogonal where the In a 1 inear initial addition, and the strain was

boundary hydrodynamic equilibration during rotational the

conditions velocity period, equilibrabut Al 1 y* rate = up

homogeneous was which period the

imposed this we

constraint resealed both run run that ~1.0.

removed. translational resealed reduced viscosity both cutoff

the we at the For a only a

velocities, velocity. y* of a ~1.0, the reduced tested the where shear time the

production were We of In due to (Gray icant found y*

translational rate of

simulations -12. rates

independent we used. properties show that used We

MD and of for Our 30

NEMD, was

step, con-

0.00017.

addition, long et ( al i.e. range .,

also using these

tributions f ietd are erties cant enough perhaps for to not method

forces

these results

reaction

1986) .
within we

contributions for the prop-

signif calculated.

the expect

statistical these

fluctuations) contributions our to be

However, properties. a reliable runs

more were

signifinot long which

dielectric to provide production

Unfortunately, estimate in excess of of the

simulations

dielectric time-steps.

properties,

need

50,000

RESULTS
0; The neous exper ture. lute Gas Properties parameters least values energy, of crystal used squares the in fit pressure lattice this study were the first obtained values by and dimer a simultaavailable struc-

potential
non-linear imenta dimer 1

between second structure

calculated virial and

coefficient, energy.

310

Pressure The pressure

Second

Virial

Coefficients:

second

virial

coefficients

were

calculated

using

(Buckingham,

1959) :

N A
B (T) = 4 P C r,r

dr c

sin%,

d%, c

sin%,

d%,

f:

db,,

. (l-e

lJ(l2)/kT

(6)

1
(6) was evaluated The are using results a nonproduct using integration the potenexpcr-

The

multiple

integral (Stroud, 197); figure

in

algorithm tial are

Murad, 1, where

1978).
they

obtained with

shown in results is at

also

compared

available in the

imental tal data

(Haar least to virial (Sagarik

and Gal lagher. *9 cm3/mol.,

1978) ,
and

The uncertainty we Our estimate results the

experimenof our

accuracy

calculated for ies the of

values pressure

be within

2 percent. than Klein

show better in previous

agreement such stud-

coef ficients et aI . ,

that et

obtained al.,

ammonia

1986;

1979).

Dielectric
We

Second used B,(T) the

Virial

Coefficients:

also

potential is

to generally to the from by:

calculate very

the

dielectric to of

second measure the to

virial

coeffi-

cient, 8, (T) sents

which

difficult part behavior

experimentally. and repre(Buck-

is the

very first

sensitive deviation

non-central the ideal

potential polarization

due

i ngham,

1959) , and is given

6 t

(T)=

- xNA 9 kT

2a JZ
r,,2

dr

,z

sin%,

d%, ,I

sin%,

d%, I,

-U(lZ)/kT -2&J ). e

(7)

where

311

-100

-200

-300

-400

6
z 5
0

-6OC

-6cN
l

= THIS

STUDY

160

200

260

30.0 W

350

400

Figure

I:

Pressure imental

Second data

Virial and

Coefficients.. Gal lagher. 1978).

The

solid

line

is

the

exper-

(Haar

312

The

results

obtained dielectric values we feel

are

compared constant

with values

some in

estimates table 1974) 2. is

of The

B,(T)

obtained in

from these and in

experimental experimental view of this

uncertainty large,

(fiacRury that our

and results

Steele, are

therefore

satisfactory.

Table

2:

Dielectric

Second

Virial

Coefficients.

Temperature

This

Study

Experiment

Ei,

cm6/mo12

373 398 423

175 145 125

618 545
410

Dimer Results existing su As Our note KJ/mol, appears et

Structure for the

and dimer

Energy: are data Oi 11 et the a linear reported and al ., dimer other 1975; in table calculated Allen, 3, which results 1975; were the Brink to as show good agreement 1970; Glasser. LJ in with Kuchit1981).

experimental al ., 1968; earlier, predict a since more the

(towder, and two

mentioned results that

properties for for value et al. the

fitted

parameters. 2. We

geometry range KJ/mol

dimer

shown would

figure be

reasonable 18.83

dimer

energy reported

8.37

14.8 (1970)

reported

by

Lewder

unreasonable

(Hinchliffe

1981;

Jorgensen

and

Ibrahim,

1980).

313

Figure

2:

Dimer

Structure.

Table

3:

Ammonia

Dimer

This 19 I (degr eel (degree) (degree) (A)

Study

Exp

or

QH

71
0 0

67
0 0

0~
#I B r, z

3.340
11.74

3.05-3.53 8.37-18.83

(KJ/mol)

314

Several existence

of

the curve,

simulations since for most

for of is

fluid the along to

ammonia experimental the

were

carried data

out (Haar curve.

along and As

the

co-

Gallagher, mentioned of is our not is siminecThe to

,978)
earlier, potential unusual very lar essary

available we found

ammonia it necessary we were found

co-existence c/k, the the

rescale

energy correctly.

parameter This the

model, and has

if been to

to to

reproduce be true model. al. by

pressure as wel

others The

since

pressure is it K.

sensitive to that to

the by u

potential Hurad, et

resealing that was

procedure we found did to not be

used find 220.6 is

used rescale in the

(198O),
value (Haar

except of c/k

The

resealed data

uncertainty be less than

experimental the data

and in

Gallagher, figures

1978) 3
and 4.

reported

1 % for

represented

Thermodynamic In be figure seen,

Properties report agreement point out in The since among (b) them results with here for the configurational (Haar we and internal Gallagher, shown as error such are property very and from energy. 1978) bars is are As can very in

3 we
the We must

experiment that what

good. fact are

have HO

only size

fluctuations dependent. especially factors,

observables true they are of (c) of errors vary (a) the

from in from

simulations,

fluctuations difficult depend the to upon

ND simulations property error to

estimate, several er the state dynamic) calculate In and figure critical

round-off

resulting algorithm of

comput-

hardware, differential

reliability equations, on the type of the

finite-difference

used
or

to

solve
steady or or to

characterization property under over

equilibrium e.g. equilibrium are

(depending and the 4 we the

study,

length

segments

which

averages

accumulated

different present of

properties. results ammonia. for the co-existence curve between the triple

points

315

200

225

250

275

300

325

350

375

400

425

TEMPERATURE.K Figure 3: Configurational tal data (Haar Internal and Gallagher, Energy. 1978). The solid line is the experimen-

60

55

50

0
; 45

w 5 g

40

35

ii 5

30

25

.+-

20

15 150 175

/
200 22s 250 276 300 T 325 WI 350 375 400 425 450 4 6

Figure

4:

Thermodynamic tal data (Haar

Co-existence and Gal lagher,

Curve. 1978)

The .

solid

line

is

the

experimen-

316 Liquid Figure

function,

structure

5 compares
GNN (r) are

our
with some

HO
the of

results

for

the

nitrogen-nitrogen x-ray diffraction MC/MD state 1977) the ., the K, studies. of

radial data tn T= 280 at of

distribution (Narten, figure

experimental the other represents data (Narten,

1977) 5, V= 277 the 26.51 K, V= and the while MD the

Also
solid

shown curve

reported a

(this The

study)

point was MC

K.
T=

cm3/rnol. 26.92 lbrahim data of

experimental The at iffe T= dashed 240 et al. K,

reported results

cm3/mo1. (1980) Hinchl curve cm3/mol. of 2.5

ine

represents cm3/moi at of

Jorgensen

V=24.97 (1981), the data

chain-dash V=26.49 and our Klein study i\ with at is

represents cm3/mol, 0976) at at 3.57

T=271.3 McDonald from at

chain-dot V=23.30 magnitude In addition,

represents The while first

T=l96 i of with

K,
a

neighbor data

peak peaks

Nartens data at around shows 3.8 i. the et and a

3.37

a magnitude

2.06.

Nartens shoulder

a clear Narten central al., 1981;

shoulder attributes molecule. Jorgensen

3.7
the

A,

while to

our the

results hydro-

show gen

a weaker bonded

shoulder our

neighbors

To

knowledge, Ibrahim. al .,

no other

HD or
and able nificant, in our

MC study 1984; reproduce especially potential. and do not

(Hinchliffe Kincaid such

and et

1980; 1986)
this has is

lmpey been sigforce

Klein, to

Scheraga,
(see not

1982;
also include

Sagarik figure any 5). explicit

shoulder we did

We fee) hydrogen all

since

bond

However, data hydrogen doubts et al ., the peak

important to to also Kincaid

differences exist. be as This strong raised and is as

between presumably those the 1982). up t0 the

simulation because by the

results models

Nartens show al though (Sagarik calculated

continue bonding have

shown

Nartens of Nar-

experiment, tens We after data also the

been

about

accuracy

1986;

Scheraga. nNN

coordination

number

first

minimum

the

first

using:

r
n NN = 47rP I,

min CNN(r) r2 dr

(8)

Figure

5:

Radial results,

Oistribution
l

Function.. the experimental

The data

sol

id

line

represents

the

HD

om

is

(Narten,

1977).

where was 12.0, tal

r,,,i,, found

is to

approximately be in 11.6 view agreement which of

5.1

(see

Figure favorably

5).
with between

The the our

calculated experimental ghR and the

value

of value

nNN of

compares the could

although values, this

disagreement be Fortuitous.

experimen-

Shear
Another

Viscosity
test of

and
a

SeJf-Diffusion
potential model accurately. of the mean lies in The square its abi 1 ity to predict coefficient, using the transport D was equation

(nonequilibrium) obtained from the

properties slope

self-diffusion displacement

318 1976) :

(ticQuarr

ie,

I im t+-

<*r2(t) >
6At

(9)

The

MD simulation the available line in

results

along

the

co-existence (OReilly extrapolation available of In f the Sagari which 7.5

curve et al., of

are

compared

in

figure that data,

6 with
the since

experimental the figure data an IO is are

data an only

1973). the

We note

dashed the

experimental 200our 298 K. are hD In in

experimental data to carry within

between %, while we et al.,

The probesti-

experimental ably mates our data, accurate of results and Most properties Evans vious of the

uncertainty percent.

values report

figure, k is

also

others show

(Impey

and

Klein,

1984;

1986)
evident

general,

Arhenuis-type

behavior

also

OReillys

agreement
NEHD

is

rather carried

satisfactory.

the of

studies

out

previously
mixtures

have

been (Evans, aware

for

the

transport and one of previs-

nonpolar Heyes,

fluids Hoover fluid

and et (Murad,

fluid

Ig8j;Hanley of only

1981;
study

1983:
polar

al ., !984). et al .,lg&).

WE are An

for

NEMO estimate

cosity fluid. available

State

can

be a useful figure 7 we

test

of

the

intermolecular our
NEMO and curve. viscosity

potential
results

model

for

a polar with
1972)

In

present

along
et in and al., the are

the
for are f4 both

experimental conditions of the on the

data

(Krynicki

Hennel, The

1963;
error

Alei bars

co-existence in is

figure within

indicative %. data We The sets. would

fluctuations uncertainty

the

calculated
reported

viscosity,
to be

experimental

also

within

4 % for

like

to curve

note as results

that is

Some usual for

of in

our MO.

simulations However, we

are have

not

exactly no

on attempt

the to in also

co-existence correct general the they

made

NEMO

such the

small

temperature with

differences. results.

although We

would

improve

agreement

experimental

319

n
I
I 1

20 figure
6:
Self-Diffusion data and (ORei Klein lly (1984).

32 ld/
Coefficients.. et al ., 1973).
l

44 T
our Sagarik

56

C-K)
HD results, et al. experimental

*o

(1986).

lmpey

320

0.04 30

0.55

0.60

0.65

0.70

0.75

0.10

DENSITY (WiAM/CC)
Figure 7:
Shear sents Viscosity.. the experimental
l

ee

are data

the (see

NEHD text).

results,

the

solid

I ine

repre-

performed that results

simulations is

at

lower in self

and the

higher shear

shear range

rates. used here.

Our We satisfy

results also

confirm found our the

ammonia for

Newtonian and

viscosity

diffusion

coefficients

closely

Stokes-Einstein

relationship kT

(S-E)

:
(10)

4r II llh

321 1.83

where
(1973)

Ah

(= For

1I

is
at for

the
p= p=

hydrodynamic 0.6834 gm/cm3

radius and T=

as

given K. K,

by

OReilly

et CP
cP

al.
and and

examp le. CP,

cP. wh ile

T=

235.4 276.2

~~,~~~=0.245 VNEMO= 0.181

qS-E=
qS_E

0.230
0.179

0.6332

gm/cm3,

Crystal As

lattice earlier, to obtain out using for we the used potential the technique the properties parameters suggested

mentioned

of
of

the
our by

solid model, Haymet

phase The et al.

(energy calculations (1981).

and

structure) were results with Harris, and 1979) Klein. the carried

The

obtained available 1961;

crystal
experimental

lattice
data

properties (Olovsson and 1978; and

Righini

are and other

et estimate

shown Templeton, reported

al., of

in

table
1959;

Ir
Reed

along and

Shipman
1978;

et

al ., et
in

1976) al .,

studies 1978: the The Klein lattice agreement

(Righini et al.. energy is in

Ouquette

The at

uncertainty al., 1976) is

the

experimental to be f

(Shipman general

reported

4.184

KJ/mol.

satisfactory.

Table

4:

Crystal

Lattice

Structure

and

Energy

This

Study

Exp

or 5.084 5.084
5.084

QH

a b c
P

Ci) (;I (A, (g/cm%

5.12
5.12 5.12

0.843

0.861-0.922

- E (KJ,hoi)

32.22

28.43-41.81

322

CONCLUSIONS We have
itly

developed

an

intermolecular induction and

potential effects, transport potential

model and has

for been

ammonia found Although not been been

which to

explica has as The

includes range studied a range of

multi-body thermodynamic before. of

reproduce ammonia

wide been wide

properties. models have as

previous and not

tested done here.

for

properties have in also

state

conditions multi-body

has

previous which are

models important

included

induction

contributions

ammonia.

List

of

Symbols

*h B, BP D Ei GNN n NA

hydrodynamic second second dielectric pressure

radius,

equation virial

(10)

coefficient coefficient

virial coefficient

self-diffusion electric field

at

molecule radial

due

to

all

other function

molecules

nitrogen-nitrogen molecular Avogadros quadrupole temperature weight number moment

distribution

Q
T T*

molecular pair central

tensor

as

defined

in

equation molecules energy,

(3) 1 and equation 2 (2)

U(12) LJO u c(&

interaction

energy

between interaction energy

Lennard-Jones interaction

dipole-dipole dipole-quadrupole

"PQ "QQ a.b,c

k NN

interaction interaction unit cell

energy energy lattice), angstroms

quadrupole-quadrupole dimensions Boltzmanns coordination of the

(crystal

constant number, defined by equation (8)

323

intermolecular the time mean square location of

separation the first

vector minimum

between in the

centers GNR(r)

of

mass

min t Ar*

displacement

Greek

symbols polarizability reduced energy shear shear shear strain parameter viscosity viscosity viscosity obtained obtained equation from from (10) NEMI the simulation Stokes-Einstein rate of the intermolecular potential

relationship, dipole number and V moment density, is the densi parameter

N/V, volume ty, pa of

where of the

is

the

number

of

molecules,

cell.

reduced length molecular orientation

3
the intermolecular angles of molecule i potential

orientation vector

BIBLIOGRAPHY

Alei,

M.
liquid

Jr., ND3.

Litchman, J. them. 1975. g7:6g21. A

W.H.. Phys..

1972. Density ST:4106 . model of hydrogen

and

viscosity

of

Allen, L.C., J.A.C.S..

simple

bonding.

Brink, C., Glasser, L., in ammonia using an guckingham, D.A.. 1959. Rev., Dill, of J.D.. nine 13:182. Allen, L.C., hydrogen-bonded

1981.
empirical Holecular

Studies in Hydrogen bonding: Association potential. J. Comput. Chem., 2:177 quadrupole moments. Quart. 1975. NH3. A OH2. systematic study

Topp, W.C.. Pople. dimers involving

324

and Duquette,

J.A.C.S., HF. G., Ellis,

97:7220. T.H..
Stoles, G..

Watts, J. free

R.O., them.

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