2352 Owicki, Lentz, Hagler, and Scheraga

Structure of Liquid Water. 111. Thermodynamic Properties of Liquid Deuterium Oxide’

John C. Owlck1,28Barry R. LentzlZbArnold T. Hagler, and Harold A. Scheraga*2C

Department of Chemistry, Cornell University, Ithaca, New York 74853 and Weizmann hstitute of Science, Rehovoth, lsrael

(Received May 27, 1975)

A statistical thermodynamic treatment of a cluster model for liquid water is adapted to DzO. When com-
pared with the results of the theory for HzO, the principal thermodynamic quantities for DzO are fit with
slightly less accuracy, but the signs of the isotopic differences in these quantities are predicted correctly.
The intermolecular vibrational spectral density of DzO is calculated (as a function of temperature) from
the normal mode vibrational frequencies of the clusters and the distribution of cluster sizes. The theory in-
dicates the occurrence of only very few clusters containing more than six molecules, the same conclusion
reached for HzO. Also, the fraction of loosely bonded noncyclic clusters of DzO increases with increasing
temperature, as was found for HzO. The results suggest that the energy required to break hydrogen bonds
in liquid DzO may be smaller than that for liquid Hz0. The similarities between the theoretical equilibri-
um cluster distributions and fractions of unbroken hydrogen bonds for DzO and HzO imply that these liq-
uids are structurally quite similar. Most of the thermodynamic differences between liquid DzO and HzO
are attributable to isotopic effects on the intra- and intermolecular vibrational frequencies of the water
clusters rather than to differences in the structures of the two liquids.

I. Introduction As an example, consider the isotopic difference in the

In the first paper in this series, Hagler, Scheraga, and
N6methy3 developed a statistical thermodynamic theory of
liquid water based on a “cluster” model. The model was re-
fined and improved by Lentz, Hagler, and Scheraga4 (here-
after referred to as LHS). This paper reports an adaptation
of that theory to DzO. The two main purposes of this study
are to explore further the validity of the LHS theory and to
investigate some of the isotope effects in the liquid water
system.
The primary criterion in assessing the validity of the
theory is its ability to reproduce a variety of experimental
results. A secondary criterion is that the values of the two
adjustable parameters of the theory for DzO should repre-
sent physically reasonable interactions among clusters and
not differ too drastically from the values obtained for H20.
Liquid DzO is generally considered to be more highly
structured than liquid HzO at the same temperature, where
the term “structure” is usually taken to mean the extent of
hydrogen bonding5 in the liquid. Experimental quantities
that have been cited6 to support the view that d20 is more
structured than H20 include the heat capacity, viscosity,
melting point, and temperature of maximum density, all of
which are higher for DzO than for Hz0.
This question also has been examined in a number of
theoretical studies.6-10 For example, using their cluster
model for liquid water,11-13 Nemethy and Scheraga6J2
found that the energy required to break a hydrogen bond in
liquid DzO was 240 cal/mol of bonds greater than in HzO.
In addition, the fraction of hydrogen bonds ( X H B )was
found to be slightly greater for DzO than for HzO. Specifi-
cally, AXHB= XHB(DZO)- XHB(HZO)varied from 0.029
at 4°C to 0.007 at 6 5 ” C , the highest temperature for which
the theory was applicable.
However, the interpretation of the observed isotopic dif-
ferences in the two liquids depends markedly on the model
employed for the liquid, and it is very difficult to provide
an accurate model of liquid water. Hence, although DzO
usually is considered to be more structured than HzO,
these structural differences are not established on firm
grounds.
The Journal of Physical Chemistry, Vol, 79, No. ?2, 1975
heat capacities: AC, = C,(DzO) - C,(HzO) = 2.3 cal/mol
deg a t 4°C.14,15 Since part of the heat capacity of the liquid
is associated with structural relaxation (hydrogen-bond
rupture),16 this value of AC, may indicate that there are
differences between the structures of liquid DzO and HzO.
However, the structures of DzO and HzO ice Ih are essen-
tially identica1,l’ and yet AC, = 1.6 cal/mol deg for the ices
a t O°C.18 The substitution of D for H will, by itself, lower
the intermolecular vibrational frequencies, and lead to a
positive contribution to AC, in both phases. Hence, struc-
tural effects are indicated not merely by the sign of AC,
but by its magnitude. The key question is whether the ad-
ditional 0.7 cal/mol deg in AC, in the liquids, as compared
to the solids, represents isotopic differences in structural
relaxation in the liquids, or nonrelaxational isotopic effects
caused, e.g., by differences in the vibrational spectral den-
sity of the two phases. This is a difficult question to resolve
conclusively at the present state of knowledge of these sys-
tems.
In an argument similar to that given above, Holtzer and
Emersonlg have shown that current hydrodynamic models
are inadequate to determine whether there is a structural
component in the difference in the viscosities of liquid Dz0
and HzO. Some of the other isotopic differences (e.g., in the
melting points) that are used in structural arguments also
are difficult to interpret, although the high temperature of
maximum density of DzO seems to be explained most easily
in terms of structural differences between liquid D20 and
HzO.
Of course, the problem arises because conclusions about
structures are drawn from thermodynamic rather than
spectroscopic data, A definitive comparison of the struc-
tures of D20 and HzO awaits an accurate experimental de-
termination of the O--O, 0.-H (0.-D), and H-H, (D-D)
pair correlation functions; a study of this type is presently
in progress.20 At present, however, the best information
available is the finding of Narten et a1.21that the low-angle
X-ray scattering patterns of HzO and DzO a t 4°C are es-
sentially identical. As noted by Frank,22this suggests that
the structural differences may be much smaller than often
Thermodynamic Properties of Liquid Deuterium Oxide
is assumed. Similar conclusions derive from near-infrared
observationsz3on liquid HzO and DzO, where the small ob-
served differences (3%)in XHBthroughout the liquid tem-
perature range are within the experimental error. In sum-
mary, it appears that the question of difference in the de-
gree of “structure” between DzO and HzO remains unre-
solved, although most authors have considered DzO to be
the more structured liquid.
11. Model and Form of t h e Partition Function
Except for isotopic differences, the model and form of
the partition function used in this study are identical with
those of LHS.4 The reader should refer to that paper for a
fuller analysis than the summary presented here.
Liquid DzO is considered to be a mixture of independent
clusters of hydrogen bonded molecules; thus, the internal
and external degrees of freedom of the clusters can be
treated separately. The external variables are themselves
assumed to be separable into translational and rotational
contributions. The internal degrees of freedom are likewise
assumed to be separable into independent vibrational and
internal configuration (cluster hydrogen bonding geome-
try) parts. The maximum term in the canonical partition
function may then be written as
where the product is taken over different sizes of clusters j ,
N j is the number of clusters of size j present in the maxi-
mum-term equilibrium distribution of clusters, and No is
Avogadro’s number.
No clusters containing more than eight molecules are
considered, because of the results of LHS for HzO; as in the
case of the LHS study, the small contribution of clusters of
size seven and eight to the equilibrium cluster distribution
tends to support this procedure. Following LHS, only one
basic cluster geometry is included for each cluster size ex-
cept the pentamer, for which two are used. The configura-
tions are as follows: monomer, dimer, “sequential” linear
trimer (central molecule both deuterium donor and accep-
tor), cyclic tetramer, cyclic pentamer, “star” pentamer (te-
tracoordinated central molecule), cyclic hexamer, cyclic
heptamer, and “bridged” octamer [the analog of tricy-
clo(2.2.2)octanel.
A. Translational Partition Function. In their transla-
tional motion, the clusters are assumed to behave as a mix-
ture of hard spheres, the thermodynamics of which has
been derived by Lebowitz and RowlinsonZ4from Lebow-
itz’sZ5solution of the generalized Percus-Yevick equation.
Effective hard-sphere diameters for the clusters were ob-
tained by LHS.4 In the translational partition function, at-
tractive inter-cluster interactions are treated in an average
way by the inclusion of an adjustable parameter ( a ) for a
constant background potential energy, which is taken to be
inversely proportional to the experimental molar volume,
V (i.e., 0: a / V ) .
B. Rotational Partition Function. Qr,,t, is taken as an
Einstein partition function based on a mean librational fre-
quency for each cluster. As above, an adjustable parameter
( d ) is introduced to treat inter-cluster interactions. d / V =
K1 is the rotational force constant for the monomer. The
force constants of larger clusters are constructed so that,
with the clusters represented as hard spheres, points on
their surfaces sweep out equal average distances during li-
brations. Mathematically, the relationship is
KI = K1(Rj/R1lZ (2)
2353
where K1 and K, are force constants, and R1 and R, are ef-
fective hard-sphere diameters. The mean librational fre-
quency for each cluster is obtained with the appropriate
force constant and the geometric mean of the principal mo-
ments of inertia of the cluster.
C. Vibrational Partition Function. Normal mode cluster
vibrational frequencies obtainedz6 with the effective pair
potential of Ben-Naim and Stillir~ger?~ (BNS) are inserted
into an Einstein partition function. Following LHS, the li-
brational frequencies calculated from the BNS potential
are first scaled by a factor of 0.67; a similar procedure was
followed by Weres and Rice28 for H20. The final normal
mode vibrational frequencies of DzO are compiled in Table
I (see paragraph at end of text regarding miniprint materi-
al).
D. Internal Configuration Partition Function. This is
the partition function for the various ways of arranging j
hydrogen-bonded water molecules to obtain a j-sized clus-
ter. Such arrangements may be accomplished by rearrang-
ing either the oxygen or deuterium atoms of a ~ l u s t e rAs .~
in LHS, one arrangement of oxygen atoms is chosen for
each type of cluster except the pentamer, for which two are
used. The different possible arrangements of deuterium
atoms (analogous to the hydrogen randomness which pro-
duces the zero point entropy of ice) are evaluated princi-
pally by molecular model building. The choices of the rele-
vant atomic configurations and the energy assigned to each
are based on the results of an extended basis set ab initio
quantum mechanical study of water molecule interactions
by Lentz and S ~ h e r a g a With
. ~ ~ one exception, these are
identical with those used by LHS.
The exception is the energy assigned to a three- or four-
coordinated molecule, and it is brought about by a differ-
ence between the lattice energies of H20 and DzO. The ex-
perimental data of Whalley30 indicate that the lattice ener-
gy (Elat) of HzO is -13,400 cal/mol while that for D20 is
-13,700 cal/mol. Lentz and ScheragaZ9obtained a value of
-12,900 cal/mol for the lattice energy of HzO. Given the
near identity of the molecular dimensions,”’ ice lattice con-
stants,17 and dipole moments32of D20 and H20, the same
value of Elatshould hold for D20. LHS attributed the dis-
agreement between ab initio and experimental results to a
neglect of third- and higher-body interactions in their com-
putation based on the ab initio calculations. To make the
theoretical internal configurational energy converge to the
correct lattice energy in the limit of an infinitely large clus-
ter, they added a correction energy of -500 cal/mol for
each three- or four-coordinated molecule in a cluster. The
same procedure is followed for Dz0 in this study, except
that the correction is -800 cal/mol for each three- or four-
coordinated molecule. The only clusters which contain
these species are the star pentamer and octamer. In the in-
ternal configurational partition function, therefore, these
clusters are slightly more stable relative to the others in
DzO than in HzO. For DzO calculations using Elat =
-13,400 cal/mol (see section IV), the correction energy was
restored to -500 cal/mol.
The reference state for the partition function is ice at 0
K in its ground intermolecular and intramolecular vibra-
tional states. Since the ab initio quantum mechanical ener-
gies are taken with respect to separated molecules at rest, it
is necessary to adjust the zero of energy to the desired ice
reference state. The procedure is discussed more fully by
LHS. The requisite thermodynamic quantities for DzO at 0
K are the sublimation enthalpy (ivlsub), 11,900 cal/mol;:’:’
the intermolecular vibrational zero point energy (ZPEinte,),
The Journal of Physical chemistry, voi. 79. NO 22, 1975
 2354 Owicki, Lentz, Hagler, and Scheraga

3 521 439 338 178 161 83

294 213 162 56 33
142
4 539 478 458 170 169 164
458 318 318 164 114 46
315 213 165
148 148 139
5 595 551 517 206 195 170
506 472 386 167 147 102
346 334 284 95 33 19
265 187 176
138 149 145
5* 705 512 479 199 191 189
408 355 313 123 113 93
294 253 208 70 59 47
196 187 46 44 36

6d 568 515 515 215 208 208

514 514 490 154 154 149
341 343 323 121 68 68
305 305 236 47 28 20
189 169 169
139 139 128

660 603 574 210 204 187

543 501 456 179
154 171
139 165
120
440 393 368
347 340 333 425 93 50
19
300 287 216
165
203 151
193 146
183

694 630 554 212 206 201

550 541 519 197 155
191 169
146
495 476 415 162
128
394 348 336 82
335 318 301 8
36 46 27
43
272 254 217
155
209 200
152 147
183

(a) msle have been sealed as described in the t e x t .

(b) For a discuseion of the nstare of these mode., sse Table 1

IT1 of LHS.
(0) Normal mode frequenoies of rhe Lsiiesoordinsred s u r
p'"t'er.
(d) Because of eoinp~Ldliionn1 difficulLiCs, the frequencies for
Li
fheas flustern are obtained by scaling the corresponding
H20 freqvanciell In Table 111 of U S . Based on a C~llperi-

son of the IsoIope effect i n cluscsrs for which bath DzO

and HzO ENS normal mode yldyaee wsre avntlabls. the

2800 cal/m01;~~
and the change in intramolecular vibration-
al ZPE upon sublimation (AZPEi,t,,), 1000 cal/m01.~0
111. Experimentally Observed Thermodynamic
Quantities and Computational Procedures
Experimentally observed values of the enthalpy and en-
tropy of DzO throughout the liquid range were obtained
from Baker's The data compilation of N6methy
and Scheraga6 was used to change Baker's reference state
to D2O ice a t 0 K.
The experimental Helmholtz free energy (to be com-
pared with the calculated Helmholtz free energy) is taken
to be equal to the observed Gibbs free energy. The experi-
mental internal energy (to be compared with the calculated
internal energy) is likewise taken to be equal to the ob-
served enthalpy.
The constant-pressure heat capacity for D2O throughout
the liquid range was taken from Eucken and Eigen's
study.14 The temperature dependent molar volume was
calculated from Kell's equation.35
Following LHS, the two adjustable parameters of the
theory, a and d , were varied to fit experiment by minimiz-
ing the x2 function:
The Journal of Physical Chemistry, Vol. 79, No.22, 1975
X2 = cT I[(Fcalcd,T - Fobsd,T)100/Fobsd,TI2+
[(Ucalcd,T- Uob~d,T)100/Uobsd,T]~)
(3)
x2 measures the sum of the squared percent deviations of
calculated from observed values of the free energy F and
internal energy U over a set of 11 temperatures from 4 to
100OC. At every step of the minimization algorithm, for
each temperature the equilibrium distribution of clusters
( N j }was determined by requiring that the free energy be a
minimum, in accordance with the maximum-term method
used to derive the partition function. As LHS noted, this
procedure does not introduce any new adjustable parame-
ters.
IV. Preliminary Results
As described in section IVA, our calculations have sug-
gested that it is difficult to obtain physically reasonable re-
sults by a straightforward best-fit adjustment of a and d
using the values of Elat and the ZPE's given in section IID.
In section IVB, we report our computations that lead to a
final choice for the values of a, d, Elat, and the ZPE's. In
section V, we discuss our principal results which were ob-
Thermodynamic Properties of Liquid Deuterium Oxide
TABLE 11: Summary of Theoretical Calculations
Calcu-
lation
no. Description aa In d b
~~
1 H,O; LHS results 5078 -23.90
2 DzO; aand d adjusted; exptl
Elatand ZPE's 5292 -23.24
3 D,O; H 2 0 values of a and d ;
exptl Elat and ZPE's 5078 -23.90
4 DzO; H 2 0 values of a, d, E,,,;
best fit ZPE's. This is the
principal vesult. 5078 -23.90
5 DzO; H,O values of a, d , Elat;
ZPElnt,, altered 5078 -23.90
a Units: cal/mol of interaction. Units of d: dyn cm4/radian2molecule. Mean monomer librational frequency in cm-l, calculated by
relating vl,b to d, as described in section IIB. Units: cal/mol. e Reduced ( x ~ ) . ~ ' ' J ~
tained with these final values.
A. Calculations with Elat = -13,700 cal/mol. The mini-
mum value of x2 for D20 is obtained with a = 95,300 cal
cm3/mol of bond and d = 1.16 X lo6 cal cm3/radian2 mol.
Physically, this corresponds to an interaction between
water molecules in neighboring clusters of 5290 cal/mol of
such interaction (compared to 6850 cal/mol in DzO ice,
based on the lattice energy) and a mean monomer libra-
tional frequency of 593 cm-l (compared to a mean libra-
tional frequency of 517 cm-l in D20 ice3". Statistically,
the fit is characterized by a reduced x 2 parameter value of
2.2137,38 (Table 11,calculation 2).
The theory predicts F quite accurately (within -4%).
The internal energy and entropy are fit somewhat less well
(within 4%), and, since the theory underestimates the
magnitude of the temperature dependence of both of these
quantities, C, is underestimated by as much as 40%. This
poor fit is not unexpected, since the calculation of the heat
capacity involves the second derivative of the free energy.
The nature of the fit is similar to that obtained for HzO by
LHS.
The values of a and d are larger by 4 and 94%, respec-
tively, for Dz0 as compared with HzO.* If the values of a
and d for H20 are used in the partition function for D20,
the calculated values of F, U, and S are all too high, and
the value of the reduced x2 parameter rises to 7.29,indicat-
ing a very poor fit (see Table 11, calculation 3). Thus, the
differences in a and d between DzO and HzO are signifi-
cant.
The adjustable parameters are intended to account for
inter-cluster interactions which otherwise have been ne-
glected. To the extent that they do, the increases in a and d
observed for D20 relative to the values for HzO suggest
that the average inter-cluster interactions are somewhat
stronger and orientationally considerably more rigid in
DzO than in H2O. However, one might expect that the
values of a and d for HzO and Dz0 should be approximate-
ly This expectation is based on the fact that the
cluster distributions obtained for the two liquids are quite
similar (Le., from calculations 1 and 2 of Table 11),imply-
ing that a cluster in Dz0 has, on the average, a set of neigh-
bors similar to those of a corresponding cluster in HzO.
Then, since the potential energy of interaction between
water molecules cannot be affected greatly by the substitu-
tion of a deuterium for a hydrogen atom, we are led to the
conclusion that the average intercluster interaction should
be approximately the same in Dz0 as in HzO.
Small increases in a and d for DzO can be rationalized
2355
% rms
error
vli< Elatd AHsu< ZPEint,,d AZPEint,,dx; e in F , U
580 -13,400 11,300 3500 1400 1.47 2.9
593 -13,700 11,900 2800 1000 2.21 3.5
426 -13,700 11,900 2800 1000 7.29 6.4
426 -13,400 11,900 2785 1285 2.27 3.6
426 -13,400 11,900 2500 1000 6.98 6.3
by arguments based on anharmonicity in the real cluster
interaction potentials, but such arguments are insufficient
to account for the very large increase in d obtained in cal-
culation 2. In fact, the large value of d predicted by the
theory results in the mean D2O monomer librational fre-
quency being greater than that for HzO (593 cm-' vs. 580
cm-l), an impossibility. The changes in the adjustable pa-
rameters (particularly d ) , thus cannot be interpreted sim-
ply in terms of their stated roles in the partition function.
Rather, they probably reflect compensations for other con-
tributions to the partition function which do not account
correctly for the effects of isotopic substitution.
One such contribution in which there are large uncer-
tainties involves the lattice energies and vibrational ZPE's
of HzO and DzO. Whalley30 has attributed the difference in
lattice energies calculated from experiment (Elat = -13,700
cal/mol for D20 and -13,400 cal/mol for HzO) to anhar-
monicities in intramolecular vibrations which cause small
differences in molecular structure sufficient to affect the
multipole interaction energies in ice. There is, however, a
€airly large uncertainty in the values of the vibrational
ZPE's which Whalley used to compute the lattice energies.
Whalley40 recently has published a new analysis of ground
state intermolecular vibrational frequencies and sublima-
tion shifts in intramolecular vibrational frequencies for
H20 only. The Elat and ZPE's calculated with the newer
data differ from those previously calculated by several hun-
dred calories per mole, which is approximately the same
magnitude as the energetic effects of the increased parame-
ters. A major source of the high values of a and d for D20
thus may be errors in the values of Elat and the ZPE's
which were used in the H20 and DzO partition functions.
B. Calculations with Elat = -13,400 callmol. We have
sought to obtain more physically meaningful results for
DzO by the following procedure: (1) fix a and d a t the
values for Hz0,39and (2)assume that the lattice energy of
HzO (-13,400 cal/mol) is also correct for DzO. These are
reasonable working assumptions.
Elat can be defined4' as
Elat = - m s u b - ZPEinter + AZPEintra (4)
where all quantities are calculated at 0 K. There are an in-
finite number of ways to apportion the 300 cal/mol alge-
braic increase in Elat of DzO among these three compo-
nents. Since m s u b is known relatively precisely, we have
chosen to regard it as fixed (11,900 cal/moP3), thus con-
straining -ZPEinter + AZPEintra to be equal to Elat +
m s u b (= -1500 cal/mol). The best least-squares fit to the
The Journal of Physical Chemistry, Vol. 79, No 22, 197.5
2356
-4WOO 7 20 40
Temperature ?C)
60 80
Figure 1. Comparison of the calculated and experimental values of
the free energy, F,as a function of temperature. The circles are ex-
perimental values for and the solid line represents the princi-
pal calculated results for D20. The squares and dashed line are the
experimental and calculated free energies, respectively, for H20,
taken from ref 4.
5 0 0 0 0 4
b
2500 I I I I l I ~ I
0 20 40 60 80
Temperature ("C)
Figure 2. Comparison of the calculated and experimental values of
the internal energy, U, as a function of temperature. The circles are
experimental values for D20,34and the solid line represents the prin-
cipal calculated results for D20. The squares and dashed line are the
experimental and calculated internal energies, respectively, for H 2 0 ,
taken from ref 4.
experimental values of F and U (minimizing x2 with re-
spect to ZPEinterwhile keeping a and d fixed at the values
for H2O) was found for ZPEinter = 2785 cal/mol and
AZPEintra= 1285 cal/mol. These values are not unreason-
able when compared with the values for H2030of 3500 and
1400 cal/mol, respectively, although the value (1285) of
AZPEintrafor D20 is higher than one would have predicted
from isotopic mass effects under the assumption that the
value for HzO is valid. The calculations carried out with
this set of parameters represent our principal results and
are summarized in Table I1 as calculation 4.
Fixing Elat, ZPEinter,and AZPEintraat their new values,
and allowing a and d to adjust to fit the experimental data,
produces a much smaller change in a and d with respect to
the values for H20 than that obtained in calculation 2; a
increases by 0.4%,while d increases by 26% (not shown in
Table 11).This is consistent with our assumption that an
important cause of the large changes in a and d in calcula-
tion 2 relative to their values for H2O (calculation 1)is the
lack of precision in the values of Elat, ZPEinter, and
AZPEintraused.
In calculation 4, most of the adjustment in Elat is
achieved by increasing AZPEintra,while ZPEjnteris affected
very little. In order to further delimit the sensitivity of our
results to variations in these parameters, we have per-
formed a final calculation (no. 5, Table 11) in which all of
the 300 cal/mol increase in Elat (from -13,700 cal/m01~~ to
The Journal of Physical Chemistry, Vol. 79, No. 22, 1975
Owicki, Lentz, Hagler, and Scheraga
100
15
0
I I
20
I 1
40
I I
60
I I
80
I
IO0
Temperature P C )
Figure 3. Comparison of the calculated and experimental values of
the entropy, S, as a function of temperature. The circles are experi-
mental values for D20,34and the solid line represents the principal
calculated results for D20. The squares and dashed line are the ex-
perimental and calculated entropies, respectively, for H20, taken
from ref 4.
I
100
I I I I I I I I I I 1
0 20 40 60 80 IO0
Temperature ("C)
Figure 4. Relaxational heat capacity and comparison of the calculat-
ed and experimental values of the heat capacity, C,, as a function
of temperature. The circles are experimental values for D20,14 and
the solid lines represent the principal calculated results for D20. The
squares and dashed line are the experimental and calculated heat
capacities, respectively, for H 2 0 , taken from ref 4.
the value for H20 of -13,400 cal/moPO) is put into
ZPEinter.The resultant fit to the experimental values of F
and U is poor, being only slightly better than that obtained
in calculation 3 (also with the values of a and d for H20,
but with experimental values of Elat and ZPE's). Thus, in-
creases in AZPEintrafrom 1000 cal/m01~~ are important in
fitting theory to experiment, at least under our constraint
of the equality of Elat for H2O and D2O.
V. Principal Results
The theoretical (calculation 4, Table 11) and experimen-
tal values of the free energy ( F ) ,internal energy (U),entro-
py (S),and constant-pressure heat capacity (C,) are pre-
sented in Table I11 (miniprint), and depicted in Figures
1-4. The LHS results for H2O also are included in the fig-
ures. The nature of the fit for our principal results is simi-
lar both to that of calculation 2 and to that of LHS for
H20. The theory correctly predicts the signs of the isotopic
differences in these thermodynamic quantities throughout
the liquid temperature range. This is significant, because
these are relatively small differences between large num-
bers and, therefore, represent a sensitive test of the theory.
The theoretical distributions of D2O clusters at 4, 50,
and 100°C are shown in Figure 5 along with the LHS H2O
distributions. The results indicate that liquid D2O is com-
Thermodynamic Properties of Liquid Deuterium Oxide 2357

r I I I I I I I

- Ai 1.35 3.40
I IOOOC
-

n
L
U
I

-i
m

0 200 400 600 800

' I 2 3 5 . 4 5 6 7 S
Cluster Species u p (cm-l)

Figure 5. Calculated distributions of the mole fractions of H20 (un-
filled bars, taken from ref 4) and D20 (hatched bars) molecules in
various cluster species at three temperatures. The "star" pentamer
is represented by 5" and is presented beside the dimer and trimer
because it, like them, is a noncyclic cluster species. The data for
H20 at 4OC were obtained by interpolation.
Figure 6. Calculated histograms of the frequency distributions of
D20, g(q), at
two temperatures. The units of g(vJ are arbitrary, and
the histograms have been normalized to the same value at both
temperatures. The smooth curves drawn through the histograms
represent a roughly averaged g(vJ. The numbers over the bracketed
regions are the sums of g(vI)over those regions.

TABLE VII: Comparison of Theoretical and

Representative Experimental Results for
Intermolecular Motions in Liquid D20a
Approx positions of
Method vibrational bands, cm'j

This theory 40 160 330 520

Infrared 165 505
Raman' 60 175 3 50 500
Inelastic neutron
scatteringd 50 160 465
a Tabulation of representative experimental results adapted
from Walrafen.45 * Reference 42. c Reference 43. Reference 44. I l l I l l I 1
0 20 40 60 80 IO0

posed primarily of cyclic pentamers and hexamers, with di-
mers, trimers, and star pentamers the next most important
species. Only about 1%of the water molecules are mono-
meric. The DzO and H20 distributions are quite similar.
They are also similar in their temperature dependence; as
was noted by LHS, increasing the temperature increases
the proportion of noncyclic relative to cyclic clusters.
Tables IV-VI (in miniprint) present the contributions of
the various terms of the partition function to the calculated
values of F, U, and S. ZPEinterhas been added to FIC and
UHB,the energies derived from the internal configuration-
al partition function, to adjust the reference zero of energy
to the bottom of the 0 K ice intermolecular potential well.
Tables IV-VI also include the isotopic differences calculat-
ed using the LHS HzO data.
Histograms representing the spectral density g(v) of the
intermolecular vibrational normal modes of DzO at 4 and
100°C are presented in Figure 6. These were calculated ac-
cording to eq 22 of LHS. Smoothed averages of the data are
also presented in Figure 6. The major features of the calcu-
lated spectra are peaks near 40, 160, 330, and 520 cm-'.
There is also a small component at 700 cm-I corresponding
to the highest frequency mode of the star pentamer. These
results are in fairly good agreement with spectroscopic
studies, the results of which are summarized in Table VII.
The red shift with increasing temperature which is found
in infrared spectra44is reproduced by the theory. This can
be seen by comparison of the sums of g(v) over the brack-
eted librational regions in Figure 6, a t 4 and 100OC.
Quantities related to the structure of the liquids (DzO
Temperolure CC)
Flgure 7. Theoretical fraction of hydrogen bonds unbroken, XHB.as
a function of temperature. The dashed line, which is for H20, is
taken from ref 4. The solid lines refer to the various D20 calculations
and are numbered as in Table 11.
and, as before, HzO from LHS) are presented in Table VI11
(miniprint). These include, as functions of temperature,
the fraction of unbroken hydrogen bonds ( X H B )hydrogen
,
, and ET)^^ as defined in sec-
bond energies [ ( E I ) , ~(EuIaq,
tion VI], the experimental molar volumes (V), and the hy-
drogen-bond relaxational heat capacity (Cp,relax = dUH%/
dT). The relaxational heat capacities are also plotted in
Figure 4.The Xu% data are presented in Figure 7, and the
hydrogen-bond energies are depicted in Figures 8-10.
VI. Discussion
Our principal results have been obtained by constraining
a and d to have the same values that LHS found for HzO
and by adjusting ZPEinter(and therefore AZPE,,,,,,) to fit
the experimental values of F and U of D20, subject to the
constraint that Elat = -13,400 cal/mol (the value for H20).
The parameters a and d retain the values originally as-
signed to them in the treatment of H20,4and thus the clus-
ter model is extended to D20 through the addition of only
one adjustable parameter (Le., ZPEi,,,,).
We noted in sections 1V.A and V that calculation 4 (the
principal results), calculation 2, and the LHS calculations
for HzO generate very similar fits to experiment. In all
cases, the major defect of the theory (as noted for HlO by
The Journal of Physical Chemistry, Vol 79, No 22, 1975
 2358 Owicki, Lentz, Hagler, and Scheraga

qc
2 2600

1 1 l I I 1 , I I
0 20 40 60 80 100 0 20 40 60 BO I00
Temperature ("C) Temperature (TI

Figure 8. Theoretical hydrogen bond energy as a function of
temperature. The dashed line, which is for H20 is taken from ref 4.
The solid fines refer to the various 1720calculations and are num-
bered as in Table 11. For a definition of (€Jag, see the Discussion sec-
tion.
Figure 9. Theoretical hydrogen bond energy, (&Iaq, as a function of
temperature. The dashed line, which is for H20, is taken from ref 4.
The solid lines refer to the various D20 calculations and are num-
bered as in Table II.

LHS) is an inability to account properly for the tempera-

ture dependence of U and s.
We turn now to a discussion of the molecular details of
the thermodynamic differences between D20 and H20, as
given in Tables IV-VI and VIII. The energy data for D2O
and H20 are comparable, because they refer to the same
reference state.
Principal Thermodynamic Functions. The isotopic dif-
ferences in translational and cluster rotational thermody-
namic functions are small compared with those arising
from vibrations. This happens for three important reasons.
First, the number of translational and rotational degrees of
freedom is comparatively small. If one neglects intramolec-
13001
I
0
l l
20
I I
40
a
I I
60
Temperature (TI
I
---__

I
80
I ]
100

ular motions, a cluster of j water molecules has three trans-
lational, three rotational, and (6.1' - 6) vibrational degrees
of freedom. According to our calculations, most of the
water molecules are in clusters with j = 5 or 6, so that vi-
brational modes predominate.
Second, translations and rotations (except for j = 1) are
fully excited in the temperature range treated, so that the
isotope effect on the contributions of these degrees of free-
dom to the overall internal energy is minimal. In contrast,
many vibrational modes are excited only weakly, leading to
a large isotope effect.
Third, isotopic substitution of the hydrogen alters the
molecular principal inertial moments much more than the
molecular mass. In the partition function, many vibrational
terms are more sensitive to the inertial moments than to
the masses, while the reverse is true for translational and
(roughly) for rotational terms. Comparatively, this en-
hances the vibrational isotope effects.
The isotopic differences in Flc and in UHB are interme-
diate in size between the vibrational and translational and
rotational differences. They result primarily from the
smaller value of AZPEi,tra in DzO.
Hydrogen-Bond Energy. Next we discuss the hydrogen-
bond energy in liquid water as well as the effects of isotopic
substitution on this quantity. I t has been noted46 that
there are a variety of ways to define the "hydrogen-bond
energy" in a given system, a fact which can lead to confu-
sion in the comparison of various experimentally or theo-
retically determined values. Any definition of this quantity
should refer to the energy changes during some well-de-
fined physical process which involves the rupture or forma-
tion of hydrogen bonds. The hydrogen-bond energy there-
Flgure 10. Theoretical hydrogen bond energy, ET)^^, as a function
of temperature. The dashed line, which is for H20, was calculated
using the partition function from ref 4. The solid lines refer to the
various D20 calculations and are numbered as in Table II.
fore is a state function of the system. In some cases, it may
be desirable to stress a particular contribution to the total
energy change for a given change in state. Then a second
part of the definition must be a statement of exactly what
components of the total energy change are to be consid-
ered.
An example will clarify this. Eisenberg and Kauzmann4'
give as one possible definition of the hydrogen bond energy
EH-bond = -(1/2)Eiat (= 6700 cal/mol of bond for H2O).
The initial state is ice Ih at 0 K; the final state is infinitely
dispersed water molecules again at 0 K. The quantum me-
chanical potential energy of the system is included in
EH.bond, but Z P E i n t e r and A Z P E i n t r a are not. E H - b o n d iS a
measure of the energy of interaction of nonvibrating mole-
cules in ice.
In this paper we consider three definitions of the hydro-
gen-bond energy which are relevant to the liquid state.
These are the theoretical quantities (Eu)aq, and
ET)^^ tabulated in Table VI11 and depicted in Figures
8-10 for both D2O and H20.
( E I )and~~ have been defined by LHS as follows.
( E I ) is~ the
~ internal configurational energy increase per
hydrogen bond ruptured in transforming ice at 0 K to the
equilibrium liquid at a given temperature and experimen-
tal molar volume.4s (471)~~ includes changes in the magni-
tudes of potential energies of interaction between mole-
cules, the effects of the background potential, and the in-

The Journal of Physical Chemistry, Vol. 79, No.22, 1975

Thermodynamic Properties of Liquid Deuterium Oxide
crease of ZPEintraupon the rupture of a hydrogen bond in
the liquid. It does not include translational, rotational, or
(intermolecular) vibrational effects. ( E u ) ~a ~quantity
, sim-
ilar to (Edaq,refers instead to the conversion of the equi-
librium liquid at a given temperature and experimental
molar volume to a hypothetical liquid composed entirely of
monomers (Le., all hydrogen bonds broken) at the same
temperature and molar volume. The energy accounting is
done in exactly the same way as it is for For mathe-
matical definitions of these quantities, the reader should
consult L H S 4
The above neglect of translational, rotational, and vibra-
tional energy changes allows one to focus on the changes in
the magnitudes of the potential energies of interaction in
the system. In actual physical processes, however, dynamic
effects (translational, rotational, and vibrational) are im-
portant. We can include them by defining the total hydro-
gen-bond energy ET)^^ to be the total internal energy
change of the system per hydrogen bond ruptured for the
process used to define ( E u ) ~Le., ~ ; ET)^^ is the sum of
( E u ) and
~ ~ changes in the translational, rotational, and vi-
brational energies.
Having defined these hydrogen-bond energies, we now
consider the theoretical values that we have obtained for
them in DzO and H2O. We have included in Figures 8-10
the results of all the calculations in Table 11.
In all three definitions, both the initial and final states
are condensed phases, so that the rupture of a hydrogen
bond does not result in as complete a loss of stabilizing in-
teractions with neighboring molecules as it does for
EH-bond. Hence, hydrogen-bond energies calculated by
these definitions are considerably smaller than EH-bond.
In contrast to EH-bond, the hydrogen-bond energies intro-
duced above are defined at temperatures other than 0 K
and, in fact, vary considerably with temperature. For ex-
ample, ET)^^ varies by -20% (-250 cal/mol of bond) over
the liquid temperature range. The temperature depen-
dence of ( E I ) and~ ~ ( E I J )arises
~ ~ primarily from the
changes of the equilibrium cluster distribution and molar
volume with temperature. For ET)^^ there is the addition-
al effect of the variation of translational, rotational, and vi-
brational energies with cluster distribution and tempera-
ture.
Our calculations suggest that the energy required to
break the hydrogen bonds in the clusters of liquid D20 is
somewhat less than the corresponding energy in liquid
H20, as seen in Figures 8-10. The main reason for this in
the case of and (EU)aq is that the change in ZPEintra
upon breaking a hydrogen bond in the liquid is less for D20
than for HzO. There are additional translational, rotation-
al, and vibrational effects for ET)^^. The differences
among the curves for different DzO calculations result from
variations in the parameters listed in Table 11. These con-
clusions, however, must be tempered by the knowledge that
the uncertainties in our calculations are not small with re-
spect to the calculated isotopic hydrogen-bond energy dif-
ferences.
Water Structure. We now consider the structural differ-
ences between DzO and HzO. Although we have not dis-
played the cluster distributions for calculations other than
no. 1 (H20) and 4 in Figure 5, those for calculations 2, 3,
and 5 did not differ greatly from those depicted. The most
significant variation occurred for calculations 2 and 3 at
high temperatures, where the contribution of the star pen-
tamer increased to approximately the same level as that of
2359
the cyclic pentamers and hexamers. Nevertheless, the equi-
librium cluster distributions for D2O and HzO are very sim-
ilar. For this reason, the calculated fractions of hydrogen
bonds in D20, XHB,does not differ significantly from that
in HzO, as shown in Figure 7. The uncertainties in the cal-
culations make it impossible to determine which liquid (if
either) is more fully hydrogen bonded. We can, however,
conclude that the isotopic differences in XHBare small,
probably less than 0.01.
There is no inconsistency in the finding that it takes less
energy to break a hydrogen bond in liquid D20 than in liq-
uid H2O (calculation 4, Figures 8-10) while, at the same
time, D20 may be (slightly) more hydrogen bonded than
HzO (calculation 4,Figure 7). The isotopic effects on these
quantities are not related in a simple way.
If one considers “water structure” to refer to the fraction
of hydrogen bonds unbroken in the liquid and to the equi-
librium distribution of clusters in the liquid, then our re-
sults indicate that DzO and H2O have a very similar struc-
ture throughout their common liquid temperature range.
This is in accord with near-infrared work of Thomas et aLZ3
and the low-angle X-ray scattering study of Narten and
LevyZ1mentioned in section I. This conclusion is relatively
insensitive to variations in a, d , Elat, ZPEint,,, and
AZPEintrain the range of values likely to be encountered
for D2O.
Consistent with our finding that the structures of the
two liquids are similar, the calculated relaxational heat ca-
pacity of D2O is approximately equal to that of H20, as can
be seen in Figure 4.In this theory, the differences between
the heat capacities of D20 and H2O arise not from relaxa-
tional effects, but principally from the lower frequencies of
the D2O cluster vibrational modes, LHS noted that the
theory underestimates the relaxational heat capacity. It is
possible that a more correct treatment of this quantity
would produce a significant contribution to the isotopic
differences in the overall heat capacity.
NBmethy and Scheraga6J1 were able to extend their
theory to explain the temperature variation of the molar
volume of liquid water by assigning molar volumes and
thermal expansion coefficients to the cluster and monomer
microphases. However, such a procedure would be both dif-
ficult and invalid for the present theory. The reason for
this is that here the molar volume of the liquid is deter-
mined by complicated packing interactions among nine
types of irregularly shaped clusters, which are too small to
be treated as separate phases. This is the same problem
which prevents us from calculating the radial distribution
function, as noted by LHS. Hence, within this theory, we
cannot explain the differences in the temperatures of maxi-
mum density of D20 and H20 except to say that these dif-
ferences must arise from the relatively small isotopic dif-
ferences in the theoretical equilibrium cluster distribu-
tions. A recurrent theme in this work has been that the dif-
ferences in thermodynamic properties between DzO and
HzO are caused primarily by isotope effects directly on the
inter- and intramolecular vibrational frequencies. It should
be pointed out that, by constraining the values of a, d , and
Elat for DzO and H2O to be equal (see section IV), we have
not allowed for differences arising from isotope effects on
the molecular geometry and dipole moment. Available evi-
suggests, however, that these molecular differ-
ences are small. Our results provide a reasonably satisfac-
tory description of the system without considering them.
Finally, LHS noted that this cluster theory has much in
The Journal of Physlcal Chemistry, Vol. 79, No. 22, 1975
2360
common with a continuum point of view: water molecules
are allowed to exist in a large number of states (clusters),
and inter-cluster interactions are found to be fairly strong.
In the present paper, the theory again provides a bridge be-
tween the traditional mixture and continuum approaches.
Although it starts from a mixture premise, it agrees with
continuum theory studies7J0 in the finding that the ther-
modynamic differences between liquid D20 and H20 are
due to rather subtle vibrational effects instead of grosser
structural changes in the liquids.
VII. Summary and Conclusions
This paper reports on the continuing study of the liquid
water system by means of a statistical mechanical "cluster"
model. A theory developed for H203!4is applied to D20 as a
further test of the theory and in order to gain insight into
the differences between these liquids.
Variation of the two adjustable parameters of the theory
to fit experimental thermodynamic quantities produces
unexpectedly large changes in the parameters relative to
their values for H20, and also some physically unreal iso-
tope effects at the molecular level. We have attributed this,
in large part, to uncertainties in the experimental values of
the 0 K ice lattice energy (Elat),intermolecular zero-point
energy (ZPE,,t,,), and changes in intramolecular zero-point
energy on sublimation (AZPE,,,,,), which are difficult to
obtain accurately. These inaccuracies have created difficul-
ties in the application of the theory, and we feel that an ac-
curate determination of the isotopic differences in these
quantities is crucial to a quantitative understanding of the
isotopic differences in the liquids.
Because of the above-mentioned uncertainties, we have
obtained our principal results by fixing the adjustable pa-
rameters and Elat for D20 a t their values for H20, and by
varying ZPE,,ter and AZPEintrato obtain the best fit to ex-
perimental thermodynamic quantities subject to the con-
straint on Elst. In this calculation, the free energy (F),in-
ternal energy ( U ) ,and entropy (S)of D2O are fit fairly well
throughout the entire liquid temperature range. The error
in the predicted heat capacity (C,) is more serious. The
size of the errors is somewhat larger than those obtained by
fitting H20 with the same theory, but, significantly, the
signs of the isotopic differences in these thermodynamic
quantities are predicted correctly. We also have calculated
t,he vibrational spectral density in the intermolecular nor-
mal mode vibrational region, and have found it to be in rea-
sonable agreement with vibrational spectroscopic results.
The results of this calculation suggest that the isotopic
differences in F, U , S, and C, result primarily from the
changes in intra- and intermolecular vibrational frequen-
cies caused by isotopic changes of the mass and principal
moments of inertia of the water molecule.
We have concluded that the energy required to break a
hydrogen bond in liquid D2O is somewhat lower than in liq-
uid H20. The similarities of the equilibrium cluster distri-
butions and the fractions of hydrogen bonds unbroken for
both D20 and H20 imply that the structures of the liquids
are quite similar.
In summary, we find that most of the thermodynamic
differences between liquid D2O and H20 are explainable
directly in terms of isotopic effects on the intra- and inter-
molecular vibrational frequencies rather than by differ-
ences in the structures of the two liquids.
Miniprint Material Available. Full-sized photocopies of
The Journal of Physical Chemistry, Vol. 79, No. 22, 7975
Owicki, Lentz, Hagler, and Scheraga
the miniprinted material from this paper only, Tables I,
111-VI, and VIII, or microfiche (105 x 148 mm, 24X reduc-
tion, negatives) containing all of the miniprinted and sup-
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code number JPC-75-2352.
References and Notes
(1) This work was supported by research grants from the National Institute
of General Medical Sciences of the National Institutes of Health, U.S.
Public Health Service (GM-14312), and from the National Science Foun-
dation (BMS71-00872 A04).
(2) (a) NSF Predoctorai Fellow and NIH Trainee at Cornell University. (b) NIH
Trainee at Cornell University. (c) To whom requests for reprints should
be addressed at Corneil University.
(3) A. T. Hagler. H. A. Scheraga, and G. Nemethy, J. Phys. Chem., 76,
3229 (1972).
(4) B. R. Lentz, A. T. Hagler, and H. A. Scheraga. J. Phys. Chem., 78, 1531
(1974).
(5) The term "hydrogen bond" is used here for both 0-He-0 and 0-De-0
interactions.
(6) G. Nemethy and H. A. Scheraga, J. Chem. Phys., 41, 680 (1964).
(7) C. G. Swain and R. F. W. Bader, Tetrahedron, I O , 182 (1960).
(8) M. S. Jhon, J. Grosh, T. Ree, and H. Eyring, J. Chem. Phys., 44, 1465
(1966).
(9) C. M. Davis, Jr., and D. L. Bradley, J. Chem. Phys., 45, 2401 (1966).
(10) W. A. Van Hook, J. Phys. Chem., 72, 1234 (1968).
(11) G. Nemethy and H. A. Scheraga, J. Chem. Phys., 36,3382 (1962).
(12) It has been notedI3 that Nemethy and Scheragal' fit their theory for
H20 to an experimental value of the entropy of H20 which did not con-
tain the ap roximately 0.8 cal/mol deg zero point entropy of ice. Their
f
D20 study, however, utilized the correct entropy: this caused an exag-
geration of the experimental thermodynamic isotopic differences. The
theoretically derived differences between the two liquids likewise were
greater than they should have been.
(13) A. T. Hagler, H. A. Scheraga, and G. Nemethy, Ann. N.Y. Acad. Sci.,
204, 51 (1973).
(14) A. Eucken and M. Eigen. Z.Nektrochem., 55, 343 (1951).
(15) G. S. Kell in "Water a Comprehensive Treatise", Vol. 1, F. Franks, Ed.,
Plenum Press, New York, N.Y., 1972, Chapter 10.
(16) D. Eisenberg and W. Kauzmann, "The Structure and Properties of
Water", Oxford University Press, New York. N.Y., 1969, p 174.
(17) K. Lonsdale, Proc. R. SOC.London, Ser. A, 247, 424 (1958).
(18) R. W. Blue, J. Chem. Phys., 22, 280 (1954).
(19) A. Holtzer and M. F. Emerson, J. Phys. Chem., 73, 26 (1969).
(20) E. Kilmin, personal communication.
(2 1) A. H. Narten, M. D. Danford, and H. A. Levy, Discuss. Faraday SOC., 43,
97 (1967).
(22) H. S. Frank, in ref 15, Chapter 14.
(23) M. R. Thomas, H. A. Scheraga, and E. E. Schrier, J. Phys. Chem., 69,
3722 (1965).
(24) J. L. Lebowitz and J. S . Rowlinson, J. Chsm. Phys., 41, 133 (1964).
(25) J. L. Lebowitz. Phys. Rev., 133, A895 (1964).
(26) Normal mode analysis was carried out identically with that for H20 in B.
R. Lentz, A. T. Hagler, and H. A. Scheraga, J. Phys. Chem., 78, 1844
(1974).
(27) A. Ben-Naim and F. H. Stillinger, Jr., in "Water and Aqueous Solutions",
R. A. Horne, Ed., Wiley-lnterscience, New York, N.Y., 1972, Chapter 8.
(28) 0. Weres and S. A. Rice, J. Am. Chem. Soc., 94, 8983 (1972).
(29) B. R. Lentz and H. A. Scheraga, J. Chem. Phys., 58, 5296 (1973): 61,
3493 (1974).
(30) E. Whalley, Trans. Faraday Soc., 53, 1578 (1957).
(31) Reference 16, p 4.
(32) T. R. Dyke and J. S. Muenter, J. Chem. Phys., 59, 3125 (1973).
(33) Reference 16, p 101.
(34) B. L. Baker, US. Atomic Energy Commission Report No. AECU-4738,
1959.
(35) G. S. Kell, J. Chem. Eng. Data, 12, 66 (1967).
(36) A. J. Leadbetter, Proc. R. SOC.London, Ser. A, 287, 403 (1965).
(37) The reduced x2.as described by B e v i n g t ~ nis. ~a~measure of the good-
ness of fit after the variance of the experimental data has been taken
into account. We have estimated the variance of ail experimental data
at 2.5%: a reduced x2 value of about 1.5 or less indicates that it is not
unlikely that the theory provides a valid representation of the data. The
theory fits D20 less well than H20. for which LHS obtained a reduced x2
value of 1.47.
(38) P. R. Bevington, "Data Reduction and Error Analysis for the Physical
Sciences", McGraw-Hill. New York, N.Y., 1969, Chapters 10 and 11.
(39) In addition to the background potential, the a parameter includes a small
contribution from the shift in ZPEintra upon the rupture of a hydrogen
bond in the liquid (see LHS4).This quantity is isotope dependent, but the
effect should be small enough to neglect at our present level of approxi-
mation.
(40) E. Whalley, in "Physics and Chemistry of Ice", E. Whalley, S.J. Jones,
Energy Parameters in Polypeptides 2361

and L. W. Gold, Ed., Royal Society of Canada, 1973, p 73.
(41) Reference 16, p 138.
(42) D. A. Draegert. N. W. B. Stone, B. Curnutte, and D. Williams, J. Opt.
SOC.Am., 56, 64 (1966).
(43) G. E. Walrafen, J. Chem. Phys., 40, 3249 (1964).
(44) K. E. Larsson and U. Dahlborg, J. Nucl. Energy, Parts A B , 16, 81
(1962).
(45) G. E. Walrafen in "Water, A Comprehensive Treatise", Vol. I, F. Franks,
Ed., Plenum Press, New York, N.Y.. 1972, Chapter 5.
(46) Reference 16, p 137.
(47) Reference 16, p 139.
(48) The difference in temperature between the initial and final states is not
important, because in this theory the relevant energies (e.g., €bt) are
taken to be temperature independent.

Energy Parameters in Polypeptides. VII. Geometric Parameters, Partial Atomic Charges,

Nonbonded Interactions, Hydrogen Bond Interactions, and Intrinsic Torsional Potentials
for the Naturally Occurring Amino Acids'

F. A. Momany,2aR. F. McGuire,2bA. W. Burgess,2cand H. A. Scheraga*2d

Department of Chemistry, Cornel1University, ithaca, New York 14853 (Received January 3 1, 1975;
RevisedManuscript Received July 10, 1975)

Empirical interatomic potentials are developed for calculating the energetically most favored conforma-
tions of polypeptides and proteins. Geometric parameters, partial atomic charges, nonbonded interaction
energies, hydrogen bond energies, and intrinsic torsional potentials are determined for each of the natural-
ly occurring amino acids. The geometric parameters were obtained from a survey of the recent structural
literature; the bond lengths and bond angles of a given type of residue appear to be similar from structure
to structure. The partial atomic charges (overlap normalized) for every atom of each amino acid were ob-
tained by the CNDOI2 method. Parameters of the nonbonded and hydrogen-bonding potentials were
taken from previous calculations on crystals of small molecules; however, the coefficient of the nonbonded
repulsive term for two atoms separated by three bonds, the central one being the bond about which rota-
tion can take place (1-4 interactions), was reduced by a factor of 2 to make the repulsive force constants
compatible with those computed from Hartree-Fock and Thomas-Fermi-Dirac repulsive potentials. In-
trinsic torsional potentials were introduced, where necessary, to reproduce experimental internal rotation
barriers. Interaction arrays for interatomic pairwise interactions were defined in order to distinguish hy-
drogen bonding, and 1-4, from 1-5, 1-6, etc., interactions. Procedures are described for carrying out con-
formational energy calculations on polypeptides and proteins, using these empirical potentials. Computer
programs for performing these calculations are available.

I. Introduction menta, and later by using MO-LCAO u charges of Del Re48

Recent investigations in this and other laboratories3-12
have emphasized the need for accurate interatomic poten-
tials to determine polypeptide and protein conformations.
The present paper provides the details of the set of poten-
tials presently in use in this laboratory.
In order to obtain a perspective on the present status of
potential functions, we begin with a short summary of the
evolution of these empirical potentials. The earliest investi-
gations of polypeptide conformation were carried out with
hard-sphere repulsive potentials, using the van der Waals
contact distance as an overlap criterion; these potentials ef-
fectively allowed for interatomic excluded volume effects,
and provided rough estimates of the allowed regions of con-
formational
Next, these potential functions were improved by replac-
ing the hard sphere by a Lennard-Jones 6-12 potential.
The attractive (dispersion) term was calculated from atom-
ic polarizabilities, and the position of the minimum of the
6-12 potential was taken to be the van der Waals contact
d i ~ t a n c e . ~ Electrostatic
",~ energies were also included by
estimating partial atomic charges, first from bond mo-
and MO A charges from Huckel theory.4a Intrinsic torsional
terms were included, with rotational barriers derived from
model A t this stage of development, hydro-
gen bonding was treated by a modification of the Lippin-
cott-Schroeder potential function.48 Using this set of po-
tentials, calculations were carried out to investigate the
conformational properties of single amino-acid residues,
homopolymers, and cyclic peptide^.^ In a few cases [cyclo-
(GlysProz) and cyclohexaglycyl],4d flexible geometry (i.e.,
bond stretching and bond angle bending) was allowed by
using appropriate force constants for these motions. When
applied to proteins (e.g., lysozyme,13 a-lactalbumin,14 and
r~bredoxin'~), united-atom potentials were used for -CH,
-CH2, and -CH3 groups to reduce the number of interac-
tions that had to be computed.
In the present paper, we report the results of our reex-
amination of the problem of interatomic potentials, where-
by we have obtained an improved self-consistent set. First,
the coefficients of the repulsive interatomic potential have
been refined by treating the packing of molecular crystals.9
In that work, it was found that the position of the mini-
mum of the interatomic potential was not the van der

The Journal of Physical Chemistry, Vol. 79, No. 22, 1975