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A resummed thermodynamic perturbation theory - A doubly associated reference
for positive and negative hydrogen bond perturbation theory for water
Bennett D. Marshall

cooperativity in water
To cite this article: Bennett D Marshall 2019 J. Phys.: Condens. Matter 31 184001

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 Journal of Physics: Condensed Matter

J. Phys.: Condens. Matter 31 (2019) 184001 (11pp) https://doi.org/10.1088/1361-648X/ab03c5

A resummed thermodynamic perturbation

theory for positive and negative hydrogen
bond cooperativity in water
Bennett D Marshall
ExxonMobil Research and Engineering, 22777 Springwoods Village Parkway, Spring TX 77389, United
States of America

E-mail: Bennettd1980@gmail.com

Received 28 September 2018, revised 24 January 2019

Accepted for publication 31 January 2019
Published 6 March 2019

Abstract
In this paper a resummed thermodynamic perturbation theory is developed which accounts
for both positive and negative hydrogen bond cooperativity in water. The theory is developed
in Wertheim’s multi-density statistical mechanics. We demonstrate that the hydrogen bonded
structure of water is controlled by positive hydrogen bond cooperativity in homodromic
hydrogen bonded clusters. Inclusion of negative anti-cooperativity in antidromic hydrogen
bonded structures has little effect on the underlying hydrogen bond structure of liquid water.
The resummed perturbation theory is shown to give hydrogen bond statistics consistent with
first principles ab initio molecular dynamics simulations. In addition, the theory is shown to
be in good agreement with experiment in the prediction of the average number of hydrogen
bonds per water molecule in a liquid at ambient conditions. Finally, we develop a full
thermodynamic model for water by including contributions to the free energy for isotropic
square well attractions. We demonstrate that the model gives good representation of saturated
liquid density, hydrogen bonding and vapor pressure. In addition, we show the full model
predicts the anomalous minima in isothermal compressibility and isobaric heat capacity.

Keywords: hydrogen bond, statistical mechanics, water, many body theory

(Some figures may appear in colour only in the online journal)

1. Introduction from ab initio calculations [4], to classical simulations using

It has been extensively demonstrated by ab initio methods
[1, 2] that hydrogen bonding in water clusters is non-pairwise
additive. That is, there is cooperativity in hydrogen bonding.
Hydrogen bond cooperativity in water can be positive or nega-
tive, depending on the geometry of the associated cluster. In
clusters which exhibit negativity cooperativity, the magni-
tude of the total energy of the cluster is less than that of the
sum over all the binary interactions. In clusters which exhibit
positive cooperativity, the magnitude of the total energy of
the cluster is greater than that of the sum over all the binary
interactions.
Water is one of the most analyzed molecules in the history
of science. Methods range from full ab initio [3], to classical
simulations using two and three body potentials developed
standard pairwise additive course grained potentials [5, 6], to
classical statistical mechanics using integral equation [7] and
perturbation [8] theories. The work in this paper will focus on
the end of this continuum of course graining and analyze the
effects of positive and negative hydrogen bond cooperativity
within a classical perturbation theory for water.
One may ask the question, ‘Why in this age of high-pow-
ered scientific computing, do we still need to work with these
arcane theories to develop approximate solutions which can
be more accurately obtained by more advanced methods?’
First, general analytical (or at least computationally negli-
gible) theories allow for deep insight, as well as the ability to
rapidly scan the effects of external variables. Second, using
classical statistical mechanics, these advances can be used
to construct ever more accurate thermodynamic models for

1361-648X/19/184001+11$33.00 1 © 2019 IOP Publishing Ltd  Printed in the UK

J. Phys.: Condens. Matter 31 (2019) 184001
complex mixtures. Simply put, one is not going to perform ab
initio calculations, or even classical molecular dynamics sim-
ulations, for a mixture composed of several hundred chemical
species. This is the domain of the classical equation of state,
which reigns supreme in commercial thermodynamics pack-
ages used to design and optimize industrial processes around
the world.
That said, results from first principles ab initio calculations
can still be employed in the development of classical pertur-
bation theories. Inclusion of binding energies calculated from
ab initio methods allows one to limit the empiricism in the
classical approaches [9, 10]. This will be our approach in the
current paper.
In this paper we extend Wertheim’s thermodynamic
perturbation theory [11, 12] to account for both positive
and negative hydrogen bonding cooperativity in water.
This work builds on a previous paper [9] which employed
second order perturbation theory (TPT2) to enforce posi-
tive hydrogen bond cooperativity in water. In this work we
extend this approach by enacting an RTPT. As will be shown,
TPT2 only provides the lowest order cooperativity correc-
tion to the more accurate RTPT theory. Also, in addition to
positive cooperativity, we include contributions for negative
(anti) cooperativity for the first time. We demonstrate that the
inclusion of negative cooperativity in antidromic hydrogen
bonded clusters has little effect on hydrogen bonded structure
when there is strong positive cooperativity in homodromic
structures. In agreement with detailed ab initio MD results,
the theory predicts that antidromic clusters are rare in liquid
water. In addition, the theory is demonstrated to accurately
predict the experimental value for the average number of
hydrogen bonds per water molecule. Finally, in section 4 we
incorporate the RTPT hydrogen bonding theory into a gen-
eral thermodynamic model for water which includes contrib­
utions due to isotropic attractions. We demonstrate that the
resulting thermodynamic model gives accurate predictions
of saturated liquid density, vapor pressure and hydrogen
bonding structure. We also show that the approach predicts
the anomalous minima in isothermal compressibility and iso-
baric heat capacity.
2. Theory
In this section  we develop a new hydrogen bonding theory
for water which includes both positive and negative hydrogen
bond cooperativity. Hydrogen bond cooperativity emerges
from non-pairwise additivity in hydrogen bonded clus-
ters. Water is modelled as a hard sphere of diameter d with
four association sites, which consist of two hydrogen bond
acceptor sites (O1, O2) and two hydrogen bond donor sites
(H1, H2) in the overall set Г  =  {O1, O2, H1, H2}.
We consider a geometric model for hydrogen bonding
known as conical square well association sites (CSW)
[13, 14]. The association contribution to the pairwise potential
when CSW association sites A and B interact is given by
φAB (12) = −εAB OAB (12)
(1)
2
B D Marshall
where
®
1 r12  rc and θA1  θc and θB2  θc
OAB (12) =
(2)
0 otherwise
and rc is the maximum distance between molecules for which
association can occur, θA1 is the angle between the center of
site A on molecule 1 and the vector connecting the two cen-
ters with θc being the maximum angle for which association
can occur. CSW sites have been successfully used to model
hydrogen bonding molecular fluids [9] and have also been
extensively employed as a primitive model to represent the
self-assembly of patchy colloids [15].
To include hydrogen bond cooperativity, we consider the
following simple model. The hydrogen bond energy of a
dimer, where the oxygen on one molecule is bonded to the
hydrogen on another, is given by εOH. A trimer cluster can
be formed in several ways as outlined in figure 1. The center
molecule in the cluster (the one bonded twice) can be bonded
at both a hydrogen and oxygen site (HOHO—top left), at both
oxygen sites (HOOH—top right) or at both hydrogen sites
(OHHO—bottom). The HOHO cluster is known to exhibit
positive cooperativity while the remaining two clusters HOOH
and OHHO exhibit negative (anti) cooperativity.
The total hydrogen bond energy of the OHOH trimer
cluster is written as
εHOHO = 2εOH + ∆εHOHO = εOH + (εOH + ∆εHOHO ) = εOH + ε+
OH .
 (3)
Where the term ∆εOHOH represents the correction for posi-
tive cooperativity. We have further defined the energy
ε+OH = εOH + ∆εHOHO which represents the effective
hydrogen bond energy of the second hydrogen bond.
It is assumed that the anti-cooperative trimer clusters
OHHO an HOOH are energetically equivalent
εHOOH = εOHHO = 2εOH − ∆εOHHO = εOH
(4)
+ (εOH − ∆εOHHO ) = εOH + ε− OH .

The term ∆εOHOH represents the correction for negative coop-
erativity, and we have defined ε−
OH = εOH − ∆εOHHO to be the
effective energy of the second anti-cooperative bond.
2.1.  Definition of the free energy
The theory is developed in the multi-density statistical
mechanics of Wertheim [11, 12, 16] where each bonding state
of a molecule is assigned a number density. The density of
molecules bonded at the set of sites α is given by ρα. It is
this assignment of separate densities to each bonding state of
a molecule which defines Wertheim’s statistical mechanics.
To aid in the reduction to irreducible graphs, Wertheim intro-
duced the density parameters σγ
σγ = ρα
(5)
α⊂γ
where γ is a subset of Г and the empty set α = ∅ is included
in the sum. Two notable cases of equation  (5) are σГ  =  ρ
and σo  =  ρo; where ρ is the total number density and ρo is
J. Phys.: Condens. Matter 31 (2019) 184001 B D Marshall

Figure 1.  Diagrams of associated trimer chains. Red circles represent hydrogen donor sites and red blue circles represent oxygen acceptor
sites.

the density of molecules not bonded at any association site Within perturbation theory, the single cluster diagrams are
(monomer density). The fraction of molecules NOT bonded at ordered in terms of the number of hydrogen bonds
the set of sites α is defined as ∞

(o)
σΓ−α ∆c
(10) = ∆cn
(6) Xα = . n=1
ρ
When considering potentials of interaction which contain a where Δcn is the sum of all diagrams which contain n associa-
hard sphere reference term, the change in free energy due to tion bonds. In terms of TPT applied to hydrogen bond cooper-
hydrogen bonding can be written exactly as ativity, Δc1 accounts for pairwise additive hydrogen bonding
Å ã contributions and Δcn (n  >  1) corrects the free energy for
A − AHS AAS ρo three body cooperative effects.
(7) = = ρln + Q + ρ − ∆c(o) /V
VkB T VkB T ρ In a recent publication, Marshall [9] developed a second
order perturbation theory TPT2 to account for positive
where V is the system volume, T is temperature, AHS is the hydrogen bond cooperativity in a four site water model. While
free energy of the hard sphere reference fluid and Q is given TPT2 can be used to incorporate hydrogen bond coopera-
by tivity, it cannot be used to enforce complete cooperativity in
 chains. For this, one must sum over all chain diagrams in what
Q = −ρ + cγ σΓ−γ .
(8) is known as resummed thermodynamic perturbation theory
γ⊂Γ
γ=∅ (RTPT). RTPT was initially developed by Wertheim [12] to
enforce complete blockage due to steric hindrance in a 2B
The fundamental graph sum Δc(o) is an infinite series of int­
(one donor and one acceptor site) association model. Marshall
egrals which encode the hydrogen bonding interactions. The
and Chapman [19] then extended this approach to enforce
functions cγ are obtained from derivatives of this sum
hydrogen bond cooperativity in 2B associating fluids.
∂∆c(o) /V In what follows, we extend the approach of Marshall and
cγ =
(9) for γ = ∅. Chapman [19] to develop an RTPT for a four site association
∂σΓ−γ
model meant to describe hydrogen bonding in water. Figure 2
Perturbation theory (TPT) within Wertheim’s multi- illustrates two classes of chain diagrams, positive coopera-
density formalism is defined as neglecting all contributions tivity homodromic chains (+chains) and negative cooperativity
to Δc(o) which contain more than a single associated cluster antidromic chains (−chains).  +chains (panel a) in figure 2 are
[11]. Effectively this allows for intra-cluster hydrogen bond chains for which all molecules in the chain which are bonded
corrections to the reference system free energy but does not twice, are bonded at an acceptor oxygen and donor hydrogen;
correct for inter-cluster corrections to the reference system exhibiting positive cooperativity. On the other hand, all mole-
free energy. While this is a severe approximation, it has been cules bonded twice in  −chains are bonded at either two acceptor
extensively demonstrated that TPT can be accurately applied oxygens or two donor hydrogens (panel b) in figure 2, therefore
to study associating fluids [17, 18]. exhibiting negative cooperativity. Note, these  +  and  −chains

3
J. Phys.: Condens. Matter 31 (2019) 184001 B D Marshall

molecule 1 and site B on molecule 2 are oriented such that a

hydrogen bond is formed [13]
2
(1 − cos θc )
(17)
κAB = .
4
For a  +chain consisting of n association bonds, we extend
the RTPT of Marshall and Chapman [19] to the current 4 site
case to obtain
−fOH )n−1 ´ 
∆cn+ = fOH (fOH+
2Ωn+1
σΓ−A (1)ghs (r12 )
  A∈Γ
OAB (12) σΓ−BC (2) ghs (r23 )
B∈Γ C∈Γ
 
× OCD (23) σΓ−DE (3) ghs (r34 ) · · ·
D∈Γ E∈Γ
OWX (n − 1, n) σΓ−XY (n) ghs (rn,n+1 )
Figure 2.  Illustration of positive cooperative (homodromic) and X∈Γ Y∈Γ
negative cooperative (antidromic) chains. 
× OYZ (n, n + 1) σΓ−Z (n + 1) d (1) · · · d (n + 1) .
Z∈Γ
form the base irreducible contributions from which all non- (18)
cyclic heterodromic clusters are created, including all clusters The positive cooperativity Mayer function is defined as
with water molecules bonded three and four times. Å ã
Equation (10) is split into a first order contribution as well εOH+
(19) fOH+ = exp − 1.
as contributions due to  +chains and  −chains kb T
∞
 Since equation (18) describes  +chains, all of the σΓ−BC rep-
(o)
∆c
(11) = ∆c1 + (∆cn+ + ∆cn− ). resent σΓ−Oi Hj . Hence, equation (18) may be simplified to the
n=2 form
For the first order contribution the result is [11] ∆cn+ 1 
= σΓ−Z fAZ λAZ σΓ−A
1  V 2
ˆ
∆c1 = 2
fAB σΓ−A (1) σΓ−B (2) OAB (12) ghs (r12 ) d (1) d(2) A∈Γ Z∈Γ
2Ω Ñ én−1
A∈Γ B∈Γ
(12) 2  2
where Ω  =  8π2 is the number of orientations, d(1)  =  dV1dΩ1 ( fOH+ − fOH ) λOH σΓ−Oi Hj . (20)
represents the volume element for integration over all orien- i=1 j=1
tations and positions, ghs(r12) is the pair correlation function 
of the hard sphere reference fluid, and f AB is the association While it is true that all σΓ−Oi Hj are equal for all i,j , they are
Mayer function given by the relation kept separated in the i, j sum in equation  (20) for counting
Å ã purposes. As can be seen, the first order graph in equation (14)
εAB is the first member (n  =  1) in the Δcn+ series. The  +chain
(13) fAB = exp − 1.
kb T diagrams can now be easily summed as
While in this work we are concerned with homogeneous ∞ ∞ 1  
∆c1  ∆cn+  ∆cn+
2 A∈Γ Z∈ΓσΓ−Z fAZ λAZ σΓ−A
fluids, the notation σγ(1) is maintained when convenient to V
+
V
=
V
=
1 − γ+
n=2 n=1
mark location in a chain. (21)
For a homogeneous fluid equation (12) can be simplified to
2 
 2
∆c1 1  γ = ( f − f ) λ σΓ−Oi Hj .
(14) = σΓ−A σΓ−B fAB λAB (22)
+ OH+ OH OH
V 2 i=1 j=1
A∈Γ B∈Γ

where λAB is given by The  −chains diagrams can be similarly written within

RTPT as
λAB = 4πκAB d3 Ihs (rc )
(15)
−fOH )n−1 ´ 
and Ihs(a) is the integral of the hard sphere reference fluid pair ∆cn− = fOH ( fOH−
2Ωn+1
σΓ−A (1)ghs (r12 )
  A∈Γ
correlation function OAB (12) σΓ−BC (2) ghs (r23 )
B∈Γ C∈Γ
ˆ a/d  
× OCD (23) σΓ−DE (3) ghs (r34 ) · · ·
(16) Ihs (a) = x2 ghs (x) dx ; x = r/d.
1  E∈Γ
D∈Γ
OWX (n − 1, n) σΓ−XY (n) ghs (rn,n+1 )
In this work Chang and Sandler’s [20] analytical solution to X∈Γ Y∈Γ

the Percus–Yevick integral equation is employed to evaluate × OYZ (n, n + 1) σΓ−Z (n + 1) d (1) · · · d (n + 1) .
Z∈Γ
Ihs (rc ). The term κAB represents the probability that site A on (23)

4
J. Phys.: Condens. Matter 31 (2019) 184001 B D Marshall

The negative cooperativity Mayer function is given by Combining equations  (11), (21) and (29), the final form for
Å ã Δc(o) is obtained
εOH−  
(24) fOH− = exp − 1. 1
kb T ∆c(o)
= 2 A∈Γ
σ f λ σ
Z∈Γ Γ−Z AZ AZ Γ−A
+ fOH λOH
ÇV 1−γ+ å
In equation (23) the densities σΓ−BC alternate between σΓ−Oi Oj   γ 2

or σΓ−Hi Hj ; while these quantities are indeed equal in the cur­ σΓ−A σΓ−B 1−γ−2
A∈{H1 ,H2 } B∈{O1 ,O2 } −
rent model, if the machinery of Wertheim’s multi-density  Ç å2
formalism is to be applied in an efficient manner, they need λ2 f (fOH− −fOH ) 
+ OH OH1−γ 2 σ Γ−HH σ Γ−A
to initially be treated independently. To this end we split the − A∈{O1 ,O2 }
infinite sum of  −chains diagrams as Ç å2 

∞
 ∞
 ∞
 ∞

+σΓ−OO σΓ−A . (30)
A∈{H1 ,H2 }
∆cn− = OO ∆cn− + HH ∆cn− + OH ∆cn− .
n=2 n=2,4,6,8... n=2,4,6,8... n=3,5,7,9... 
(25)
Where the first sum on the right-hand side of equation  (25) For the non-cooperative case ε− +
OH = εOH = εOH , which yields
accounts for  −chains terminated on each end with molecules γ−  =  γ+  =  0, and the first order result in equation  (14) is
bonded at an oxygen site, the center sum accounts for chains recovered.
terminated on each end with molecules bonded at donor Note, equation  (30) accounts for all homodromic and
hydrogen sites, and the last sum accounts for  −chains which antidromic chains as depicted in figure 2. However, all pos-
are terminated by a molecule bonded at a hydrogen on one sible heterodromic chains and larger associated non-cyclic
end and a molecule bonded at an oxygen site on the other. clusters are also generated from these base irreducible
Simplifying the form of equation (23) for each of these cases contributions.

Ç å2
OO ∆cn− 1 fOH  n−1 n

V = 2 σΓ−OO σΓ−A 2n−1 λnOH (fOH− − fOH ) (σΓ−OO σΓ−HH ) 2

A∈{O1 ,O2 }
Ç å2
HH ∆cn− 1 fOH  n−1 n

V = 2 σΓ−HH σΓ−A 2n−1 λnOH (fOH− − fOH ) (σΓ−OO σΓ−HH ) 2

A∈{H1 ,H2 }
Ç å
OH ∆cn− fOH   n−1 n

V = √
σΓ−OO σΓ−HH σΓ−A σΓ−A 2n−1 λnOH (fOH− − fOH ) (σΓ−OO σΓ−HH ) 2 . (26)
A∈{H1 ,H2 } B∈{O1 ,O2 }


Further rearranging equation (26) 2.2.  Evaluation of bonding fractions

Ç å2
»σ  With the graph sum Δc(o) now defined, we focus on the self-
OO ∆cn− 1 n−1
V = 2 fOH λOH σΓ−OO
Γ−HH
σΓ−A γ− consistent solution of the relevant densities. The density of
A∈{O1 ,O2 }
Ç å2 molecules bonded at the set γ is given by [16]
»σ  n−1  
HH ∆cn− 1 ργ
2 fOH λOH
Γ−OO
V = σΓ−HH σΓ−A γ− = cτ .
A∈{H1 ,H2 } ρo
P(γ)={τ } τ
(31)
Ç å
  The density of molecules bonded at site A is obtained from
OH ∆cn− n−1
V = fOH λOH σΓ−A σΓ−A γ− . equation (31) as
A∈{H1 ,H2 } B∈{O1 ,O2 }
(27) ρH1 = ρH2 = ρO1 = ρO2 = ρo cH .
(32)
Where Since each first order pair interaction is treated equivalently, all
√ one site densities in equation (32) are equal. In equation (32)
(28) γ− = 2λOH (fOH− − fOH ) σΓ−OO σΓ−HH .
for cH and in the following analysis we omit the subscripts i in
The sums in equation (25) can now be evaluated as the sites (Hi) for notational simplicity. For molecules bonded
Ç å2 at two association sites

∞ »σ 
OO ∆cn− 1 γ−
ρOH = ρO1 H1 = ρO1 H2 = ρO2 H1= ρO2 H2 
2 fOH λOH
Γ−HH
V = σΓ−OO σΓ−A 2
1−γ−
n=2,4,6,8...
Ç
A∈{O1 ,O2 }
å2 = ρo (cOH + cO cH ) = ρo cOH + c2H

∞ »σ    (33)
HH ∆cn−
= 12 fOH λOH Γ−OO
σΓ−A γ− ρHH = ρO1 O2 = ρH1 H2 = ρo cHH + c2H .
n=2,4,6,8...
V σΓ−HH
A∈{H1 ,H2 }
2
1−γ− 
Ç å

∞
OH ∆cn−
  2
γ− Again, for the two site densities, we drop the subscripts in the
= fOH λOH σΓ−A σΓ−B 2 .
n=3,5,7,9...
V
A∈{H1 ,H2 } B∈{O1 ,O2 }
1−γ− notation Oi Hj  for notational simplicity. For molecules bonded
(29) three or four times

5
J. Phys.: Condens. Matter 31 (2019) 184001 B D Marshall
   
ρOHO = ρHOH = ρo 2cOH cH + cHH cO + cO c2H = ρo 2cOH cH + cHH cH + c3H
 2 2  γ− = 2λOH ρXHH (fOH− − fOH )
2
ρHOHO = ρo cH cO + 2cOH + cHH cOO + cOO cH cH + cHH cO cO + 4cOH cO cH
  γ+ = 4λOH ρXOH (fOH+ − fOH ) (44)
= ρo c4H + 2c2OH + c2HH + 2cHH c2H + 4cOH c2H .
(34)  ∂γ−
∂σΓ−HH = λOH (fOH− − fOH )
Combining the results of equations (32)–(34) we can solve for ∂γ+
the densities of molecules bonded k times ∂σΓ−O1 H1 = λOH (fOH+ − fOH ) .
 
ρ1 = 4ρH = 4ρo cH ρ2 = 2ρHH + 4ρOH = ρo 6c2H + 4cOH + 2cHH
 
ρ3 = 4ρHOH = ρo 8cOH cH + 4cHH cH + 4c3H
  2.3.  Thermodynamic functions
ρ4 = ρo c4H + 2c2OH + c2HH + 2cHH c2H + 4cOH c2H . (35)

In  2.2 we derived the relations for the relevant densities in
From these results, and the fact that the sum over all bonding
RTPT. In this section  we develop the necessary thermody-
states must equal the total density, the fraction of molecules
namic functions. For a perturbation theory with no cyclic clus-
which are unbonded Xo  =  ρo/ρ can be evaluated as
ters we have the general result
1
Xo = 4 2
. ∆c(o) 1
(1 + cH ) + (4cOH + 2cHH ) (1 + cH ) + 2c2OH + c2HH (45) = σΓ−A cA .
 V 2
A∈Γ
(36)
We will also require the fraction of molecules NOT bonded The Helmholtz free energy is obtained from equations (7), (8)
at site H and (45),

ρXH = σΓ−H = σΓ−O = ρHOH + 2ρOH + ρHH + 3ρH + ρo . AAS

(46) = ln Xo + 2cH XH + 4cOH XOH + 2cHH XHH .
(37) NkB T
Using equations  (32)–(34) to eliminate the densities in
The association contribution to the chemical potential is eval-
equation (37)
uated with the general relation [16]
XH ρHOH ρOH ρHH ρH
= +2 + +3 +1 µAS ∂∆c(o) /V
Xo ρo ρo ρo ρo (47)= ln Xo − .
3 kb T ∂ρ
= (2cOH + cHH ) (1 + cH ) + (1 + cH ) . (38)
 The density derivative is evaluated as
Now the fraction of molecules NOT bonded at both sites OH
XOH ρOH ρH 2 ∂∆c(o) /V ∂ ln ∆OH
= +2 + 1 = cOH + c2H + 2cH + 1 = cOH + (1 + cH ) = (2XH cH + 4XOH cOH + 2XHH cHH ) ρ .
Xo ρo ρo ∂ρ ∂ρ
(39)
(48)
as well as the fraction of molecules not bonded at both donor
hydrogens (or acceptor oxygens) The association contribution to the pressure can now be cal-
culated as
XHH XOO ρHH ρH
= = +2 + 1 = cHH
Xo Xo ρo ρo PAS µAS AAS
= − = − (2XH cH + 4XOH cOH
+ c2H + 2cH + 1 = cHH + (1 + cH )
2 (40) ρkb T kb T Nkb T
 Å ã
∂ ln ∆OH
with cH, cOH and cHH obtained from equations (9) and (30) +2XHH cHH ) 1 + ρ . (49)
∂ρ
2ρXH fOH λOH 2
γ− 
cH = cO = + 2ρfOH λOH XH
1 − γ+ 2
1 − γ− This completes the derivation of the resummed associa-
tion theory for water which exhibits both positive and nega-
4ρ2 λ2OH fOH (fOH− − fOH ) XHH XH (41)
+ 2
tive hydrogen bond cooperativity. While in this work we are
1 − γ− focused on hydrogen bond cooperativity, the general rela-

tions developed provide a complete second order perturba-
4ρ2 fOH λOH XH2 ∂γ+ tion theory solution for water. These results could similarly be
cOH = (42)
2 ∂σΓ−O1 H1

(1 − γ+ ) applied to study the effects of steric hindrance in the hydrogen
Å ã bonding theory of water. One would simply need to define an
cHH = cOO = 8fOH λOH ρ2 XH2 γ−
+
3
γ− ∂γ− appropriate Δc(o) in equation (30).
2
1−γ− (1−γ−2 )2 ∂σΓ−HH
The development of RTPT for water has been the sub-
4λ2OH ρ2 fOH XH2 (fOH− −fOH ) 16λ2OH ρ3 XH2 XHH fOH (fOH− −fOH ) ject of this derivation. It would be possible to develop an
+ 1−γ− 2 + 2 γ− ∂σ∂γ−
.
(1−γ−2 ) Γ−HH
RTPT for hydrogen bonding molecules with any number of

(43) acceptor and donor sites; however, a general simplified form
In equations (41)–(43) we have enforced XH = XHj = XOk and for molecules with any number of donor and acceptor sites
XHH = XOO. Finally, γ± and the corresponding derivatives are would not be possible. Each case would require a separate
given by derivation.

6
J. Phys.: Condens. Matter 31 (2019) 184001
Table 1.  Summary of hydrogen bonding parameters.
εOH/kb (K) rc/d θc
1587.7 1.27 30°
2 R+ for R−  =  0.8, 0.9, 1.
Figure 3.  Plot of δ+  =   XOH /XH versus R+ using both RTPT and
TPT2. Bottom panel gives a view of the low R+ limit. In this
figure there is no negative cooperativity (R−  =  1).
3.  Numerical results
In this section  we apply the theory developed in section  2
to study the effects of positive and negative hydrogen bond
cooperativity in water. Following our recent TPT2 theory
[9] for hydrogen bond cooperativity, we choose the pairwise
hydrogen bond energy εOH to be equal to the experimentally
measured [21] dissociation energy of the water dimer of 13.2
kJ mol−1. Similarly, the critical radius rc  =  1.27d is chosen to
coincide with the first minimum of the oxygen–oxygen pair
correlation function as measured by Soper et al [22]. Finally,
we choose the critical angle θc  =  30° to be consistent with the
approach of Soper et  al [22]. Table  1 summarizes the input
parameters to the association model. Note, if the hydrogen
bonding theory is evaluated in terms of the reduced density
ρ*  =  ρd3, there is no need to specify the actual diameter d.
The effective energies of the second hydrogen bond in a
−
cooperative ε+ OH and anti-cooperative εOH cluster are defined
as
ε+
OH = R+ εOH
(50)
ε−
OH = R− εOH
where R+  ⩾  1 and 0  ⩽  R−  ⩽  1.
3.1.  A comparison of RTPT to TPT2 for positive hydrogen
bond cooperativity
We begin by neglecting negative hydrogen bond coopera-
tivity (R−  =  1) and incorporating positive hydrogen bond
7
B D Marshall
Figure 4.  Plot of the fraction of unbonded sites versus R+. Solid
curve gives RTPT and dashed curve TPT2. In this figure there is no
negative cooperativity (R−  =  1).
Figure 5.  δ+ (top blue curves) and δ− (bottom red curves) versus
cooperativity R+  >  1. Specifically, we compare the RTPT
solution developed in section  2, to a second order perturba-
tion theory (TPT2) which truncates the sum in equation (20)
for n  >  2. In this limit, the new approach reduces to the
TPT2 theory of Marshall [9]. However, in this work Ihs in
equation  (16) is evaluated using the Percus–Yevick solution
of Chang and Sandler [20], while in the TPT2 approach of
Marshall, Ihs was evaluated by assuming the product r2ghs(r)
was equal to its contact value [13] within the entire bond
volume.
The reduced density is fixed at a liquid like density ρ*  =  0.8
and the temperature is held constant at T  =  298.15 K. In our
comparisons we consider the ratio δ+  =   XOH /XH2 which pro-
vides a measure of the deviation from a first order (TPT1)
result. For δ+  =  1 there is no hydrogen bond cooperativity,
while for larger values of δ+ hydrogen bond cooperativity has
a stronger effect on hydrogen bond structure. Figure 3 plots
δ+ versus R+ for both TPT2 and RTPT solutions. As can be
seen, RTPT shows a rapid increase in δ+ as R+ is increased.
The TPT2 solution is only in agreement with RTPT for small
R+. This shows that hydrogen bond cooperativity is a very
strong perturbation. RTPT sums all irreducible chain dia-
grams, while TPT2 only accounts for complete cooperativity
in a hydrogen bonded trimer, with larger associated clusters
created from combinations of cooperative trimer and pair-
wise additive dimer contributions. The effect on the degree
of hydrogen bonding can be seen in figure 4, which plots the
fraction of unbonded association sites XH versus R+. RTPT
shows a much faster reduction of XH with increasing R+ as
compared to TPT2.
J. Phys.: Condens. Matter 31 (2019) 184001
Figure 6.  Fraction of unbonded association sites (left) and association contribution to the chemical potential (right) calculated using RTPT.
Figure 7.  Fraction of water molecules bonded k times at a reduced
density of ρ*  =  0.8.
3.2.  Positive and negative cooperativity in RTPT
In this subsection we evaluate how the inclusion of nega-
tive anti-cooperativty (panel b of figure  2) affect hydrogen
bonding in fluids which also exhibit positive cooperativity
(panel a of figure 2). As before, the reduced density is fixed at
a liquid like ρ*  =  0.8 and the temperature is held constant at
T  =  298.15 K.
Figure 5 plots δ+  =   XOH /XH2 and δ−  = XHH /XH2 versus
R+ for several values of R−. Increasing negative coopera-
tivity (decresing R−) has a strong effect on δ− when posi-
tive hydrogen bond cooperativity is weak (R+ near unity).
However, for systems with strong positive cooperativity
(R+  >  1.1), the inclusion of negative cooperativity only has a
small effect on hydrogen bond structure.
This is further demonstrated in figure  6 which plots the
fraction of unbonded association sites as well as the asso-
ciation contribution to the chemical potential versus R+ for
several values of R−. Inclusion of negative anti-cooperativity
only affects XH and µAS for systems with weak positive coop-
erativity R+  <  1.1. The RTPT developed in this work predicts
that the effects negative cooperativity should be negligible in
systems with strong positive cooperativity. Put another way,
associated clusters with long runs of bonds which do not
exhibit positive cooperativity (antidromic) should be rare in
systems with strong positive cooperativity.
3.3. R+ and R− from ab initio calculations
In this section we use values of R+ and R− obtained from ab
initio calculations. We obtain R+ from Ojamae and Hendersen
8
B D Marshall
Figure 8.  Example of energetically unfavorable antidromic
associated cluster.
[1] who, using MP2 calculated the non-additive contribution
to a HOHO (figure 1) hydrogen bonded trimer to be 9% of
the entire energy of the cluster. Similarly, for R− we employ
the MP2 results of Xantheas [2] who calculated the repulsive
three body contributions HOOH and OHHO to be 0.3 and 0.5
kcal mol−1 respectively. In this work, both anti-cooperative
trimer structures are assumed to be identical. Hence, we take
the average value of 0.4 kcal mol−1, which corresponds to
~4.5% of their calculated trimer binding energy. From these
MP2 results R+ and R− are found to be
R+ = 1.18
R− = 0.91. (51)

In figure 7 we show calculations for the fraction of mol-
ecules bonded k times χk. We split χ2 into two contributions:
the fraction of molecules bonded at an acceptor and donor site
χAD, as well as the fraction of molecules bonded at both donor
sites χDD which in our model is equal to molecules bonded
twice at both acceptor sites χAA. Figure 7 displays the frac-
tions as a function of temperature for a constant reduced den-
sity of ρ*  =  0.8.
As can be seen in figure  7, the theory predicts that mol-
ecules which are only bonded (twice) at both acceptor oxy-
gens or both donor hydrogens will be rare (small χDD). In
contrast, the fraction of molecules bonded (twice) at both an
acceptor site and donor site are common (large χDA). Hence
the theory predicts that the liquid hydrogen bonded structure
is dominated by homodromic, or at least mostly homodromic
(heterodromic), hydrogen bonded structures. With antidromic
hydrogen bonded clusters, such as those show in figure  8,
J. Phys.: Condens. Matter 31 (2019) 184001
Table 2.  Comparison of ab initio molecular dynamics and
RTPT for the hydrogen bond statistics of liquid water at ambient
conditions. The table presents the percentage of water molecules
bonded at i acceptor (rows) and j  donor (columns) sites. In this
table we include Lee and Tuckerman’s results for the Luzar [24]
definition of hydrogen bonding.
Lee and
Tuckerman [23] RTPT
No. of donors
No. of
acceptors 0 1 2 0 1 2
0 0 0 1 0.056 0.3455 0.504
1 1 8 16 0.3455 5.622 13.865
2 0 11 63 0.504 13.865 64.891
Table 3.  Comparison of the experimentally measured and RTPT
predicted values of the average number of liquid phase hydrogen
bonds per water molecule at T  =  298 K.
Experimental [22] RTPT
3.58 3.58
being relatively rare. Xantheas [2] demonstrated using ab
initio calculations that the minimum energy structures of
small water clusters were homodromic with the largest non-
additive many body (>2) contributions to the cluster energy.
In this work we reach a similar conclusion to Xantheas using
a liquid state theory.
We now compare RTPT predictions of hydrogen bonded
structure to the first principles ab initio molecular dynamics
results of Lee and Tuckerman [23] at T  =  300 K. For this
comparison we must now choose the value of the hard sphere
diameter d. For this we choose
(52) d = 2.77 Å
to correspond to the first maximum in the oxygen–oxygen
pair correlation function calculated by Lee and Tuckerman.
This corresponds to a reduced density of water (@ 300 K)
of ρ*  =  0.71. Lee and Tuckerman calculated hydrogen bond
statistics for several different geometric hydrogen bonding
definitions and demonstrated that they all gave qualitatively
similar results.
Table 2 compares RTPT predictions to those of Lee and
Tuckerman for the hydrogen bond statistics of liquid water
at ambient conditions. The table  compares calculations for
χij, which represents the fraction of water molecules bonded
at i acceptor and j  donor sites. Overall the two approaches
are in good agreement. However, the comparison is qualita-
tive as the definition of hydrogen bonding between the two
approaches is not entirely consistent. Importantly, qualita-
tively both approaches predict that χ02 and χ20 are small com-
pared to χ11. This agrees with the discussion around figure 7,
providing further evidence of the dominance of homodromic
hydrogen bonded structures. Note, the entries in table 2 from
the ab initio simulations which are identically 0, are the result
of poor statistics, not the complete absence of these bonding
states.
9
B D Marshall
Table 4.  Square well potential parameters and diameter regressed
from vapor pressure and liquid density data.
ε/kb (K) λ/d d(Å )
222.016 1.916 2.859
We can also compare RTPT predictions for the average
number of hydrogen bonds per water molecule (Nhb) to the
experimental results of Soper et  al [22]. Table  3 gives this
comparison. As can be seen, RTPT gives an excellent predic-
tion of this quantity. Note, the RTPT definition of hydrogen
bonding (rc  <  1.27d, θc  <  30º) is consistent with the defini-
tion of Soper et al [22] in their determination of Nhb. For this
reason, the comparison in table 3 is quantitative.
In a previous publication [9] we demonstrated that TPT2
also gave an accurate prediction of Nhb. However, RTPT does
show an improvement for the following reason. The hard
sphere reference system integral Ihs given by equation (16) is
evaluated in a more rigorous fashion. In the previous TPT2
approach we had assumed Ihs had the same form as in the
PC-SAFT [25] equation  of state, which assumes r2ghs(r)
remains constant in the bond volume and equal to its contact
value. This approximation of constant r2ghs(r) in the bond
volume loses accuracy for rc  >  1.05 d. If we apply TPT2 to
calculate Nhb at ambient conditions with our current Ihs we
obtain Nhb  =  3.37. A significant underprediction as compared
to the result of Soper et al [22].
4.  A general equation of state for water
The free energy contribution in equation (46) only accounts
for attractions due to hydrogen bonding. To calculate general
properties of water (density, vapor pressure, heat capacity
etc…) we must include contributions to the free energy for
isotropic dispersion attractions. The total Helmholtz free
energy is then given by
A = AHS + AAT + AAS .
(53)
Where AHS is the free energy of a hard sphere fluid, AAT is
the free energy contribution for isotropic attractions, and AAS
is given by equation  (46). For the isotropic attractions we
assume they are of the square well variety with well depth ε
and range λ. We evaluate AAT with a standard first order per-
turbation theory [26]
AAT
(54) = −2πρd3 εIref (λ) .
N
The integral Iref(λ) is the integral of the reference system cor-
relation function over the square well range. Here we employ
the recently developed associated reference perturbation
theory (APT) approach of Marshall [8] to account for the
trans­ition to tetrahedral symmetry on the square well refer-
ence fluid. APT gives the reference fluid integral as
Å ã
1
(55) Iref (λ) = Ihs (λ) + χ4 − Ihs (rc )
πρd3
J. Phys.: Condens. Matter 31 (2019) 184001 B D Marshall

Figure 9.  Comparison of theory (curves) to experimental data [27] (circles) for the T  −  ρ phase diagram (left) and vapor pressure (right).

Figure 10.  Same as figure 9 except for the isothermal compressibility [28] (left) and isobaric heat capacity [29] (right) at atmospheric
pressure.

where χ4 is the fraction of water molecules bonded four times,

which is evaluated through equation (35).
With the addition of the attractive contribution, the theory
is now parameterized by λ, ε, d, εOH, rc, θc, R+, R−. Our goal
in this section is not to develop the most accurate engineering
equation  of state for water, but to demonstrate the predicta-
bility of the RTPT approach using physically justified param­
eters for the hydrogen bonding theory. Hence, we do not adjust
any of the hydrogen bonding parameters (εOH, rc, θc, R+, R−)
to experimental thermodynamic data, instead using the physi-
cally justified parameters developed in section  3. However,
to reasonably apply the theory described by equation  (53)
as a full thermodynamic model for water we must adjust the
parameters λ, ε, d to reproduce water thermodynamic data.
We adjust these three parameters to saturated liquid density
and vapor pressure data of pure water in the temperature range
0 °C  ⩽  T  ⩽  200 °C. The regressed parameters can be found
table 4.
The diameter listed in table 4 certainly seems reasonable,
as the Lee and Tuckerman value used in section 3 was 2.77
angstroms. The square well depth and range are similar to
those used in the APT of Marshall [8].
Figure 9 compares theoretical predictions of the T  −  ρ
phase diagram and vapor pressure to experimental data.
Overall agreement is quite good, although the theory does not
represent the density maximum of water. TPT assumes the
structure of the fluid is unchanged with hydrogen bonding.
Using the APT reference fluid of equation (55), we account
for the decrease in number of isotropic square well attractions
when water undergoes a structural transition near ambient
Figure 11.  Comparison of RTPT predictions (curve) to the
spectroscopic data of Luck [30] (circles) for the fraction of free OH
groups in saturated liquid water.
conditions, however this is not enough to force a density
maximum. The theory does qualitatively predict the anoma-
lous minima in isothermal compressibility and isobaric heat
capacity. Theoretical predictions of these quantities are com-
pared to experimental data in figure 10. The theory underpre-
dicts heat capacity by ~10%, but the temperature dependence
of the heat capacity is in good agreement with the exper­
imental data for T  >  0 °C.
Now attention is turned back to the hydrogen bonded struc-
ture of the liquid state. Figure 11 compares RTPT predictions
of the fraction of free OH groups for a saturated liquid to the
spectroscopic results of Luck [30]. As can be seen, the theory
predictions are in good agreement with the data over a very
wide temperature range. As hydrogen bonding parameters
were not adjusted to thermodynamic data, this result is a pre-
diction of the RTPT theory.

10
J. Phys.: Condens. Matter 31 (2019) 184001
The results in figures 9–11 demonstrate the RTPT theory
can be applied in the context of a general thermodynamic
model for water without adjustment of hydrogen bonding
potential parameters to thermodynamic data.
5. Conclusions
In this paper we have developed a RTPT to account for posi-
tive and negative hydrogen bond cooperativity in water. For
positive cooperativity, it was demonstrated that TPT2 gave
the limiting RTPT result for weak cooperativity only. It was
then demonstrated that inclusion of negative cooperativity in
antidromic bonds does not significantly affect the thermo-
dynamics when the strong positive cooperativity of water is
accounted for. This implies that antidromic (−chains) runs of
association bonds are rare in water. This idea was supported
by comparison to the first principles simulations of Lee and
Tuckerman [23]. Further, when paired with a contribution for
isotropic attractions, the RTPT theory was shown to give an
accurate thermodynamic model for water without adjusting
hydrogen bonding parameters to thermodynamic data.
Most importantly, RTPT gives a simple theory for water
which predicts hydrogen bonded structure consistent with ab
initio molecular dynamics (table 2). This could be useful in
the interpretation of water spectroscopy data, by estimating
the hydrogen bonded structure which corresponds to a given
vibrational spectrum [31].
ORCID iDs
Bennett D Marshall https://orcid.org/0000-0002-3079-5946
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