”The Physics and Chemistry of Water”

1 – The water molecule and

hydrogen bonds in water

Stoichiometric composition H2O – the average

lifetime of a molecule is ≤ 1 ms due to proton
exchange (catalysed by acids and bases).

O-H bond Re (Å) θe ( ◦ )

Isolated molecule 0.9584 104.45
Gaseous, experimental 0.9572 104.47
Liquid, ab initio 0.991 105.5
Liquid, Neutron diffraction 0.970 106
Hydrogen bonding weakens the covalent bonds
(cf. bond angles in a tetrahedral structure: 109.47◦.)
These structural parameters also apply (within
the Born-Oppenheimer approximation) to isotopi-
cally substituted water, e.g. D2O, HDO and H218O.
 Molecular size

The van der Waals diameter is ≈ 2.8 Å, with

about 5 % variation along different axes (similar
to isoelectronic Ne). Molecular volume ≈ 18 Å3.

van der Waals ”diameters” for water

(Figure from Chaplin)

Radial distribution of Ar and water Oxygen

(From Franks)
 What is so special with water . . .
if anything at all?
• ”Water has precisely the properties one would
expect from such a molecule.”
• ”Water has unique properties, and is unsur-
passed in complexity for a molecule of this
size.”
• ”Water is essential (necessary?) for life.”

Comparison with H2S

e−-binding
Re (Å) θe (◦) energy (eV) µe (D)
H2O (g) 0.9572 104.52 10.085 1.85
H2S (g) 1.328 92.2 7.43 0.97
The bond angle difference is due to differences in
electronic structure (greater separation between
3p and 3s atomic energies in S relative to the
2p-2s energies in O).
 Electronic structure

Contrary to common belief, the electron distri-

bution does not show enhanced electron density
where lone pairs in a sp3-hybrid orbital would
occur.

(From Chaplin)

Although the lone pairs of electrons do not ap-

pear to give directed electron density in isolated
molecules, there are minima in the electrostatic
potentials in approximately the expected posi-
tions.
 Molecular orbitals for water

The occupied molecular orbitals

(as electron probability distri-
butions of the isolated molecule)
with the lowest energy (most
negative) molecular orbitals at
the top. The calculated energies
are -559 eV, -37 eV, -19 eV,
-15 eV and -14 eV. It can be
seen that the three highest
energy orbitals are orthogonal
around the oxygen atom, with
two lowest energy orbitals (1s2
and mostly 2s2 ) approximately
spherical (at the top). There
are no obvious sp3 hybridization
characteristics. The highest
energy orbital (1b1 ) is predom-
inantly p2z in character and
mainly contributes to the ”lone
pair” effects. These orbitals
are appreciably changed in ice
and water, with the 3a1 orbital
being shown experimentally to
contribute most to hydrogen
bonding.

(Figure from Chaplin).

 Vibrational modes

Symmetric Asymmetric
stretch, ν1 stretch, ν2 Bend, ν3
H2 O (g) 3657 cm−1 3756 cm−1 1595 cm−1
H2 O (l) 3490 cm−1 3450 cm−1 1645 cm−1
H2 O (s) 3277 cm−1
D2O (g) 2727 cm−1
D2O (l) 2671 cm−1 2788 cm−1 1178 cm−1

Librational (rocking) modes – restricted

rotations due to H-bonds

In liquids, IR and Raman spectra are compli-

cated by coupling effects (vibrational overtones,
combined vibrational and librational modes, in-
tramolecular H-bond stretching or bending, clus-
ter vibrations, oxygen-oxygen coupling modes . . . )
 Uncoupled OD ν1 bands, in 11 mol-%
D2O in H2O, at various P and T

A: 20◦ C/0.1 × 108 MPa, B: 100◦ C/1 × 108 MPa, C: 200◦ C/2.8 ×
108 MPa, D: 300◦ C/4.7 × 108 MPa, E: 400◦ C/3.9 × 108 MPa. A-D
correspond to a constant density of 1000 kg/m3 . (From Franks)

• The bands are asymmetrical; the shoulders on the high-

frequency sides have been attributed to different contribu-
tions from H-bonded and non-H-bonded O-H groups, the ra-
tio of which varies with T and P .
• The bands shift to higher frequencies with both increasing T
and/or P , indicating a reduced influence of H-bonds.
• In the high T /P limit, where H-bonds are broken, the peak is
close to 2650 cm−1 , still greater than the 2727 cm−1 found in
D2 O vapour, suggesting that the vibrations are still perturbed
by surrounding molecules.
 Uncoupled OH and OD stretch bands

IR spectra of small amounts of HDO in CCl4,

liquid H2O or D2O, and crystalline H2O or D2O.

(From Tanford)
 Water’s isotopic variations

Nucleus Abundance (%) Nuclear spin

1
H 99.985 1/2
2
H 0.015 1
16
O 99.759 0
17
O 0.037 5/2
18
O 0.204 0

Zero-point motion (RMS) Density maximum

OH-stretch (Å) Bending T (◦C) Vm (cm3)
H2 O 0.067 8.7◦ 3.984 18.011
D2O 0.056 7.4◦ 11.185 18.014

(At 11.185 ◦ C Vm for H2 O is still less than for D2 O!)

• The structural parameters Re and θe apply

also to isotopically substituted H2O (within
the Born-Oppenheimer approximation).
• However, zero-point motion depends on the
nuclear mass, and H2O is larger than D2O due
to the differences in vibration amplitudes (but
the molar volume of D2O is larger due to weak-
ened H-bonding...!).
 The hydrogen bond in water

A hydrogen bond is formed when a H atom is

attracted by rather strong forces to two atoms
instead of only one (the convention is that an
O-H hydrogen atom is being donated to the O-
atom acceptor on another H2O molecule).

Some bond strengths in water (kJ/mol):

O-H covalent bond 492
Hydrogen bond 23.3
van der Waals attraction 1.3

• The H-bond has a partly covalent character,

though the magnitude of this is disputed.
• Small deviations from linearity (up to about
± 20◦) have a minor effect, while the strength
is exponentially decaying with separation.
• Since water molecules are well separated in
most condensed phases, there is plenty of room
for bending and stretching of the bonds.
• It is strong enough to result in about 1016 wa-
ter dimers per cm3 in the gas phase.
The misfit between tetrahedral angles and the
water HOH bonds results in a non-linear H-bond.
While the most favourable configuration of a dimer
is a straight H-bond, these are average parame-
ters in condensed water at 4◦C:

(Figures from Chaplin)

H-bond patterns are random in water (and some

ice phases) so that there is an equal probability
for a particular site around a molecule to be oc-
cupied by a donor or an acceptor.
 Hydrogen bonding is a
cooperative process

This cooperativity is a fundamental property of

liquid water. A hydrogen bond in water can be
250 % stronger than in a water dimer!

• Cooperative H-bonding increases the O-H bond

length while causing a 20-fold greater reduc-
tion in the H· · ·O and O· · ·O distances, com-
pared to dimer H-bonds.
• In hydrogen-bonded chains (such as DNA),
unzipping may occur as a result of breaking
of a few hydrogen bonds in the chain.
• This supports formation of large clusters: in
water at 0◦C H-bonded clusters span over 400
molecules.
• Cations may induce strong cooperative hydro-
gen bonding due to polarization of water O-H
bonds by cation-lone pair interactions:
Cation+ · · ·O-H· · ·O-H
 Hydrogen bond kinetics

• The hydrogen bond network is essentially com-

plete at ambient temperatures.
• H-bond lifetems are 1-20 ps.
• Broken bond lifetimes are about 0.1 ps.
• Dissociation of water is extremely rare, about
once per 1016 times the hydrogen-bond breaks.
• Broken bonds are most likely to reform as the
last hydrogen bond, so that the lifetimes of
clusters are usually much longer than the H-
bond lifetimes.

The H-atoms may possess parallel (ortho-water) or anti-

parallel (para-water) nucelar spin. The equilibrium is all-
para at 0 K, changing to about 3:1 ortho:para at higher
temperatures. The equilibrium may take months to estab-
lish in ice, and about an hour in liquid water. This slow
equilibration is a direct consequence of the preference for
broken H-bonds to re-form rather than re-orient.
 Structural implications of Hydrogen
bonding in water

• Only 42 % of the volume of ice is filled with

the van der Waals volume of the molecules,
compared to 74 % in a close-packed structure.
• Each ice water molecule has only 4 nearest-
neighbours, compared to 12 in close-packing
of spheres.
• The structuring of water carries information
about solutes and surface over significant dis-
tances, up to distances of the order of nanome-
ters.
 General references
• F. Franks, Water: a matrix of life, 2nd ed., Cambridge:
Royal Society of Chemistry 2000.
• Website by M. Chaplin, London South Bank Univer-
sity, http://www.lsbu.ac.uk/water/index.html. An ex-
tensive site explaining many properties of water.
• C. Tanford, The hydrophobic effect: Formation of mi-
celles and biological membranes, New York: Wiley 1973.