What is a liquid?

Dr Fernando Bresme Department of Chemistry Room 165 f.bresme@imperial.ac.uk

Dr F. Bresme, Chemistry, Imperial College London 1

Liquids and solutions (22 lectures +2 comp labs)

What is a liquid, structure and dynamics?: (Bresme) Introduction to computational methods for liquids: (Bresme). Interactions and polarity in liquids: (Welton) Electrolytes: (Kornyshev) Electron transfer Marcus theory: (Kornyshev) Liquid Interfaces: (Bresme) Ionic liquids and ionic liquid interfaces: (Kornyshev and Welton) Liquid crystals and complex fluids: (Seddon) Computational Labs: simulation of water, simulation of liquid-vapour interfaces. (Bresme)

Liquids and solutions (22 lectures + 2 comp labs)

What is a liquid?, structure, dynamics and statistical geometry: L1-2: 18th Jan, L4: 20th Jan, L7: 3rd Feb - Bresme Introduction to computational methods-Comp Lab: L5: 20th Jan - Bresme Liquids and Polarity: L3: Jan 20th, L6: Jan 25th - Welton Computational lab on polar liquids, water: Jan 24th and 31st - Bresme Theory of Liquids II: L9 and L10: Feb 10th - Kornyshev Theory of Electrolytes: L11-L13: Feb 14th and 17th Kornyshev Intro to Interfaces-comp lab: L8 (3rd Feb) Bresme Computational lab on interfaces liquid-vapour: Feb 21st and 28th Bresme Electrode-electrolyte interfaces: L15-L16: 24th Feb - Kornyshev Ionic liquids and ionic liquid interfaces: L14: Feb 17th Welton, L17-18: March 2nd - Kornyshev

Liquids and solutions (22 lectures + 2 comp labs)

Charge transfer in liquids and interfaces: L19-20: March 9th - Kornyshev Liquid crystals and complex fluids: L21-L22: March 16th - Seddon Problem class: March 13th - Kornyshev

Whats is a liquid?
The liquid state: Kinds of liquids and general properties Intermolecular forces and model potentials in liquids Statistical Mechanics treatment of liquids:
particle distribution functions radial distribution functions and strucure factor Thermodynamic properties of liquids: internal energy, pressure (virial series) the radial distribution function and the free energy: the work theorem

Dynamics in liquids

References
J.P. Hansen and I.R. McDonald, Theory of Simple liquids, Academic Press, 2006 M. Tuckerman, Statistical Mechanics: Theory and Molecular Simulation, Oxford D. Chandler, Introduction to modern Statistical Mechanics, Oxford University Press, 1987. D.A. McQuarrie, Statistical Mechanics, University Science Books, 2000

The Liquid State

Landau and Lifshitz, Course on Theoretical Physics 5: Statistical Physics (Pergamon Press 1958) Chaper VI. Unlike solids and gases, liquids do not allow a general calculation of their thermodynamic quantities or even their temperature dependence The central difficulty in a theoretical description of liquids is that the system cannot be decomposed into independent or weakly interacting degrees of freedom (like in a gas) or the independent modes of vibration in a solid (Einstein crystal)

BUT we can now estimate the properties of ordinary and complex liquids (e.g., computer simulations, and statistical mechanics approximations)

The liquid phase and the phase diagram

P liquid solid TP vapour T CP T fluid vapour CP liquid solid coexistence TP

At low pressures matter exists as a dense solid or as a dilute vapour. At higher pressures a 3rd state of matter appears liquid state Interaction strength in liquids near their triple-point (TP) is similar to that in solids.

Liquids and the classical approximation

The temperatures at which many Liquid liquids appear are high enough that a Ne classical approximation is accurate.
Ar Kr Na Li H2 CH4 HCl CCl4

TTP / K /
24.5 84 116 371 454 14.1 91 159 250 0.78 0.30 0.18 0.19 0.31 3.3 0.46 0.23 0.09

/a
0.26 0.083 0.046 0.054 0.11 0.97 0.12 0.063 0.017

rot/T

%2# $ ! ( " =' * & m )

2 1/ 2

de Broglie thermal wavelength

Classical behaviour:
!

6.1 0.083 0.094 0.001

Atoms:

" << a,, a # $ %1/ 3

" rot
!2 = 2 I kB

Molecules: T > " rot

Quantum effects should be small with some exceptions. Classical approximationseparation of thermodynamic properties arising from thermal motion from those due to interactions between particles.

E N = KN + UN

Liquid Helium

Alfred Leitner

The phase diagram

Strength intermolecular interactions condensed phases: liquids, solids
P liquid solid CP gas T fluid CP liquid

|U att |" kB T
TP vapour T

|U att |" kB T
coexistence TP

solid

!
KN "1 |U N |
liquids

E N = KN + UN

KN << 1 |U N |
solids

KN >> 1 |U N |
dilute gas

Kinds of Liquids
Spherical molecules (Ar, Kr): van der Waals interactions, steep repulsive interactions Diatomic molecules and polar liquids (H2, N2, HCl): quadrupole, dipole moments Metals (e.g. Na, Hg): long range coulombic forces, softer repulsion, screening effects relevant Molten Salts, Ionic liquids (NaCl, BMIM): electrically neutral on a local scale; long range coulomb interactions, electric screening important. Associated liquids or hydrogen bonded liquids (water, glycerol): strong angular correlation effects. Liquids consisting of large molecules: internal degrees of motion (alkanes, liquid crystals)

BMIM

Liquid Properties
Property
T [Melting/boiling] Density (103 kg/m3) [liq/ solid] PTP (bars) Heat of vap. (J/kg-1 mol-1) Surface tension (mN/m) Compressibility (m2/N) Diffusion (m2/s) *

Argon
84 / 87.5 1.41/1.64 0.71 6.7 13.1 2x10-9 1.6x10-9 0.12

Benzene
278.5 / 353 0.90/1.0 0.027 25 28.9 8.7x10-10 1.7x10-9 0.15

Water
273 / 373 1.0/0.92 4e-3 41 73 5x10-10 2x10-9 0.59

Sodium
371 / 1165 0.93/0.95 ~10-6 107 190 1.9x10-10 4.3x10-9 84

Thermal conductivity (W K-1 m-1)

Intermolecular interactions and model potentials

The most important feature of the interaction is the strong repulsion appearing at short range (overlap of the outer electron shells). Attractive interactions vary slowly with distance, play a smaller role in determining the general structure of a liquid .
! U(r N ) =

#
1"i< j"N

! u2 (rij ) +

3 1"i< j<k"N

# u (r

! ! ! ij,r jk,rki ) + "

Coulomb, Dispersion,, polarization, charge transfer

!

Pair-wise additivity approximation

! U(r N ) = ! ! ! ! u2 (rij ) = u2 (r12 ) + u2 (r13 ) + ...+ u2 (r23 ) + ... #
1"i< j"N

Good approximation [exceptions;polarization, many body interactions (metals)]

Intermolecular interactions and model potentials

Hard Sphere model: no attraction, Lennard-Jones (LJ) model: attractive no liquid phase! BUT structure = liquid (1/r6), liquid phase. Good representation structure ( perturbation theories) of dispersive interactions.

$" for r < # u(r) = % & 0 for r > #

Hard spheres

+$ # '12 $ # ' 6 . u(r) = 4 " -& ) * & ) 0 ,% r ( % r ( /

!
LJ

Polystyrene colloids, 720 nm diameter

gas phase data

Liquid-vapour coexistence: LJ vs experiment

Reduced units

T* =

kB T * , # = #$ 3 "

" = 1.654 #10$21 J, % = 0.3405 nm

!
!

Statistical Mechanics treatment of liquids: distribution functions

The idea: Particle Densities and distribution functionskey to the thermodymamics properties:
! ! exp[#$ U( r N )] dr N #n N! % (n ) ! n n-particle density " N ( r ) = ! ! (N # n)! % exp[#$ U( r N )] dr N

(N,V,T)

! ! " (n ) ( r n )dr n ! Probability of finding n particles with coordinates in the volumen N drn, irrespective of the positions of the remaning N-n particles.

! ! N! " (n ) ( r n ) dr n = % Hence # N (N $ n)!

Density in a ! ! ! N " (1) ( r ) dr = N % " (1) ( r ) = = " uniform fluid # N N V

! For an ideal gas

" (2) = " 2 (1# N #1 ) N

Statistical Mechanics treatment of liquids: distribution functions

! (n) ! ! ! n ! N (r1, r2 , , rn ) (n) n-particle distribution function gN (r ) = n (1) ! ! N (ri ) !
i=1

! ! " n g(n ) ( r n ) = " (n ) ( r n ) N N

The n-particle distribution function measures the extent to which the structure of a fluid deviates from complete randomness (g=>1)

Pair correlation function and radial distribution function

2 particle distribution function, or pair correlation function conditional probability that a particle will be found at r2 given that another particle is at r1.

! ! ! ! " (2) ( r1, r2 ) g( r1, r2 ) = N 2 "

RDF

! ! g ( r1, r2 )
(2) N

! ! Isotropic fluid => g ( r , r2 ) 1

(2) N

is a function of

! ! ! =| r " r | # g(r) r12 2 1

! Average density of particles at distance r from a particle at the origin

1st and 2nd coordination ! shells

"g(r)

! Monoatomic liquid near the triple point temperature: ~12.2 neigbours vs 12 in the ! fcc crystal
The coordination number

rmin
!

lim g(r) "1$ N $1

r "#

n(rmin ) = 4 " # $ 0 r 2 g(r) dr

rmin

Radial distribution Function: General behaviour

Liquids vs Solid fcc Liquid vs. Gas

See Chandler

RDF: simulations vs experiments

Argon: classical vs quantum vs experiment
C.N.~12

Water: classical vs experiment OO RDF.

C.N.=4.5!!

maximum at 2! no maximum at 2!

Radial distribution Functions: molecular fluids

Site-site distribution function Density of atoms of species , at position r given that an atom of species is at the origin.

! " # g$# ( r )

70 K, 0.81 g/cm3

! r
h-bond

1 2

1 2

298 K, 1 g/cm3

Hydrogen bonding

Radial distribution function: charged systems

Ionic liquids: Molten salts and RTIL
[PF6]-

liq

+NaCl,T ~1000 K

+++ 323K ++, --

Charge ordering!

Pair correlation function: Experimental determination

Need to probe distances of the order of the particle diameter. Angstroms (atoms), micrometers (colloids). Atoms/molecules: x-rays and neutron diffraction.

! kin

"

! kout

1 S(k) = N

! ! ! exp[i k ( ra " rb )] #
N a,b=1

The Structure Factor

! colloids (micrometer size): microscopy (confocal)

Structure factor: connection to g(r)

1 S(k) = N ! ! ! # exp[i k (ra " rb )]
N a,b=1

! ! ! S(k) = 1+ " $ dr [g(r) #1] exp[i k % r ]

Liquid metals: Na, 0.927 g cm-3, 373 K.

!
g(r) S(k)

The structure factor is connected to the isothermal compressibility through:

! lim S( k ) = # k B T $ T !
k "0

1 % $V ( "T = # ' * V & $P )T

Thermodynamic properties from Radial distribution Functions

The idea: if atoms interact thorugh a pairwise-additive force, thermodynamics properties can be expressed in terms of integrals over g(r). Internal energy (classical):
p2 E N = KN + UN = N + 2m
N

# u(| r
i> j=1

!
j

! " ri |)

N(N "1) < U >= 2

! ! !N ! % # " # dr3 "drN exp{"$U( r )} ( ! ! 1 ! *dr1 dr2 + N # dr g(r) u(r) u( r12 )' # ! ! ! ' !" dr "dr exp{"$U( r N )} * 2 # # 1 N & )

g(r, !,T )
!

3 E N = NkB T + 2 " N# $ dr r 2 g(r) u(r) 2

< U >= 2 ! " ## " dr r 2 g#$ (r) u#$ (r)

0

Pressure

"P 2% " # = 1$ # 3

, 0

& du(r) ) dr r 3 ( g(r) ' dr + *

Pressure equation or virial theorem.

Statistical mechanics definition of the equation of state of the liquid

!

Radial distribution Functions: thermodynamic properties

Example: the hard sphere potential
"P 2 $ #% 3 g(% ) low density 2 $ #% 3 = 1+ & 1+ # 3 3

First two terms in the virial expansion

The virial expansion, and the second virial coefficient, B2(T)

!
% "P = 1+ & Bi (T) # i$1 ,, B2 (T) = 2 ' # i= 2

% 0

dr r 2(1$ e$ "u( r) )

Vir van

Many equations of state of liquids (fluids) follow this functional form

!

Experiments of B2(T) yield quantitative information about intermolecular forces => pair potentials. The same approach can be used in solutions. e.g. colloidal dispersions in water (osmotic pressure)
2nd virial coefficient of water

Radial distribution Functions: the work theorem

The g(r) provides a route to obtain (Helmholtz) Free energies (work).

" " ! " g( r1, r2 ) = exp["# w( r1, r2 )]

w(r): reversible work for a process in which two particles move from infinity to distance r, in a bath of all other particles [(N,V,T)] => Helmholtz free energy!. Proof

! ! "dw( r1, r2 ) = ! dr1

! ! ! ! N ! "# U (r N ) $ " $ dr3 drN ("dU(r ) /dr1) e d ! # = kB T ! ln g( r1, r2 ) ! ! ! "# U(r N ) dr1 $ $ dr3 drN e

Mean force

w b in th p b

Potential of mean force

water 298 K 1 bar g(r)

w(r) = "kB T ln g(r) u(r) = "kB T ln g(r)

for # $ 0

We can use the same idea to calculate the effective interaction betwee two ions in solution, or two colloids in a colloidal suspension!!

w(r)