Elective Molecular Modelling CE433 Session2 AJH 2016 17

Elective Module:
CE4-33 Molecular Modelling of Fluids
Session 2: Classical Statistical Mechanics:

Theory of the Liquid State
Molecular Modelling of Fluids Session 2 – Slide 1 © Imperial College London

Key messages from last time
•  The system sizes we are dealing with are
overwhelmingly large
–  in terms of numbers of particles / molecules
•  This has important consequences in terms of
other key results
–  direction of spontaneous change: the probability of
change in the opposite direction is vanishingly small
–  allows us to simplify maths
•  use crude version of Stirling’s approximation
•  work with Taylor expansions including only a few terms
–  The extremely peaked nature of the Boltzmann
distribution
•  most important configuration is overwhelmingly so
•  Boltzmann’s equation: S = kB ln ⌦
–  where S is the entropy, kB is Boltzmann’s constant and
Ω represents “the number of ways”
•  in the molecular context, the number of microstates
•  in the ensemble context, the number of system states
•  Microstate:
–  the set of all the quantum states of all the molecules
•  Macrostate:
–  what we generally just call the state
–  many microstates correspond to the same macrostate

•  Principle of equal a priori probabilities

–  each microstate exists with equal probability
•  Stirling’s approximation: ln N ! ⇡ N ln N N
•  Boltzmann distribution law:
exp( "i ) exp( "i )
P ("i ) = P ⌘
i exp( "i ) q
–  where β = 1 / kBT, εi is the energy (level) associated with
molecule i, and
–  q is the molecular partition function

•  The concept of ensembles:

–  assembly of replicas of the system
–  each replica shares three macroscopic variables in
common
•  The canonical (NVT) ensemble
–  constant number of particles, volume and temperature
•  Measured properties are time averages
•  The ergodic hypothesis:
–  the ensemble average of a quantity is equal to the time
average

•  State of subsystem / member of ensemble

–  set of position and momentum coordinates of all the
molecules
•  more to follow in today’s lecture
•  Principle of equal a priori probabilities
–  each state of subsystem exists with equal probability
•  Canonical / Boltzmann distribution
exp( Ei ) exp( Ei )
P (Ei ) = P ⌘
i exp( Ei ) Q
–  where β = 1 / kBT, Ei is the energy associated with
subsystem i, and
–  Q is the canonical partition function
•  Link to macroscopic thermodynamics:

–  Partition function leads to macroscopic thermodynamic
properties
✓ ◆
@ ln Q
U= A = kB T ln Q
@ N,V
✓ ◆ ✓ ◆
@A @A
p= ; µ=
@V N,T @N V,T

–  Other thermodynamic quantities then obtained from

standard thermodynamic relationships:
•  enthalpy: H = U + pV
✓ ◆
@U
•  isochoric heat capacity: CV =
@T V
✓ ◆
@H
•  isobaric heat capacity: Cp =
@T p
•  Gibbs free energy: G = H T S = U + pV T S
@A
= A + pV = A V @V N,T

–  Other thermodynamic quantities then obtained from

standard thermodynamic relationships:
•  entropy:
✓ ◆ 2
✓ ◆
@Q 1 kB T @Q
A = U TS = TS = TS
Q
@ N,V Q @T N,V
2
✓ ◆
kB T @Q
i.e., kB T ln Q = TS
Q @T N,V
✓ ◆ ✓ ◆
kB T @Q @ ln Q
so S = kB ln Q + = kB ln Q + kB T
Q @T N,V @T N,V
Today’s Lecture
Session 2: Classical Statistical Mechanics

Thermodynamics from Q
•  Recall: Canonical distribution

exp( Ei ) X
P (Ei ) = ; Q= exp( Ei )
Q i
•  We can use this to evaluate thermodynamic
quantities, if we have expressions for quantised
energies, Ei
–  actually very rare
or, for systems of independent particles, if we
have expressions for quantised energy levels, εi
–  via the relationship between q and Q
Example: Ideal Gas Equation
•  Ideal-gas particles have no

interaction with each other
–  so are independent of each other
•  Each ideal-gas molecule

behaves like a “particle in a box”
–  only motion is translation
•  assuming ideal gas is monatomic
–  which we can decompose into components in each of
the Cartesian (x, y, z) directions

Ideal Gas Equation
•  From quantum theory, energy levels
corresponding to translation of a particle in a
box are given by:
n2x h2
"x = 2
; nx = 1, 2, . . .
8mlx
nx, ny and nz are quantum ♯s;
n2y h2 h is Planck’s constant;
"y = 2
; ny = 1, 2, . . . m is the particle mass;
8mly lx, ly and lz are box dimensions
n2z h2
"z = 2
; nz = 1, 2, . . .
8mlz
–  see e.g., Atkins Physical Chemistry
Ideal Gas Equation
•  These expressions allow us to evaluate the

molecular partition function, q
•  We then use the relationship between q and Q
to give us the canonical partition function.
•  However, there is a caveat here:
–  Equation 1.39 (Q = qN ) applies to distinguishable
particles
–  Ideal gas particles are indistinguishable
–  For indistinguishable particles, we over-counted right at
the start:

Indistinguishable Particles
•  Recall our example: how many ways can we

distribute three distinguishable particles among
three energy levels?
2! 3! 2! 3! 2! 1! 1!
1! 2! 3! 1! 1! 3! 2! 6 ways!
0! 1! 1! 2! 3! 2! 3!
Indistinguishable Particles?
2! x!
1! x! 1 way!
0! x!
•  Over-counting is by a factor of 6 = 3 × 2 = N!
•  Analogously, Equation 1.39 must be modified

to correct for this over-counting:
N
q
Q= (Equation 1.52)
N!

Ideal Gas Equation
•  Recall the expressions for the εi and definition

✓ of◆q :
2 2
nx h X "i
"x = 2
; nx = 1, 2, . . . q = exp
8mlx kB T
i
•  whence ( !)
XXX h2 n2x n2y n2z
qideal = exp 2
+ 2 + 2
n n n
8m l x l y l z
x y z
(Equation 2.3)
•  from which Q can be obtained, and then A, and

finally the ideal gas equation via p = (@A/@V )N,T
–  Left as an Exercise; see Chapter 2 for the solution.
Statistical Mechanics in Practice
•  Recall again: Canonical distribution

exp( Ei ) X
P (Ei ) = ; Q= exp( Ei )
Q i
•  Unfortunately, except in special cases
–  such as the “particle in a box” that we just looked at
•  which leads to ideal gas EoS
we do not have expressions for quantised
energy levels, εi , or for the energies Ei
•  Hence, we cannot write down Q or P(Ei)

•  However, we do often have an expression for

the Hamiltonian, H
–  sum of potential and kinetic energies of particles
•  H is a function of positions and momenta of
the particles / molecules
•  Leads to a problem …

•  Problem: we cannot know both position and

momentum exactly
–  Heisenberg’s Uncertainty Principle
•  Instead, we know r to within dr and p to within

dp (say)
•  Leads to identification of system state:

System state
Particle i
Position ri
Volume element,
(exaggerated!) size
dr

System state
Particle i
Position ri
Volume element,
(exaggerated!) size
dr

System state
Particle i
Position ri
Volume element,
(exaggerated!) size
dr

System state
Particle i
Position ri
Volume element,
(exaggerated!) size
dr

System state
Particle i
Position ri
Volume element,
(exaggerated!) size
dr

System state
Momentum pi
Momentum element,
Position ri
size dp
Volume element,
(exaggerated!) size
dr
Momentum of
Particle i

System state
Momentum pi
Momentum element,
Position ri
size dp
Volume element,
(exaggerated!) size
dr
Momentum of
Particle i

System state
Momentum pi
Momentum element,
Position ri
size dp
Volume element,
(exaggerated!) size
dr
Momentum of
Particle i

System state
Momentum pi
Momentum element,
Position ri
size dp
Volume element,
(exaggerated!) size
dr
Momentum of
Particle i

System state
Momentum pi
Momentum element,
Position ri
size dp
Volume element,
(exaggerated!) size
dr
Momentum of
Particle i

System state
Positions
r1, … , rN

System state
Positions
r1, … , rN
and momenta
p1, … , pN

System state
Can loosely identify system state j
(
(j)
In state j, lies in volume element dri centred on and ri
•  particle i (j)
has momentum in element dpi centred on pi
–  where i = 1,…, N includes all N particles / molecules in system,
and dri , dpi are infinitesimals
(j)
•  energy of particle i in element dHi centred on Hi
–  dH is infinitesimal
System state j
Can loosely identify system state j
8 ⇣ ⌘
< “position in the interval r(j) ± dr/2 ”
i
•  particle i ⇣ ⌘
: “momentum in the interval p(j) ± dp/2 ”
i
–  where i = 1,…, N includes all N particles / molecules in system,

and dri , dpi are infinitesimals
⇣ ⌘
(j)
•  “energy of particle i in the interval Hi ± dH/2 ”
–  dH is infinitesimal
System state j
•  In a sense: system has an energy (Hamiltonian)

corresponding to positions and momenta
“inside” some region of phase space
–  phase space: 6N-dimensional space defined by
positions and momenta
•  3N for positions (x, y, z); 3N for momenta (px, py, pz)
•  P (system has this energy) must be

proportional to the size of the region
–  the bigger the region, the more likely the system has
energy corresponding to that region

Probability densities
•  This in turn leads us to think about probability

densities
–  rather than direct probabilities, i.e., :
N N (N ) N N N N
P (Ei ) “P H r , p ” f r ,p dr dp
rN ⌘ r1 , r2 , . . . , rN ; drN ⌘ dr1 dr2 . . . drN
pN ⌘ p1 , p2 , . . . , pN ; dpN ⌘ dp1 dp2 . . . dpN
•  f (N)(rN, pN ): phase-space probability density

function
–  or, simply, probability density
Probability densities
•  f (N)(rN, pN ) is a probability density since,

multiplied by a volume (drNdpN) of a phase-
space element, it yields a probability.
f (N ) (rN, pN )drN dpN ⌘ f (N ) (r1 , r2 , . . . , rN , p1 , p2 , . . . , pN )

⇥ dr1 , dr2 , . . . drN , dp1 , dp2 , . . . dpN
⌘ “P (H)”
is the “probability that the physical system is in a
microscopic state represented by a phase point lying in the
6N-dimensional phase-space element drN dpN ”

What does f (N)(rN, pN ) look like?
•  By rules of probability, f (N)(rN, pN ) drNdpN must

normalise,
Z i.e.,:
Z
... f (N ) (rN, pN )drN dpN = 1
–  so dimensions f (N)(rN, pN ) are “1 / (rN pN )”
•  Heisenberg uncertainty principle:

–  each product of r and p ! h
•  Planck’s constant
–  dimensions of h: length × momentum
•  Expect f (N)(rN, pN ) = 1 / h3N × “something”
•  We expect the form to be reminiscent of

exp( Ei )
P (Ei ) =
Q
so we expect, e.g., !
1 exp H(rN, pN )
f (N ) (rN, pN ) =
h3N Q
but the form turns out to be
!
(N ) N N 1 1 exp H(rN, pN )
f (r , p ) =
N ! h3N Q

!
(N ) N N 1 1 exp H(rN, pN )
f (r , p ) =
N ! h3N Q
–  the 1 / N ! accounts for indistinguishability of particles (or
molecules)
–  This is exactly analogous to the over-counting we
encountered previously, in adjusting Equation 1.39,
Q = qN
for distinguishable particles, to Equation 1.52,
Q = q N/N !
for indistinguishable particles
•  Similarly
X Z Z
Q= exp( Ei ) “ . . . exp( Ei )”
i
becomes
Z Z
1
Q= ... exp( H(rN, pN ))drN dpN
N !h3N

Separating the contributions
•  To progress further, we need the Hamiltonian,

H , for the system of interest.
•  Generally, H (rN,pN ) separates:
–  sum of kinetic energy
•  K (pN )
–  and potential (“configurational”) energy
•  V (rN )
•  Consequently,
Z Z partition function
Z Z factorises:
1
Q= ... exp( K(pN ))dpN ... exp( V(rN ))drN
N !h3N
(Equation 3.5)
The kinetic (ideal) contribution
Z Z Z Z
1
Q= . . . exp( K(pN ))dpN . . . exp( V(rN ))drN
N !h3N
•  First integral: independent of the potential
–  To examine this, doesn’t matter what intermolecular
potential we choose
–  pick simplest: V (rZN ) = 0 Z
–  Second integral: exp(0)drN = drN = V N
✓ Z ◆
1
–  so QV=0 = exp( K(p N
))dp N
V N
N !h3N
–  Partition function of fluid with only kinetic energy
•  no potential energy; KE only
•  ideal gas
(for simple, spherical molecules)
XN
N p2i Particle mass
•  Kinetic energy: K p =
(spherically symmetric molecules) i=1
2m
Z –  whereby
Z N ZZZ
Y ✓ ◆
p2i
... exp K pN dpN = exp dpi
i=1
2m
•  Since no interactions between particles, all momenta
–  and all components of momenta
are independent. Allows factorisation:
ZZZ ✓ ◆ N Z !
p2i Y p2x,i
exp dpi = exp dpx,i
2m i=1
2m
Z ! Z ! !
p2y,i p2z,i
⇥ exp dpy,i exp dpz,i
2m 2m
(for simple, spherical molecules)
Z 1
2 2
p
•  Standard integral: exp( ↵ u )du = ⇡/↵
1
–  whereby
Z ! Z ! Z !
p2x,i p2y,i p2z,i
exp dpx,i = exp dpy,i = exp dpz,i
2m 2m 2m
r
2⇡m
=
Z Z –  so that N ZZZ
Y ✓ ◆ ✓ ◆3N/2
p2i 2⇡m
. . . exp K pN dpN = exp dpi =
i=1
2m
•  Finally:
Z Z ✓ ◆3N/2
1 2⇡m
3N
. . . exp K pN dpN = 2
⌘⇤ 3N
h h
(Equation 3.9)
–  Modelling
Molecular Λ is the thermal
of Fluids de Broglie wavelength Session 2 – Slide 45 © Imperial College London
The ideal free energy
•  Equation
Z Z 3.5 Z Z
1
Q= ... exp K(pN ) dpN . . . exp V(rN ) drN
N !h3N
•  thus becomes
1 VN
Qideal =
N ! ⇤3N
•  whereby
Aideal = kB T ln Qideal
= kB T ln V N ln N ! ln ⇤3N
= kB T N ln V (N ln N N) N ln ⇤3
= N kB T ln(V /N ) + 1 ln ⇤3
The ideal gas equation
•  In other words, we have the ideal free energy
✓ ◆
Aideal N
= ln 1 + ln ⇤3 = ln ⇢ 1 + ln ⇤3
N kB T V
(Equation 2.8)
•  Once we have the ideal free energy, we can use
standard thermodynamic relationships to
obtain other properties
•  For example, recall the Fundamental Equation
X
dU = T dS pdV + µi dNi
i
•  and the definition, A = U – TS
•  This gives us X
dA = SdT pdV + µi dNi
i
•  From this, one can obtain expressions for both the
pressure and✓ the◆chemical potential:
✓ ◆
@A @A
p= ; µi =
@V Ni ,T @Ni V,T,Nj6=i
•  or, for a pure component:
✓ ◆ ✓ ◆
@A @A
p= ; µ=
@V N,T @N V,T

•  Recalling that we had
✓ ◆
Aideal N
= ln 1 + ln ⇤3 = ln ⇢ 1 + ln ⇤3
N kB T V
(Equation 2.8)
it is now straightforward to obtain the ideal gas

equation via p = (@A/@V )N,T :
pideal 1
= , i .e., pV = N kB T
N kB T V
•  Finally, recalling kB = R/NA and N = n NA
pV = nRT
The configurational integral
•  Recall:
Z Z Z Z
1
Q= ... exp K(pN ) dpN . . . exp V(rN ) drN
N !h3N
•  So now:
3N Z Z
⇤ ⇤ 3N
Q= . . . exp V(rN ) drN ⌘ Z (Equation
3.11)
N! N!
−  Non-spherical molecules: Q has same general form but Λ–3 ! “Λ*–3 ”
◦  i.e., “Λ* ” incorporates all rotational and vibrational contributions
Z Z is the
–  Z = . . . exp N N
V(r ) dr configurational
(Equation 3.12) integral
•  Take care:
–  There is some variation among authors concerning the
exact terminology
•  some people say “configurational integral”, some say
“configuration integral”
•  Z is often called the configuration(al) partition function
–  and, in particular, the notation:
•  Many physicists use Z to represent the (full) partition
function, and Q to represent the configurational integral(!).
•  Many authors use subscript(s) N, or NVT
–  e.g., ZN
–  e.g., QNVT
•  Is very important!!
•  McQuarrie (in Statistical Mechanics):

–  “ZN is called the Classical Configuration Integral. Since
the intermolecular forces depend on the relative
distances between molecules this integral is, in
general, extremely difficult and is essentially
responsible for the research in equilibrium statistical
mechanics.”

“Separating the probabilities”
•  Recall
P (Hi ) ⌘ P (H(rN , pN )) = f (N ) (rN , pN )drN dpN
–  is the probability of the particles being in the 6N-
dimensional element of phase space drNdpN"
•  f (N)(rN,pN )drNdpN is the probability (not simply f (N)(rN,pN ))
because the probability must depend on the size of the
element of phase space."
N N
–  so could express this simply as" P (r , p )
–  Analogous to the partition function, we factorise:
P rN , p N = P rN P p N

Separating the probabilities
•  Recall !
(N ) N N 1 1 exp H(rN, pN ) ⇤ 3N
f (r , p ) = ; Q= Z
N ! h3N Q N!
so
( )( )
1 1 exp V(rN ) exp K(pN )
f (N ) = 1
N ! h3N N! Z ⇤ 3N
( )( )
exp V(rN ) exp K(pN )
= 3N 3N
;
Z h ⇤
Notice that the 1/N! cancels 3N 2 3N/2
⇤ = 2⇡m/ h
Molecular Modelling of Fluids Session 2 – Slide 54 so Planck’s const cancels too
© Imperial College London
•  Collecting:
P (H) ⌘ P rN , pN = f (N ) drN dpN

( ) ( )
exp V(rN ) N exp K(p N
) N
= dr dp
Z h3N ⇤ 3N
= P rN ⇥ P pN
•  P (pN ):
–  of no further interest Equation 4.3

•  P (rN ):
–  the probability that a given (“labelled”) molecule is in
each of the 3-dimensional volume elements dr1 … drN,
i.e., 0 1
molecule 1 (say) in dr1
B and molecule 2 in dr2 C
B C
B and molecule 3 in dr3 C
P rN = Prob B C
B .. C
@ . A
and molecule N in drN
–  probability of any molecule in each element would be
more useful
Building something useful
•  P (rN ) is not particularly useful as it stands

–  usually, molecules are indistinguishable
•  probability of any molecule in each element would be preferable
•  Build up a step at a time:
–  System can “choose” any molecule to occupy dr1
•  molecule 1 or molecule 2 or … or molecule N
–  Probability theory:
“P (1 or 2 or . . . or Nor ) = P (1) + P (2) + . . . + P (Nor )”
exp V(rN )
so ⇢(1)⇤ (rN ) = N P (rN ) = N drN
Z
represents
P (any molecule in dr1 while given molecules occupy dr2 … drN)
Building something useful
•  ρ(1)* (rN ) is not particularly useful either

–  relates to one molecule
•  indicated by superscript “(1)”
but is a function of positions of all the molecules
–  We integrate out r2 … rN
•  yields a function depending only on position r1:
Z Z
(1) N
⇢ (r1 ) = . . . exp V(rN ) dr2 . . . drN
Z
Z Z
N
⌘ . . . exp V(rN ) drN 1
Z
is called a (singlet) density function and relates to
P (any molecule in dr1, irrespective of the positions of the rest)
More useful …
•  Similarly
–  system has (N – 1) choices for second molecule, so
exp V(rN )
⇢(2)⇤ (rN ) = N (N 1) drN
Z
represents P (any molecule in dr1 and any other in dr2
while given molecules occupy dr3 … drN)
–  relates to two molecules
•  indicated by superscript “(2)”
but is a function of positions of all the molecules
–  We integrate out r3 … rN
•  yields a function depending only on positions r1 and r2:

More useful …
Z Z
(2) N (N 1)
⇢ (r1 , r2 ) = . . . exp V(rN ) dr3 . . . drN
Z
Z Z
N (N 1)
⌘ . . . exp V(rN ) drN 2 (Eqn. 4.9)
Z
is called a pair density and relates to
P (any molecule in dr1, any other in dr2, irrespective of
the positions of the rest)
•  By analogy: n and N-particle densities:
Z Z
(n) (n) n N!
⇢ (r1 , . . . , rn ) ⌘ ⇢ (r ) = ... exp V(rN ) drN n
(N n)!Z
exp V(rN )
⇢(N ) (rN ) = N !
Z
Density functions:
relation to probabilities
Z Z
•  Recalling Z = ... exp V(rN ) drN
and integrating out ! normalisation properties:
exp V(rN )
⇢(N ) (rN ) = N !
Z
Z Z Z Z
(N ) N N exp V(rN )
. . . ⇢ (r )dr = N ! . . . drN = N !
Z
1 (N ) N
–  so ⇢ (r )drN
N!
is P (any molecule in dr1, any in dr2, …, any in drN)

Density functions:
Z Z
•  Recalling Z = ... exp V(rN ) drN
and integrating out ! normalisation properties:
Z Z
(1) N
⇢ (r1 ) = . . . exp V(rN ) drN 1
Z
Z Z Z Z
(1) (1) N
⇢ (r1 )dr1 ⌘ ⇢ (r)dr = . . . exp V(rN ) drN = N
Z
1 (1)
–  so ⇢ (r)dr
N
–  is P (any molecule in dr1 irrespective of the positions of
the remainder)
Density functions:
•  Keeping in mind
Z Z Z
(1) N
⇢ (r1 )dr1 = . . . exp V(rN ) drN = N
Z
–  Imagine simple, homogeneous fluid
•  ⇢(1) (r) = ⇢(1) , or simply ⇢
Z Z
(1) N
–  so ⇢ (r)dr = N = ⇢ dr = ⇢V =) ⇢ =
⇣ V ⌘
Equations
–  i.e., ρ(1)(r) is the number density at r 4.15, 4.16 & 4.17

Density functions:
•  Analogously, for the Zpair Zdensity

(2) N (N 1)
⇢ (r1 , r2 ) = . . . exp V(rN ) drN 2
Z
ZZ Z Z
(2) N (N 1)
⇢ (r1 , r2 ) dr1 dr2 = . . . exp V(rN ) drN
Z
= N (N 1)
1
–  So ⇢(2) (r1 , r2 ) dr1 dr2
N (N 1)
is P (any molecule in dr1, any molecule in dr2,
irrespective of the positions of the remainder)
•  “P (molecule at r1 and another at r2)”
Density functions ! g (r)
•  Define n-particle distribution function:

(n) n
(n) n ⇢ (r )
g (r ) = Qn (1) (r )
i=1 ⇢ i
–  e.g., pair distribution function

(2)
(2) ⇢ (r1 , r2 )
g (r1 , r2 ) = (1) (Equation. 4.21)
⇢ (r1 )⇢(1) (r2 )
•  If we also define P (r2 |r1 ) = (1/N 1)⇢† (r2 |r1 )dr2
⇢(2) (r1 , r2 )dr1 dr2 = ⇢(1) (r1 )dr1 ⇢† (r2 |r1 )dr2 ,
so ⇢(2) (r1 , r2 ) = ⇢(1) (r1 ) ⇢† (r2 |r1 )
Density functions ! g (r)
•  Pair distribution function becomes:

(1) †
(2) ⇢ (r 1 ) ⇢ (r2 |r1 )
g (r1 , r2 ) = (1)
⇢ (r1 )⇢(1) (r2 )
•  If system is isotropic: ⇢† (r2 |r1 ) ⇢† (r) ⌘ ⇢(r)
•  If homogeneous: ⇢(1) (r) = N/V ⌘ ⇢
•  If both isotropic and homogeneous:
(2) ⇢(r)
g (r1 , r2 ) g(r) = (Equation. 4.24)
iso,homog ⇢
(Pair) radial distribution function
Importance of g (r)
•  Tells us about structure:

Importance of g (r)
•  Link to experiment
–  closely related to structure factor (scattering function)
from scattering experiments
and computer simulations
–  accumulated as a histogram by
counting molecules in concentric
shells around origin molecule,
averaged over all molecules

Importance of g (r)
•  Crucial role in theories of fluids

–  Arises out of approximation that intermolecular
potential is expressible as a sum of effective pair
interactions:
N X
X N
V(rN ) = (ri,j ) Equation 4.25
i j>i
–  Demonstrate by example …

g(r) leads to the Energy equation
N N
•  hH(r , p )i = hV(rN )i + hK(pN )i
l l l
U = U residual + U ideal
X
•  By definition hxi = xi P (xi )
•  whence Z Z
i
U residual = . . . V(rN )P (V(rN ))drN

Z Z
1
= . . . V(rN ) exp( V(rN ))drN
Z
(Equation 4.26)
Statistical-mechanical average of V
•  Incorporating equation
0 4.25 gives:
1
Z Z N X
X N
1 @
U residual = ... (ri,j )A exp V(rN ) drN
Z i j>i
•  Examine double sum in detail:

1,2 + 1,3 + 1,4 + ... + 1,N (N 1 terms)
N X
X N + 2,3 + 2,4 + ... + 2,N (N 2 terms)
(ri,j ) = + 3,4 + ... + 3,N (N 3 terms)
i j>i .. .. .. ..
. . . .
( shorthand: i,j ⌘ (r)i,j ) + N 1,N (1 term)
1 2 1
](terms) = (N 1) (N 1) + (N 1) = N (N 1)
2 2
•  Integral of sum becomes a sum of N(N – 1)/2

integrals: ⇢Z Z
residual 1
U = ... (r1,2 ) exp( V(rN ))drN
Z
Z Z
+ ... (r1,3 ) exp( V(rN ))drN
Z Z
+... + ... (r1,N ) exp( V(rN ))drN
Z Z
+ ... (r2,3 ) exp( V(rN ))drN + . . .
Z Z
+ ... + ... (rN 1,N ) exp( V(rN ))drN

Energy equation
•  All ϕ(ri,j) equivalent, whereby all integrals

identical, thus:
Z Z
residual N (N 1)
U = ... (r1,2 ) exp( V(rN ))dr1 dr2 . . .drN
2Z
•  Now we factorize the integral
–  ϕ(r1,2) depends on r1 and r2 only
ZZ Z Z
residual N (N 1)
U = (r1,2 ) ... exp( V(rN ))dr3 . . .drN dr1 dr2
2Z
ZZ Z Z
N (N 1)
⌘ (r1,2 ) ... exp( V(rN ))drN 2
dr1 dr2
2Z

Energy equation
•  Carrying forward:
ZZ Z Z
residual N (N 1)
U = (r1,2 ) . . . exp V(rN ) drN 2
dr1 dr2
2Z
•  Next recall Equation 4.9
Z Z
(2) N (N 1)
⇢ (r1 , r2 ) = ... exp V(rN ) drN 2
Z
and compare:
Z Z
residual 1
U = ... (r1,2 )⇢(2) (r1 , r2 )dr1 dr2
2

•  Carrying forward: Z Z
residual 1
U = ... (r1,2 )⇢(2) (r1 , r2 )dr1 dr2
2
•  Now recall:
–  Equation 4.21 ⇢(2) (r1 , r2 ) = g (2) (r1 , r2 ) ⇢(1) (r1 ) ⇢(1) (r2 )
(2)
–  Isotropic system: g (r1 , r2 ) g (2) (|r2 r1 |) ⌘ g(r1,2 )
–  Homogenous system ⇢(r) ⇢
•  equations 4.15–4.17
•  whereby ZZ
residual 1 2
U = ⇢ (r1,2 )g(r1,2 )dr1 dr2
2
Energy equation
•  Carrying forward: ZZ
residual 1 2
U = ⇢ (r1,2 )g(r1,2 )dr1 dr2
2
•  Integral over vector r1, r2 but integrand depends
only on (scalar) r1,2
@r1,2
–  transform: r1,2 = r2 r1 =1 dr1,2 = dr2
@r2
–  in spherical polar coordinates
Z Z ⇡ Z 2⇡ Z 1
2
dr1,2 = r1,2 sin ✓ d✓ d' dr1,2
✓=0 '=0 r=0
•  whereby
Z Z ⇡ Z 2⇡ Z 1
1 2
U res = ⇢ 2
(r1,2 ) r1,2 g(r1,2 ) sin ✓ d✓ d' dr1,2 dr1
2 r1 ✓=0 '=0 r1,2 =0
Energy equation
•  Carrying
Z Zforward:
⇡ Z 2⇡ Z 1
res 1 2 2
U = ⇢ (r1,2 ) r1,2 g(r1,2 ) sin ✓ d✓ d' dr1,2 dr1
2 r1 ✓=0 '=0 r1,2 =0
Z ZZZ
•  Integrate out r1: dr1 ⌘ drx,1 dry,1 drz,1 = V
•  Integrate out angular dependences ! 4π
•  Yields: (Equation 4.37)
Z 1
U residual = 2⇡⇢2 V 2
(r1,2 ) r1,2 g(r1,2 ) dr1,2
0
Z 1
or U residual = 2⇡⇢N 2
(r1,2 ) r1,2 g(r1,2 ) dr1,2
0

Energy equation
•  “Human” interpretation:

Virial
•  A similar argument leads to the pressure

equation or virial
–  will present just an outline
•  for details, see e.g., McQuarrie, Statistical Mechanics; Hansen
and McDonald, Theory of Simple Liquids; …
•  Begin with A = – kBT ln Q, whereby

✓ ◆ ✓ ◆
@ ln Q @ ln Q
p = kB T pV = kB T V
@V N,T @V N,T
•  but, keeping in mind ideal gas equation

pV = N kB T + (pV )residual
Virial
•  Residual part:
–  obtained from force, – dϕ(r1,2) / dr1,2, between a specified
molecule and all other molecules, accounted for in
concentric shells at increasing separation, r :

Virial
–  obtained from force, – dϕ(r1,2) / dr1,2, between a specified
molecule and all other molecules, accounted for in
concentric shells at increasing separation, r :
–  for each shell, force is divided by surface area (4πr2dr) !
pressure
d (r1,2 )
p(r1,2 ) = ⇢g(r1,2 )
dr1,2
–  multiplied by volume contained within shell ! pV for each
shell
d (r1,2 ) 4 3
p(r1,2 )V = ⇢g(r1,2 ) ⇥ ⇡r1,2
dr1,2 3
Virial
•  (carried forward)
d (r1,2 ) 4 3
p(r1,2 )V = ⇢g(r1,2 ) ⇥ ⇡r1,2
dr1,2 3
–  integrate from r = 0 to ∞ ! total (pV)residual per molecule
Z 1
4⇡⇢ d (r1,2 ) 3
pV(1) = g(r1,2 )r1,2 dr1,2
3 0 dr1,2
–  Multiply by N / 2 ! contribution for all N molecules
•  factor of half avoids counting each pair interaction twice
Z 1
residual 2N ⇡⇢ d (r1,2 ) 3
pV(N ) ⌘ (pV ) = g(r1,2 )r1,2 dr1,2
3 0 dr1,2
Virial
•  (carried forward) Z 1
residual 2N ⇡⇢ d (r1,2 ) 3
pV(N ) ⌘ (pV ) = g(r1,2 )r1,2 dr1,2
3 0 dr1,2
•  Now combine with ideal part:
Z 1
2N ⇡⇢ d (r1,2 ) 3
pV = N kB T g(r1,2 )r1,2 dr1,2
3 0 dr1,2
•  Usual to express in terms of compressibility
factor,
Z ⌘ pV /N kB T = p/⇢kB T

Virial
•  whence we obtain the pressure equation or

virial:
Z 1
p 2⇡⇢ d (r1,2 ) 3
Z= =1 g(r1,2 )r1,2 dr1,2
⇢kB T 3kB T 0 dr1,2
–  NB:
•  don’t confuse Z with the configurational integral
•  this equation is not the same as the virial equation of
state (or virial expansion)

In the last few slides …
•  We demonstrated the usefulness of g(r) in

expressing thermodynamic properties
–  such as the energy and pressure
of a many-particle system in terms of one-
dimensional integrals
–  rather than the N-dimensional integrals inherent in the
full ensemble averages
•  Expressions are simpler in form; difficulty is

shifted to determining g(r)

Z 1 Z 0
2 2
exp( ↵ u )du = 2 exp( ↵2 u2 )du
1 1
Z 1 click
= 2 exp( ↵2 u2 )du
0
since the integration variable (u) appears in the integrand only as its square.
s⇢
Z 1 Z 1 2
2 exp( ↵2 u2 )du = 2 exp( ↵2 u2 )du
0 0
s ⇢Z Z
1 1
= 2 exp( ↵2 u2 )du exp( ↵2 v 2 )dv
0 0
s ⇢Z Z
1 1
= 2 exp( ↵2 (u2 + v 2 ))dudv .
0 0
In polar coordinates, u2 + v 2 = r2 ; area element du dv r d✓ dr, hence

v( )
Z 1 u Z ⇡/2 Z 1
u
2 exp( ↵ u )du = 2 t
2 2
exp( ↵2 r2 )rd✓ dr
0 ✓=0 r=0
s⇢  s⇢ p
1
⇡ exp( ↵2 r 2 ) ⇡ 1 ⇡
= 2 =2 = .
Molecular Modelling of Fluids 2 2↵2
Session 2 – Slide 87
r=0 2↵2
2© Imperial College London
↵
Virial
•  A similar argument leads to the pressure

equation or virial:
Z 1
p 2⇡⇢ d (r1,2 ) 3
Z= =1 g(r1,2 )r1,2 dr1,2
⇢kB T 3kB T 0 dr1,2
where Z is the compressibility factor
(Note that this is not the same as the virial equation of state (or
virial expansion))

Elective Molecular Modelling CE433 Session2 AJH 2016 17

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Elective Module:

CE4-33 Molecular Modelling of Fluids

Session 2: Classical Statistical Mechanics:

Molecular Modelling of Fluids Session 2 – Slide 1 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 3 © Imperial College London

• Principle of equal a priori probabilities

Molecular Modelling of Fluids Session 2 – Slide 4 © Imperial College London

• The concept of ensembles:

Molecular Modelling of Fluids Session 2 – Slide 5 © Imperial College London

• State of subsystem / member of ensemble

• Link to macroscopic thermodynamics:

Molecular Modelling of Fluids Session 2 – Slide 7 © Imperial College London

– Other thermodynamic quantities then obtained from

Molecular Modelling of Fluids Session 2 – Slide 8 © Imperial College London

– Other thermodynamic quantities then obtained from

Session 2: Classical Statistical Mechanics

Molecular Modelling of Fluids Session 2 – Slide 10 © Imperial College London

• Recall: Canonical distribution

• Ideal-gas particles have no

• Each ideal-gas molecule

Molecular Modelling of Fluids Session 2 – Slide 12 © Imperial College London

• These expressions allow us to evaluate the

Molecular Modelling of Fluids Session 2 – Slide 14 © Imperial College London

• Recall our example: how many ways can we

• Analogously, Equation 1.39 must be modified

Molecular Modelling of Fluids Session 2 – Slide 16 © Imperial College London

• Recall the expressions for the εi and definition

• from which Q can be obtained, and then A, and

• Recall again: Canonical distribution

Molecular Modelling of Fluids Session 2 – Slide 18 © Imperial College London

• However, we do often have an expression for

Molecular Modelling of Fluids Session 2 – Slide 19 © Imperial College London

• Problem: we cannot know both position and

• Instead, we know r to within dr and p to within

Molecular Modelling of Fluids Session 2 – Slide 20 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 21 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 22 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 23 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 24 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 25 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 26 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 27 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 28 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 29 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 30 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 31 © Imperial College London

Molecular Modelling of Fluids Session 2 – Slide 32 © Imperial College London

Can loosely identify system state j

Can loosely identify system state j

– where i = 1,…, N includes all N particles / molecules in system,

• In a sense: system has an energy (Hamiltonian)

• P (system has this energy) must be

Molecular Modelling of Fluids Session 2 – Slide 35 © Imperial College London

• This in turn leads us to think about probability

• f (N)(rN, pN ): phase-space probability density

• f (N)(rN, pN ) is a probability density since,

f (N ) (rN, pN )drN dpN ⌘ f (N ) (r1 , r2 , . . . , rN , p1 , p2 , . . . , pN )

Molecular Modelling of Fluids Session 2 – Slide 37 © Imperial College London

• By rules of probability, f (N)(rN, pN ) drNdpN must

– so dimensions f (N)(rN, pN ) are “1 / (rN pN )”

• Heisenberg uncertainty principle:

• We expect the form to be reminiscent of

Molecular Modelling of Fluids Session 2 – Slide 39 © Imperial College London

•  Principle of equal a priori probabilities

•  The concept of ensembles:

•  State of subsystem / member of ensemble

•  Link to macroscopic thermodynamics:

–  Other thermodynamic quantities then obtained from

–  Other thermodynamic quantities then obtained from

•  Recall: Canonical distribution

•  Ideal-gas particles have no

•  Each ideal-gas molecule

•  These expressions allow us to evaluate the

•  Recall our example: how many ways can we

•  Analogously, Equation 1.39 must be modified

•  Recall the expressions for the εi and definition

•  from which Q can be obtained, and then A, and

•  Recall again: Canonical distribution

•  However, we do often have an expression for

•  Problem: we cannot know both position and

•  Instead, we know r to within dr and p to within

–  where i = 1,…, N includes all N particles / molecules in system,

•  In a sense: system has an energy (Hamiltonian)

•  P (system has this energy) must be

•  This in turn leads us to think about probability

•  f (N)(rN, pN ): phase-space probability density

•  f (N)(rN, pN ) is a probability density since,

•  By rules of probability, f (N)(rN, pN ) drNdpN must

–  so dimensions f (N)(rN, pN ) are “1 / (rN pN )”

•  Heisenberg uncertainty principle:

•  We expect the form to be reminiscent of

•  To progress further, we need the Hamiltonian,

•  McQuarrie (in Statistical Mechanics):

•  P (rN ) is not particularly useful as it stands

•  ρ(1)* (rN ) is not particularly useful either

•  Analogously, for the Zpair Zdensity

•  Define n-particle distribution function:

–  e.g., pair distribution function

•  Pair distribution function becomes:

•  Tells us about structure:

•  Crucial role in theories of fluids

•  Examine double sum in detail:

•  Integral of sum becomes a sum of N(N – 1)/2

•  All ϕ(ri,j) equivalent, whereby all integrals

•  A similar argument leads to the pressure

•  Begin with A = – kBT ln Q, whereby

•  but, keeping in mind ideal gas equation

•  whence we obtain the pressure equation or

•  We demonstrated the usefulness of g(r) in

•  Expressions are simpler in form; difficulty is

•  A similar argument leads to the pressure