Bi 2:

Mt s kin thc v
Vt l thng k

Under construction.

Khng gian pha

Xt mt h c in N ht
Trng thi ca h c xc nh bi ta r v xung
lng p ca tt c cc ht
Khng gian pha: 6N bin, = (r,p) hoc (q,p)
S thay i trng thi theo thi gian tun theo cc
phng trnh c hc c in
H =K V p
H
H
qk =
, p k =
pk
qk

Chuyn ng ca h theo thi gian m t bi mt

qu o trong khng gian pha (t)
Do tnh tt nh ca cc phng trnh Newton, qu
o ny khng bao gi ct chnh n!
Poincare: nu i lu th h c th quay tr v
trng thi ban u!

Poincare recurrence time > tui v tr i vi

h v m

Tp hp thng k

i lng o c A()
Gi tr o c bng thc nghim l gi tr trung bnh
theo thi gian
t
1
Aobs = Atime = A t time = A t dt
t obs 0
obs

Gibbs: ly trung bnh theo tp hp vi phn b cn

thit!
Aobs = Aens = A

mt xc sut trng thi iu kin v

m nht nh: NVE, NVT, NPT...

Tp hp: bao gm cc bn sao ca h nhiu trng

thi khc nhau

(,t) mt xc sut

nh l Louville:
d
=0
dt

s h trong tp hp khng thay i theo thi

gian

tp hp chuyn ng theo thi gian trong khng

gian pha nh mt cht lng c nn bng 0!
N

= ri
p

r
i
p
t
i=1

Khi t v cng ln, ta c tp hp cn bng:

=0
t

khi , khng ph thuc thi gian!

v ta c A = A
time
ens

H ergodic: any point in phase space is accessible

from any other point
H non-ergodic: some region of phase space is not
accessible from outside

Trng s & hm phn hoch:

=Q 1 w
Q= w

A=Q

A w

ty thuc vo cch ly trng s ta c cc tp hp

khc nhau

M phng Monte Carlo: cho php to ra mt tp hp

cc trng thi theo mt xc xut cho trc, khi

1
A=
K

A k
k=1

Tp hp vi chnh tc

N,V,E = constants

Q NVE = H E

1 1
Q NVE =
dr dp H r , pE
3N
N! h
S =k B ln Q NVE

entropy

Phng php ng lc hc phn t (MD): to ra tp vi

chnh tc (E=constant), ng thi bo ton xung lng
tng cng

Tp hp chnh tc

N,V,T = constants
H ()/ k B T

w ()=e

Q NVT = e

H ()/ k B T

F =k B T ln Q NVT

Nng lng t do Helmholtz

1 1
K / k T
V
Q NVT =
dp
e
dr
e

3N
N! h
1
Q NVT =
Z NVE
2
3N /2
N ! h / 2mk B T
B

Z NVT = dr e

V p r /k B T

r /k B T

configurational integral

Tp hp ng nhit ng p

N,P,T=constants

w =e

H PV / k B T

Q NPT = e

H PV / k B T

P/k BT

= e
V

G=k B T ln Q NPT
PV / k B T

Z NPT = dV e

dr e

Q NVT

Nng lng t do Gibbs

V p r /k B T

Tp hp chnh tc ln

,V,T=constants

w =e

H N / k B T

Q VT = e

H N / k B T

PV =k B T ln Q VT

= e
N

N /kBT

Q NVT

phng trnh trng thi

nh lut ng phn

Mi bc t do ng vi kch thch nng lng kT

H
pk
=k B T
pk

H
qk
=k B T
qk

S bc t do = 3NN c
Nc l s rng buc (constraint)

Nhit tc th

Nhit o c bng thc nghim l nghit

trung bnh theo thi gian
Trong m phng c th tnh nhit t mt trng
thi vi m ca h
T nh lut ng phn ta c:

p i
3N
K =
=
kBT
2
i=1 2 mi

Nhit tc th:
N

p i
2K
1

T=
=

3Nk B 3Nk B i=1 mi

Trong trng hp c Nc rng buc:

2
p

2K
1
i

T=
=

3NN c k B 3NN c k B i=1 mi

N

Nhit trung bnh:

T = T

p sut tc th

T trng thi vi m ca h c th tnh c p sut

tc th
T nh lut ng phn ta c:
q k p k =k B T
suy ra:
1
3

p k = f =
Vp
qk
tot
k

tot

ri f i =N k B T
i=1

Lc tng cng bng ngoi lc + ni lc:

ext
internal
f tot

i =f i fi

Ngoi lc cn bng vi p sut ln cc bc tng:

1
3

ext

i i =PV
i=1

Hm virial

1
1
internal

W ri f i
= ri r V p
3 i=1
3 i=1
i

PV = N k B T W

p sut tc th:

hoc

P= k B T W = P ideal gas P ex
V
P= k B T W = P ideal gas P ex
V

Tng tc cp
V p = v (r ij )
i< j

1
1

W = ri f ij = ri r v r ij
3 i i j
3 i i j
ij

1
W = w r ij
3 i i j
dv r
w r =r
dr

hm virial cho tng tc cp

Nhit dung ring

N,V,T=constants
E= H
2

E = H H
H 2 H 2
C v=
2
kBT

N,P,T=constants
H 2 H 2
C p=
2
k BT

Thc hnh lp trnh

Gi s gi ngu nhin trong Fortran 90

Vector ngu nhin trong khng gian 3 chiu

S ngu nhin theo phn b Gauss

To cc trng thi ca h kh l tng N ht trong

th tch V vi vn tc theo phn b MaxwellBoltzmann

Gi s gi ngu nhin
(pseudo-random number)
u(0,1)
program test1
integer, dimension(1) :: seed
integer :: k
real :: u
call random_seed(size=k)
call random_seed(put=seed(1:k))
call random_number(u)
print *,u
end program test1

phn b u

To vector n v ngu nhin trong

khng gian 3 chiu
Trong h ta cu ta c:

(0, )

(0,2 )

d =sin d d =d (cos )d
Chn 2 s ngu nhin u v v:

=2 u
x=sin cos
y=sin sin
z=cos

u , v (0,1)
1

=cos (2 v1)
Trong h ta tr:

x= 1t 2 cos
y= 1t 2 sin
z=t

t=2 v1

To s ngu nhin theo phn b Gauss

Tnh sin, cos trn my tnh kh mt thi gian !!

Phn b Maxwell-Boltzmann