Bi 4:

M phng Monte Carlo

(tip theo)

Under construction.

M phng h kh lng
Cc nguyn t (phn t) c coi
l cc ht hnh cu.
Cc ht c tng tc.
S dng iu kin bin tun hon.
M phng:
- Trng thi kh
- Trng thi lng
- Git cht lng (ng tn ti 2 pha)

Th nng tng tc
V =i v 1 ( ri )+ v 2 (r ij )+ v 3 ( ri , rj , rk )+...
i

tng tc vi
trng ngoi

i< j

tng tc cp

tng tc 3 ht
(ng k i vi cht lng,
~ 10% tng th nng)

V i v 1 ( ri )+ v eff
2 (r ij )
i

i< j

th nng hiu dng cho

tt c cc tng tc a ht

Th nng Lennard-Jones

[(

v (r ij )=4
r ij
LJ

) ( )]

LJ 6-12
experiments on liquid argon

12

r ij

ht

Mt s loi th nng hiu dng khc

(a) Hard-sphere (HS)

(r <)
v (r )=
0 (r )
(b) Square well (SW)

(r < 1 )
v (r )= ( 1r < 2 )
0 (r )
(c,d) Soft-sphere

v (r )=( / r )
long-ranged
short-ranged

v (r )r1
v (r )r12

Tch th nng LJ
repulsive LJ

attractive LJ
1/6

r min = 2

Tch th nng LJ
repulsive LJ

attractive LJ
1/6

r min = 2

Monte Carlo

Trong 1 bc Monte Carlo:

Chn ngu nhin 1 ht i

Dch chuyn ht i theo mt bc ngu nhin vi mt bin

ti a cho trc.

Cn dch chuyn vi xc sut nh nhau ti mi

im trong xm.

 E= E
n
i

new

old

m
i

E= v (|r r j|)v (|r r j|)

ji

Phng php Metropolis: chp nhn dch

chuyn vi xc sut
k nm =min {1, exp( E )}
E = V

Chn ngu nhin trong khong (0,1).

Nu < k nm : chp nhn dch chuyn
Nu k nm : quay li trng thi c

Bin dch chuyn ti a

Thng thng, chn r max 0.3

Trong qu trnh m phng, c th iu chnh bin
dch chuyn ti a r max sao cho khong 50% s
dch chuyn c chp nhn.
if (mod(ntrial,nadjst) .eq. 0) then
ratio = real (naccpt) / real (nadjst)
if (ratio > 0.5) then
drmax = drmax * 1.05
else
drmax = drmax * 0.95
endif
naccpt = 0
endif

Chn ht cho dch chuyn

Cc cch chn sau l tng ng:

chn 1 ht ngu nhin trong mi bc MC

chn mt cch tun t t ht th nht ti ht

cui cng (MC cycle)

chn tt c cc ht cng 1 lc

Ct th nng LJ

gim thi gian tnh, ch tnh th nng cho khong

cch r< r c

Thng thng chn cut-off r c=2.5

Sau cn hiu chnh li nng lng ton phn

E full E c E LRC = E c 2 N r v r dr
rc

rc
E LRC =8/ 9 N

rc
8/3 N

LRC: long range correction

iu kin bin tun hon

Ct th nng vi iu kin bin tun hon

r c< L

Box

(-L/2, L/2)

(-L/2,L/2)

(-L/2,L/2)

x(i) = x(i) L * anint( x(i) / L )

y(i) = y(i) L * anint( y(i) / L )
z(i) = z(i) L * anint( z(i) / L)
xij = x(i) x(j)
xij = xij L * anint( xij / L)

S dng h ta rt gn:
x = x/L y=y/L z=z/L
x(i) = x(i) anint(x(i))
xij = xij - anint(xij)

nh hng ca PBC ln kt qu m phng

Khng m t c bin thin bc sng di hn kch

thc hp ( > L), do vy khng tt khi m phng h
chuyn pha (ti chuyn pha xy ra bin thin mt
kch thc ln).

L6

Kch thc hp phi ln:

Khng tt i vi th nng tng tc xa (e.g. Coulomb):

v (r )r

<d

Trong mt s trng hp c th to nn tnh bt ng

hng ca cht lng
Trng ngoi cn c tnh cht tun hon ging nh hp
m phng

Tuy nhin, PBC c s dng rng ri v kh tt khi

m phng:

H vi cc tng tc tm ngn (short-range)

H cch xa iu kin chuyn pha.

M phng h ng nhit ng p
(NPT=constant)

dV exp( PV )V d s A( s )exp( V p (s))

A NPT =

Z NPT
s=( s1 , s2 ,... , sN )
1

s= L r
L=V

scaled
coordinates

Dng phng php Metropolis vi phn b cn bng:

eq

p ( s )exp(( PV + E p ( s))+ N ln V )

To trng thi mi n t trng thi c m bng cch

dch chuyn ngu nhin 1 ht
n
m
si = si + s max (2 1)
hoc thay i ngu nhin th tch:
V n=V m+ V max (2 1)

Chp nhn trng thi mi vi xc sut:

k nm =min(1, exp( H nm ))
1

H nm = E p + P (V n V m ) N ln (V n /V m )

Tnh thay i th nng khi thay i th tch

Thc hnh

Vit chng trnh m phng Monte Carlo cho h kh Argon

trong iu kin N,V,T=const vi tng tc Lennard-Jones:

= 3.349 Angstroms

kB= 140 Kelvin

iu kin bin tun hon.

Vit chng trnh m phng h trn trong iu kin

N,P,T=const.
Tnh nhit dung ring CV v CP ph thuc vo nhit T.

Hin th kt qu m phng

Rasmol

VMD: Visual Molecular Dynamics

nh dng file: PDB (Protein Data Bank)

open(15,file='x.pdb')
do i=1,N
write(15,'(a,i5,2x,a,a,i6,f12.3,2f8.3)') &
'HETATM',i,'AR ','GAS',i,x(i),y(i),z(i)
enddo
write(15,'(a)')'END'
close(15)