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1

2 i

3 Verlet

4 1 1 MD t N r 1 (t), r 2 (t),, r N (t) ṙ 1 (t), ṙ 2 (t),, ṙ N (t) MD a 1, a 2, a 3 r i (i =1,,n)

5 1 2 T =0K r i + m 1 a 1 + m 2 a 2 + m 3 a 3 (m 1,m 2,m 3 =0, ±1, ±2,, ± ), (i =1,,n) (1.1) 1.1 a 1 =(a 1x,a 1y,a 1z ), a 2, a 3 r i =(x i,y i,z i )(i =1,,n) a 1, a 2, a 3 m 1,m 2,m 3 (3,N) R(i, j) i =1 X i =2 Y i =3 Z j N N = n m 1 m 2 m 3 n m 1,m 2,m 3 parameter N 256 MKS 1A=10 10 m LJ A σ 1.2 MD

6 1 3 (1/2, 1/2, 1/2) (1/4, 1/4, 1/4) (3/4, 3/4, 3/4) (1/4, 1/4, 1/4) (1/4, 3/4, 3/4) (3/4, 1/4, 3/4) (3/4, 3/4, 1/4) MD MD MD ξ 1 ξ x i = x i + ξδ (1.2) x i x i δ 10 % 0 ξ 1 ξ =2ξ 1 MD

7 1 4 32bit 2 32 IR(IY)=513*IY R(IY)=DFLOAT(IY)/ D0 IR(IY) IR(IY) R(IY) IY IY IY IY=IR(IY) R(IY) IY=IR(IY) X=R(IY) X 1 x 1 MD 4σ σ

8 5 2 g(r) r r r + dr ρ4πr 2 g(r)dr 4πr 2 dr ρ g(r) =1 g(r)?? 0 δ r =0 r g(r) =0 n(r) = r 0 ρ 4πr 2 g(r)dr (2.1) r g(r) X n(r) g(r) g(r) r r + dr ρ4πr 2 g(r)dr g(r) R r c dr NG(0:1000) 0 r ij NN=INT(r ij /dr) (NN-1)*dr NN*dr NN

9 2 6 NG(NN)=NG(NN)+1 NG NN 1 NN=INT(r ij /dr +0.5) g(r) NN*dr NG(NN) N/2*NT ANG(NN)=4πr 2 g(r)dr N NT NT NT=1 n(r) ANG(NN) 0 g(r) ANG(NN)/4πr 2 drρ g(r) minimum image convention MD r h r h g(r) g(r) MD i j MD j j MD j i j i j g(r) R MD j j i R minimum image convention x MD L x L y L z x L x CLX CLXH=CLX*0.5d0

10 2 7 DX=R(1,I)-R(1,J) IF(DX.GT.CLXH) DX=DX-CLX IF(DX.LT.-CLXH) DX=DX+CLX MD DX L x /2 L X /2 x MD IF FORTRAN INT(X) MOD(X,1) DX=DX-CLX*INT(DX/CLXH) IF IF IF 1/4 g(r) 40 g(r) 0.1 CHARACTER*1 A(40)/40* / CHARACTER*1 ASTER/ * /,ONE/ 1 /,ZERO/ 0 /,BLANK/ / g(r) GR DO 200 J=1,NR GR=G(J) IK=INT( GR*10.0D D ) IF(IK.GT.40) IK=40 A(1)=ZERO A(11)=ONE A(IK)=ASTER WRITE(*,110) X(J),G(J),N(J),A

11 FORMAT(1H,3F6.2,3X,40A1) A(IK)=BLANK 200 CONTINUE WRITE X(I) FORMAT g(r) 10.0D0 g(r) d0 g(r) g(r) =1 11 1

12 9 3 Verlet MD MD q p dq dt = p m, dp dt = mω2 q, m d2 q dt = 2 mω2 q (3.1) E = p2 2m mω2 q 2 dq dt = P, dp dt = Q, d 2 Q = Q (3.2) dt2 E = 1 2 P Q2 P P t =0 P Q P 0 Q 0 P = P 0 cos t Q 0 sin t, Q= P 0 sin t + Q 0 cos t (3.3) t t n = n t Q P Q n P n Q n P n Q n+1 P n+1

13 3 Verlet 10 t t = n t t (3.3) MD Verlet leap frog t n = n t Q n t n 1/2 P n 1/2 (1) n Q n F n F n = Q n (2) dp/dt = F P n+1/2 = P n 1/2 + F n t (3.4) t n+1/2 P n+1/2 P n+1/2 = P n 1/2 Q n t (3.5) leap frog (3) n +1 Q n+1 dq dt = P Q n+1 = Q n + P n+1/2 t (3.6)

14 3 Verlet 11 (4) Q n P n P n 1/2 P n+1/2 P n P n = 1 2 (P n+1/2 + P n 1/2 ) (3.7) Q 0 P 1/2 (3.4) (3.7) P n 1/2 P n P n = P n 1/2 + F n t 2 (3.8) n =0 Q 0 P 0 P 1/2 = P 0 F 0 t 2 (3.9) 3.1 Verlet t Q 0 P 0 Q n P n E n = 1 2 (P n 2 + Q 2 n) Verlet S n = 1 ( [P 2n )] 4 ( t)2 Q 2 n (3.10) Q 0 =1.0, P 0 =1.0 t = Q n,p n,e n,s n ˆP n, ˆQn, Ê n E n S n?? E n S n

15 3 Verlet 12 S n 10 E n t 0.1, 0.05, 0.02, 0.01, 0.005, 0.002, t =0.2 Q, P, E t t/ t δx x ˆx δx = x ˆx x Q P E t t δx = A( t) k ln δx =lna + k ln t k MD t t t

16 3 Verlet 13 t Verlet t t t =0.001, , , , , , , , , Q, P, E t t/ t 1 Verlet 3 t t t

17 3 Verlet 14 t t t = 1 E i+1 E i (3.11) N i Verlet 0 t t 20

18 3 Verlet Q 0 =1.0, P 0 = Verlet Q n P n Verlet P n+1/2 = P n 1/2 Q n t (3.12) Q n+1 = Q n + P n+1/2 t (3.13) 3.13 n n 1 Q n = Q n 1 + P n 1/2 t (3.14) P n+1/2,p n 1/2 Q n+1,q n,q n 1 Q n+1 ( 2 ( t) 2) Q n + Q n 1 = 0 (3.15) Q n = Aλ n λ λ 2 ( 2 ( t) 2) λ + 1 = 0 (3.16) λ 1,λ 2 Q n = Aλ n 1 + Bλ n 2 (3.17)

19 3 Verlet 16 (1) cos α =1 1 2 ( t)2 λ 1,2 = e ±iα t α = t ( t) ( t)5 + t n P n P n = 1 2 ( Pn+1/2 + P n 1/2 ) = Q n+1 Q n 1 2 t (3.18) (2) Q 0,P 0 Q n,p n ( ) t Q n = Q 0 cos nα + P 0 sin nα (3.19) sin α ( ) sin α P n = P 0 cos nα Q 0 sin nα (3.20) t (3) [ S n = 1 Pn ( sin α t ) 2 Q 2 n ] (3.21) ( ) 2 sin α =1 1 t 4 ( t)2 S n E n 1 8 ( t)2 Q 2 n ( t)2 3.7 Verlet t = 2π 2π t = Q, P, E δq, δp, δe, δx = (δq) 2 +)δp) 2

20 3 Verlet t = 2π δq, δp, δe, δx t δe t ( t) k δq, δp ( t) t = 2π 4 Verlet t =2 t = 2π 4 (Q n,p n ) Q Q n Q(t) =Q 0 cos(αt)+ α α = 2 ( ) π cos 1 1 π2 8 P 0 1 π2 16 sin(αt) = ˆQ(t) =Q 0 cos t + P 0 sin t 2 Verlet E t

21 18 4 Verlet MD MD (Rahman Stillinger m d2 r = F (r) (4.1) dt2 t r(t) r (1),r (2),r (3),r (4),r (5) X k = 1 k! ( t)k r (k), (k =0, 1, 2, 3, 4, 5) (4.2) t X k (t) t + t X k (t + t) X 0(t + t) =X 0 (t)+x 1 (t)+x 2 (t)+x 3 (t)+x 4 (t)+x 5 (t) (4.3) X 1 (t + t) =X 1(t)+2X 2 (t)+3x 3 (t)+4x 4 (t)+5x 5 (t) (4.4) X 2(t + t) =X 2 (t)+3x 3 (t)+6x 4 (t)+10x 5 (t) (4.5) X 3(t + t) =X 3 (t)+4x 4 (t)+10x 5 (t) (4.6) X 4(t + t) =X 4 (t)+5x 5 (t) (4.7) X 5(t + t) =X 5 (t) (4.8)

22 4 19 X 0(t + ) F (X 0(t + )) X 2(t + ) δ = 1 F (X 0 (t + )) ( t) 2 X 2 m 2(t + ) (4.9) 0 ( X k (t + ) δ X k (t + )=X k(t + )+C k δ (4.10) C k C k Nordsieck Gear C k Gear C 0 = 3 20,C 1 = ,C 2 =1,C 3 = 11 18,C 4 = 1 6,C 5 = 1 60 (4.11) 4.1 d 2 Q = Q (4.12) dt2 t, Q 0,P 0 = Q 0 X k (n t) t =0 X 0 (0) = Q 0, X 1 (0) = P 0 t, X 2 (0) = 1 2 Q 0( t) 2,X 3 (0) = 1 6 P 0( t) 3 X 4 (0) = 1 24 Q 0( t) 4, X 5 (0) = P 0( t) 5 (4.13) Q 0 =1.0, P 0 =1.0, t = ( ) X 0 (n t), X 1(n t),e n X 0 t (n t), X 1(n t) t

23 4 20 X 0 (n t), X ( 1(n t),e n X 0 (n t), X ) 1(n t) t t ˆQ n, ˆPn, Ê n , 0.1, 0.05, 0.04, , 0.02, 0.01, , 0.005, t=1.0 Q, P, E ln E =ln E n+1 E n

24 4 21 t Verlet d 2 Q dt 2 = Q 2adQ dt (4.14) Q Q = P E = 1 2 (P 2 + Q 2 ) t =0 Q(0) = Q 0,Q (1) (0) = P 0 Q (2) (0) = Q 0 2aP 0 Q (3) (0) = 2aQ 0 +(4a 2 1)P 0 Q (4) (0) = (4a 2 1)Q 0 +4a(1 2a 2 )P 0 Q (5) (0) = 4a(2a 2 1)Q 0 +(1 12a 2 +16a 4 )P 0 (4.15) [ Q(t) =e at Q 0 cos( 1 a 2 t)+ P ] 0 + aq 0 sin( 1 a 2 t) 1 a 2 [ P (t) = Q(t) =e at P 0 cos( 1 a 2 t) Q ] 0 + ap 0 sin( 1 a 2 t) 1 a 2 (4.16) (4.17)

25 4 22 a = E = 1 2 (P 2 + Q 2 ) de dt = P dp dt + QdQ dt = P ( Q 2aP )+QP = 2aP 2 (4.18) E(t) E(0) = 2a E(0) t 0 P (t ) 2 dt (4.19) t E(0) = E(t)+2a P (t ) 2 dt (4.20) 0 t A(t )dt t 0 0 [ ] 1 A(t )dt = t 2 A(0) + A( t)+a(2 t)+ + A((n 1) t)+1 2 A(n t) ( t) 2 (4.21)

26 23 5 [ ( ) 12 ( ) ] 6 σ σ φ LJ (r ij )=4ɛ r ij r ij (5.1) r ij = r i r j i j H = m 2 ṙ2 1 + m 2 ṙ2 2 + φ(r 12 ) (5.2) m r 1 = φ(r 12) r 1 = φ(r 12) r 12 r 12 r 1 = φ(r 12) r 12 r 1 r 2 r 12 (5.3) m r 2 = φ(r 12) r 2 = φ(r 12) r 12 r 12 r 2 = φ(r 12) r 12 r 2 r 1 r 12 (5.4) m =39.9m u = kg ɛ = 120kK = J σ =3.4A = m m u m, ɛ, σ MKSA σ m ɛ

27 5 24 ɛ, σ 1 A g/mol MPa, GPa 5.1 Verlet 2σ 5.2 τ = mσ 2 ɛ s τ 0.02 ps 1000 m(v 1 + v 2 ) 0 t t

28

29 26 6 r c t fcc r c g(r) 0 r 1 r 2 1(r r 2 ) t r c

30 6 27 r c 0 φ sh (r) =φ(r) φ(r c ) (6.1) r c n c E = E c φ(r c)nn c +2πNρ r c φ(r)r 2 dr (6.2) fcc 3. T eq 1 2 m iv 2 i = 3N 2 kt eq (6.3) i

31 6 28 i 1 2 m iv 2 i = 3N 2 kt (6.4) T T v i = sv i (6.5) s s 3N 2 kt = i 1 2 m iv i 2 = s 2 i 1 2 m iv 2 i = s2 3N 2 kt (6.6) s = 3N kt 2 1 i m 2 iv 2 i (6.7) T T MD

32 6 29 A 0 A i A 0 (A i A 0 ) 2 A i = A 0 + A i A 0 = A M M (A i A 0 ) (6.8) i=1 (δa i ) 2 = (A i A i ) 2 = ( A i A 0 ( A i A 0 ) ) 2 = (A i A 0 ) 2 ( A i A 0 ) 2 = 1 M (A i A 0 ) 2 ( A i A 0 ) 2 M i=1 (6.9) M

33 6 30 / 6.1 Verlet 1) 5.4 FORTRAN

34 6 31 N = 256 ( ) fcc L x,l y,l z 2) 3) 4) K(v) = i 1 2 m iv 2 i (6.10) U(r) = i<j φ(r ij ) (6.11) E = K(v)+U(r) (6.12) P = 1 3V [ m i v 2 i i i<j ] dφ(r ij ) r ij dr ij (6.13) T = 2 K (6.14) 3Nk

35 6 32 k C V = 2 3N (δk)2 K 2 (6.15) 5) g(r) g(r) MD x L x alx alxh (3,N) x r c rcut2 do 2000 i=1,n-1 do 1000 j=i+1,n xx=x(1,i)-x(1,j) if(xx.gt.alxh) xx=xx-alx if(xx.lt.-alxh) xx=xx+alh Y Z rr=xx*xx+yy*yy+zz*zz if(rr.gt.rcut2) go to 1000 r=dsqrt(rr) g(r) 1000 continue 2000 continue g(r) DO DO

36 6 33 6) r i (0) δ(t) = 1 r i (t) r i (0) 2 (6.16) N i 6Dt x, y, z r i (0) r i (t) r i (0) if(x(1,i).gt.alx) then x(1,i)=x(1,i)-alx x0(1,i)=x0(1,i)-alx endif if(x(1,i).lt.0.0d0) then x(1,i)=x(1,i)+alx x0(1,i)=x0(1,i)+alx endif N = 108 1) fcc ( 84K ɛ/k 0.7 t 0.02ps 0.01 ) 100 t

37 6 34 2) 3) N = M m M/m M A M m A m A M = A m (6.17) (δa M ) 2 = m M (δa m) 2 (6.18) M m A M ± M (δa m) 2 (6.19) 1 A M ± M (δa)2 (6.20)

38 6 35 A M ± (δa) 2 (6.21) (6.20) D δ(t) δ(t) 6D δ(t) lim t 6t N 1 N(N 1) 2 N r c r c N 100 N 2 N r c r t r t ntable(j,i) i j ntable(j,i) i nnum(i) r t rtab2

39 6 36 do 2000 i=1,n-1 nn=0 do 1000 j=i+1,n xx=x(1,i)-x(1,j) if(xx.gt.alxh) xx=xx-alx if(xx.lt.-alxh) xx=xx+alx y z rr=xx*xx+yy*yy+zz*zz if(rr.gt.rtab2) go to 1000 nn=nn+1 ntable(nn,i)=j 1000 continue nnum(i)=nn 2000 continue do 4000 i=1,n-1 nmax=nnum(i) if(nmax.eq.0) go to 4000 do 3000 nn=1,nmax j=ntable(nn,i) xx=x(1,i)-x(1,j) if(xx.gt.alxh) xx=xx-alx if(xx.lt.-alxh) xx=xx+alx y z rr=xx*xx+yy*yy+zz*zz if(rr.gt.rcut2) go to continue 4000 continue

40 6 37 ntable(j,i) j r t j>i i ntable(i) i-1 npoint(i) nn=0 do 2000 i=1,n-1 npoint(i)=nn do 1000 j=i+1,n rr=xx*xx+yy*yy+zz*zz if(rr.gt.rtab2) go to 1000 nn=nn+1 ntab1(nn)=j 1000 continue 2000 continue npoint(n)=nn do 4000 i=1,n-1 nstart=npoint(i)+1 nend=npoint(i+1) if(nened-nstart.lt.0) go to 4000 do 3000 nn=nstart,nend j=ntab1(nn) 3000 continue 4000 continue

41 6 38 npoint(i) i-1 i ntab1(i) i=npoint(i)+1 npoint(i+1) x, y, z m m N = 256 N = 108 N = 108, N= 256 CPU CPU CPU (

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