Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://cryst.geol.msu.ru/literature/kurs/2012_03_protasov.pdf Äàòà èçìåíåíèÿ: Fri Apr 6 09:25:59 2012 Äàòà èíäåêñèðîâàíèÿ: Mon Oct 1 22:02:28 2012 Êîäèðîâêà:

..




Perovskite - type complex oxides structure modeling using partially covalent approximation
: , .. : , .. : . .

2011



1. 1.1 1.1.1 1.1.2 1.1.3 - 1.1.4 GULP 2 3 3 3 5 7 8

2. 2.1 2.2 2.3 2.4

10 10 12 19 24

3. , - 3.1 3.2 31 31 37
3

3.3 ABO (A=Ca; B=Zr, Ti, Sn) 42



45 46

1



, . . , . ABO3. . , . , .. , . . .. . «-»[5].

2


1. 1.1.
, , . , . , . , . . . , , . , . , . .

1.1.1.


. " ". : U (-U ­ , ), E 3


, (-E - , ), L (-L - , ) . . . (, , 1999). "-" , , , . . . ( ), , , . -. NaCl. Na+ Cl- U. : Na Cl, , I Na, , F Cl. Na S, D. , NaCl Hf. ( ) , . (, 1975). , :

U
,
m

H
H
f

f m

H

k

I
l

F,

(1-1)

-

H



-

, I - , F - , m = k+l - () , k - , l - (, , 1999). I , . , . . 4


, , , F. . - , , , . :

E

H

f m

H



,

(1-2)

(1-1) (1-2) , U E :

U

E
k

I
l

F,

(1-3)

(, , 2004).

1.1.2.
(, , 2004), . . , . . , . Mz+Xz2- z2*e2/R2 z2*e2/R, z ­ , ­ , R ­ . , , ­ . . . (, 1975). 5


, , , , . ( ) . (b/Rn)
exp( R / ) , b

-

( ) (, , 1999). , . , , " " . ( -- ). , R-6 (, , 2004). ( ) :
6 ) cij / Rij ,

Vij ( Rij )
Z = z*e,

Z i Z j / Rij

ij

exp( Rij /

ij

(1-4)



, -- . , . . ( ). - , -, . - c (, .) (, , 1999).

. 6


, . 1/2Kr2, K ­ . , , . .

1.1.3 - , - -
, , zi f*zi, f 0 ( ) 1 ( ) . - :

Vij ( Rij , f )


f 2 Z i Z j / Rij


ij

exp( Rij /

ij

6 ) cij / Rij .

(1-5)







, , 0 (, , 1989). , . , (1-5) (1-4) . . :
0 ( Rij

VM

Dij {1 exp[

ij

Rij )]}2

Dij .

(1-6)

7


0 Rij (1-6)

i j, Dij ­ i-j,
ij

- ,
ij

- .

1

2

ij

. Dij

ij



, (f=1) Vij V - . , - . , (, , 1999). V(R, f) = (1 ­ f 2)V(R), V
-

(1-7) (1-8)

(R, f) = f 2V-(R).

, :
Vij ( Rij , f )
2

f 2 Z i Z j / Rij
ij

ij 0 ij

e xp( Rij /

ij ij

)
0 ( Rij 6 Rij )]} cij / Rij .

(1 f ) Dij {e xp[2

(R

Rij ) 2 e xp[

(1-9)

1.1.4 GULP
, . , WMIN, EMIN, METAPOCS, PLUTO, CASCADE, GULP . . . : , , ( 15 -20 å). , . -. GULP (Gale, Rohl, 2003). . : 8


1)





­, (conjugate gradients) (rfo). 2) . 3) . 4) P-T . 5) -. 6) : , , , , . , - . 7) : , . 8) -. 9) (electronegativity equilization model); 10) . , , , , . GULP ( .., 2012). ,

9


2. 2.1
ABX3. , A , B, X. . 2-1 , A 12- , B 6- . X B A. Pm-3m. SrTiO3. P B, , . : BO6-, , (. 2-2).

. 2-1. . 2-2. , . A. . X , X, ¼ 10


. B ¼ , (. 2-3.). , X F ( ), 4 12 (. 2-4).

. 2-3. . 2-4. ( ­ ). . . , . (H, F, Cl, Br, I) (Na, K, Rb). - OH-, , 50% 50% (, MgSn(OH)6). , 6-. ­ (0+6), (1+5), (2+4), (3+3), , (V0+Re6+), (K++Nb5+), (Sr2++Ti4+) (La3++Fe3+). Li+ Eu
2+



BAX3, SrLiF3 EuLiH3. , , XBA3. ,

11


Na3OCl Cl- 12- Na+, O2- Na+ (Mitchell, 2002).

2.2



, , Pm-3m. (RX+RB).

(. 2-4). , , : (RX+RA)=

, RA , . :

.

=1, . 0.8 1.11. 0.8 ,

1.11 . , p-T . , Pm-3m,

, : 0.9 .
2+

1.05.

, CaTiO
3



(Pnma) Ca2+ 12- 8-. ("") Ti6 , 12


. , . (. 2-5). : 0.81 1.11, (Mitchell, 2002). , 6 - . , , (Lufazo, Woodard, 2001). , , (Glazer, 1972). ( . .,1976). , . , . : , a, b c . , . , , "+", , "-". "0" , . . 2-5 , a0a0c+ a0a0c-, z . , . . , ("+"), ("-") .

13


()

()

. 2-5. z. () ­ , () ­ .

.

2-6.



.

a0b0c0. 26 , 15- . (Howard, Stokes, 1998) - , . 8 26-, , , , , . 15 , (. 2-7).

14


. 2-7. , . (Howard, Stokes, 1998).

. 2-8. Pm-3m, I4/mcm

. 2-9. Pnma

Pm-3m, .

Cmcm .

, , , . , a0a0c- , I4/mcm. . 2-8. a b , a=b= ap, , 15


, c=2ap. , Z=4. . , a0b-c+ ( Cmcm) , (. 2-8). a+b-c- ( Pnma) a b (. 2-9). p-T , , . . , CaTiO3 , Pbnm a-a-+. 1512±13 I4/mcm ( ­ a0a0-), 1635±2 K ­ Pm-3m (Yashima, Ali, 2009). . , , . , RbNiF3 P63/mmc, 2 898 ( Mitchell, 2002). 15- , 5% . a+b-c-, Pnma (Lufazo, Woodward, 2001). .2-6. 6- . , AX12 (. 2-10). (. 2-10, ). a0b0c- , (. 2-10, ). , . a0a0c+ , , 16


, (. 2-10, ). . a0b-b- . , . , ­ . , , .

. 2-10. . , ­ , ­ . a-a-a
-



. . , 17


, (. 2-10, ). a+a-a- , GdFeO3. , . ( Pnma x z), , . . . 2-6, a+a-a-, a-a-a- a0a0a0 ( a+a+a
+

AA3M4O12, ). , , (Woodward, 1997) . , , . POTATO (Woodward, 1997). GULP (Gale, Rohl, 2003). . , . New5 (Miller, 1990). , , YAIO3, 6 - . -, Y ( Ca2+ Ba2+) AlO6, . , a+a-a- a-a-a-. a+a-a- , . a-a 18
-


a- . a+a-a

-

- . < 0.975 a-a-a
-

, =.

0.975 < <1.02 . , - . a0a0a
0

,

. , . (Woodward, 1997). ,

2.3
ABO3 , (BaTiO3), (S r R u O 3), (LaFeO3), (Y B a 2Cu3O7), (LaCoO3), -, , , (LaAlO3: Nd), ( L a 2C u O 4). B, B-O-B 180. B . B
3+ 3+

.

(A2BB O 6) , . B , B3+ , , , B-O-B-O-B. B-B , (0.4 ). LnFeO3 ( Ln - ) 19


. , - , . , a c . 0.03-0.07µB/ , . LnMnO3 . , Mn
3+

M n 4 +, .
4+

25 35% Mn

Mn .
3+

3+

M n 4 +,









Mn3 +, Mn 4 +, Mn M n 4 +. Co3+ Co4 +, Cr Fe (Pena, Fierro, 2001). , . . , , . , , . , . , , . , L a N i O 3, Ni
III

,

LaTiO3 d-, . LnCrO3 ( L n - ) LaCrO3 . . , 0.27 Dy 0.37 Yb, 0.23 . Cr4 +, p-. 20


Cr-O Ln-O. L a M n O 3 720 . , , . LaCoO3 . 400 , 823 K; 823 1200 K , , , , 1200 .
III



Co











Co

,
3+

Co3 +. Co Co
2+

Co

III



Co . Co

IV

3+

1200 ,

, . , , . . , SrxLa 1 -xM n O 3 x = 0 Mn 3 +. , x Mn
4+

. 0.2

B . . , . 0.5 -5 -1, 0.1 -1. 3, d-. SrTiO3, d- (Ti4 +), , , 500 , (35 K) (7000 -1). TiO6 . TiO6 , - . () . d-. d3. MTiO3 ( M = Ca , Sr , Ba ) A B O 3 ( A = La , Gd, Y; B = Al, Ga) Cr3 +. Cr3 + , , - , . . , SrTiO3 . , - Cr3 ++Ti 4 + Cr4 ++Ti 3 +, (Pena, Fierro, 2001). . 90- . , . . 22


, . , . , NO . , , NO. , . . , , , , . . . , , , . , , . , -. , . (Pena, Fierro, 2001).

23


2.4



, . , . , , . 2-1. CaTiO3, 1839 (1798--1873). , . .. . . . , , . , 1957 . CaTiO3. Pbnm (Buttner, Maslen, 1992), . , . Pbnm GdFeO3. , , . , 1894 . ­ . , - . . , ­ Na0,5REE0,5TiO3 ­ . , Na0,5Ce0,5TiO3 Pbnm ( GdFeO3). Na+ + Ce3+ Sr2+ + La2+,
2xNax

Sr1

-

LaxTiO3. Ce3+ Sr2+ La2+ 24 (




I4/mcm). , Ce- , (Mitchell, Chakhmouradian, 1999 ( )
).

NaNbO3 1959 . . Pbma, , [010]. NbO6 9.50 80 [100] [010]. Na-, 8 9. . , NaNbO3 Pbnm. , (Muhll et. al., 1984), Pbma Pbnm. SrTiO3 , . , 1984 . . , , Na . , (~ 85% SrTiO3). (2.5-5% SiO2). , , SrTiO3 (a=3.905 ). , Pm-3m (Mitchell et al., 2000). . , 1971 . (~0.2 ) , 1971 . ( 50 ) . , , PbTiO3 P4mm (Glazer, Mabud, 1978). Bi Fe . 25


1963 Nb- (Ca,Na)(Nb,Ti,Fe)O3, . , , . GdFeO3, CaTiO3, .. Ti
4+

Nb5+ Fe3+

. , , , CaTiO3Ca2Nb2O7-Ca2NbFeO6-NaNbO3 (Mitchell et al., 1998). (Na,La,Ce)(Nb,Ti)O3 . , , , . o La>Ce, , La 3









x(CaZrO3)=0.93,



x(CaZrO3)=0.22, x(CaSnO3)=0.20. , Sc3+, Cr3+, Fe3+, Ce3+, La3+, Hf4+, Nb5+, U4+, Th4+. , 26


. (800-1000), , , , . CaZrO3 ZrO2-CaCl2-Na2CO3 700. CaZrO3 1100. , CaTiO3. , CaO CO2 . , ZrO2 CaO . CaTiO3 Cl, F, S CaZrO3. Zr. . SiO
2



. , U Th 2.5­2.8 Ma - . , , ­ . Ca2(Al, Fe3+)2O5 , , , , , . Pcmn (Redhammer et al., 2004). [101] . BO4­, , BO6­ . ( , ) ( ). , 27 ,
















.

, . Ca2Fe2O5 , . ( , ). . Mg Mn, , . , ( . 4-1) Ca2Fe2O5, Pnma. , (Berggren, 1971). , , , 400 660 . , ( ), . , , . , 400 (Mg, Fe)SiO4 -(Mg0.9Fe0.1)SiO4. (Mg, Fe)SiO3 (Mg,Fe)O 660 . - , - . 580 , (Mg,Fe,Al)(Si,Al)O3 CaTiO3. , (Wang et. al., 1996; Horiuchi et al., 1987).

28


. 2-1. , , . CaTiO
3

. Pnma Pbnm,I 4/mcm P m3m P c2(1)b
3 3

a 5.388 5.4652 3.9052 5.4940 3.9090 5.4479 3.9050 5.4027 5.4253

b 5.447 5.4652 3.9052 15.4610 3.9090 5.5259 3.9050 14.6779 14.7687

c 7.654 7.7476 3.9052 5.5510 3.9090 7.7579 4.1560 5.5923 5.5980

Z 4 4 1 8 1 4 1 4 4 4 1 4 4 4 2

C (Buttner, Maslen, 1992) (Mitchell, Chakhmouradian, 1999) (Mitchell et al, 2000) (Muhll et al., 1984) (Krivovichev, Chakhmoundian, 2000) (Mitchell et al., 1998) (Glazer, Mabud, 1978) (Redhammer et al., 2004) (Berggren, 1971) (Galuskin et al., 2008) (Wang et. al., 1996) (Horiuchi et al., 1987) (Zhao et al., 1994) (Wyckoff , 1963) (Yang et al., 1993);

(Na, REE, Ca)Ti2O6,(Na,La,Th)Ti O3 SrTiO
3

NaNbO3 (Na, REE) (Nb, Ti)O

P m3m P bnm P 4mm

(Ca,Na) (Nb, Fe, Ti)O PbTiO
3 5

Ca2(Al,Fe3+)2O Ca2Fe2O5 CaZrO3 CaSiO
3 3

P nma P nma Pbnm Pm¯3m Pbnm P bnm P a3 P 2(1)/n

5.556(1) 5.715(1) 7.960(1) 3.599 4.7787 5.3603 8.1100 5.4139 3.599 4.9313 5.4884 8.1100 5.6012 3.599 6.9083 7.6660 8.1100 7.7769

MgSiO

NaMgF3 K2NaAlF6 Na2NaAlF6




Na2LiAlF6 CuPb2Cl2(OH)4 Ga(OH)3 In(OH)3 In(OH)3(H2O)0 MgSn(OH)6 CaSn(OH)6 (Cu,Zn,Fe)Sn(OH) FeSn(OH)6 ZnSn(OH)6 MnSn(OH)6 FeGe(OH)6 NaSb(OH)6 (Fe,Mn)Sn(OH)6
6 .25

P 2(1)/n P 4mm P mn2(1) I m3 I mmm P n3 P n3 P 4(2)/nnm P n3m P n3m P n3 P 4(2)/n P 4(2)/n P n3

5.2842 5.8700 7.4865 7.7943 7.5440 7.7449 8.1221 7.5860 7.6900 7.8000 7.8744 7.5940 8.0100 7.7570

5.3698 5.8700 7.4379 7.7943 7.5600 7.7449 8.1221 7.5860 7.6900 7.8000 7.8744 7.5940 8.0100 7.7570

7.5063 5.4940 7.4963 7.7943 7.5580 7.7449 8.1221 8.1030 7.6900 7.8000 7.8744 7.4880 7.8800 7.7570

2 1 8 8 8 4 4 4 4 4 4 4 4 4

(Ross, Mitchell, 2003) (Rouse, 1971) (Scott, 1971) (Mullica et al., 1979); (Brich, 1993); (Basciano et al., 1998); (Basciano et al., 1998); (Morgenstern-Badarau I.J, 1976); (Moore, Smith, 1967); (Cohen-Addad, 1967); (Basciano et al., 1998) (Ross et al., 1988); (Schrewelius, 1938) (Morgenstern-Badarau, Michel, 1976);

30


3. ,

-

3.1.
(Galuskin et al., 2008). CaZrO3-CaTiO3-CaSnO3 x(CaZrO3) = 0.93, x(CaTiO3) = 0.22 x(CaTiO3) = 0.20. , Sc, Cr, Fe, Ce, La, Hf, Nb, U, and Th. CaZrO3 , , . CaSnO
3













. . CaZr1-xTixO3 (Krayzman et al., 2006; Levin et al., 2006), CaZr1-xSnxO3 CaSn1-xTixO3 . , CaZrO3, CaTiO3, CaSnO3 - . , - CaTiO3, CaSnO3 CaZrO3 ­ Pnma. CaTiO3 ( = 0.97), CaSnO ). , CaTiO3, CaZrO3 (Bassoli et. al., 2008; Mather, Islam, Figuriendo, 2007; Davies, Islam, Gale, 1999; Davies et. al., 2000) . .
3

( =0.93) CaZrO3 ( =0.92) (Woodward, 1997). Ti4+, Sn4+ Zr4+ (0.61, 0.69 0.72 å,


, CaTiO3 (Bassoli et. al., 2008) . (Corgne, Allan, Wood, 2003; Alfreddson et. al, 2005) MgSiO
3

CaSiO

3



O-Si-O. (Corgne, Allan, Wood, 2003) , (Alfreddson et. al, 2005), MgSiO3 . (Hu, Xie, Ma, 2010) BaTiO3 PbTiO3, , . , . . , BaTiO3 (. 3-1). (Khan, Islam, Bates, 1998; De Souza et. al, 1999; Islam, 2000; Islam, Davies, 2004; Jones, Islam, 2008) La- LaCoO3, LaFeO3, LaGaO3, LaMnO3, LaScO3, LaYO3. (. 3-1).

32


. 3-1. a, b, , K < s> < > , , . BaCeO3 BaCeO3 BaPrO3 BaThO3 BaTiO3 BaTiO3 BaZrO3 BiFeO3 CaSiO CaSiO
3 3

(Wu et.al., 2004) (Kruth et al., 2007) (Stokes, Islam, 2010) (Stokes, 2010) (Hu, Xie, Ma, 2010) (Hu, Xie, Ma, 2010) (Stokes, Islam, 2010) (Stokes, 2010) (Corgne, Allan, Wood, 2003) (Watson, Wall, Parker, 2000) (Bassoli et. al., 2008) (Mather, Islam, Figuriendo, 2007) (Davies, Islam, Gale, 1999) (Davies et. al., 2000) (Islam, 2000) (Jones, Islam, 2008)



a, å 4.427 6.2422 6.213 6.213 4.012 4.001 4.188 5.564 3.599 3.662 5.411 5.3796 4.011 5.608 3.82 5.6 3.991 4.199 5.588 3.572 3.566 5.3812 5.3907 4.02 5.591 3.823 5.565 4.44467 6.2347 6.181 6.181

b, å

c, å

U, 136.68

K

< s>

< >

6.2304 6.2153 8.8179 8.7763 6.221 6.221 4.005 4.035 5.564 5.588 4.035 6.214 6.214 8.789 8.789 8.722 8.722 215 134 191 144

13.904 13.867 289.5 281 171 77.7 5.12

CaTiO3 CaTiO3 CaZrO3 CaZrO3 LaCoO3 LaFeO3

5.439

5.4405

7.689

7.6436

149.4

197.89

5.4446 5.4423 7.6401 7.6802 146.41 7.985 7.862 8.017 7.855 5.665 5.557 5.762 5.556 146.64 55.18 16.39 2.55 2.54

33


LaGaO3 LaGaO3 LaMnO3 LaMnO3 LaMnO3 LaScO3 LaYO3 MgSiO MgSiO
3 3

(Islam, 2000) (Khan, Islam, Bates, 1998) (Souza et. al, 1999) (Souza et. al, 1999) (Souza et. al, 1999) (Islam, 2000) (Islam, 2000) (Corgne, Allan, Wood, 2003) (Alfreddson et. al, 2005) (Tealdi et.al, 2006) (Tealdi et.al, 2006) (Hu, Xie, Ma, 2010) (Hu, Xie, Ma, 2010) (Mather, Islam, 2005) (Beale et al., 2009) (Islam, 2000)



3.875 5.485 3.904 5.541 5.528 3.82 6.052 4.8244 4.784 3.770 5.3501 3.985 3.861 6.0744 5.533 4.095

3.875 5.527 3.904 5.522 5.582 3.823 6.086 4.7787 4.775 3.770 5.3312 3.97 3.904 6.1312 5.453 4.101 4.156 4.152 8.5421 8.6504 5.9834 5.9944 139.82 13.496 13.137 144.31 15.71 2.65 7.5473 7.5482 5.3347 5.3461 5.936 4.903 5.89 4.932 8.512 6.901 8.511 6.899 301 281.97 4.8454 4.9313 6.8416 6.9083 5.553 5.583 7.818 7.89 5.481 5.496 7.752 7.781 143.25 139.69 13.511 13.332 139.84 139.87 16.79 52.71 33.54 18.69 25 2.02 2.16 2.18 2.19

NdCoO3 NdCoO3 PbTiO PbTiO SrTiO
3 3

SrCeO3
3

SrZrO3

34


(Mather et al., 2007) , (. 3-2). CaTiO3, TiO2, CaO. , VO O1 O2 . , , , CaTiO3 . Va VO , , . , , ( >3.6 ), . Fe4+. VO, , , . O1 O2, , O2. , (Pnma) (0k0) O2. (Calleja et al., 2003) VO [001]90o. T=10 K 2.3 , , Ti (001). ( ) ­ 1.2 . (Davies et al., 2000) CaZrO3 SrZrO3. CaTiO3 (Mather, Islam, Figuriendo, 2007), o . CaZrO3, SrZrO3 - . AO . , SrZrO3 ZrO2 SrO2, , 35


SrTiO3. , , A . .. ( , .) , 3-1 3-2.

36


3.2
. 3-3() , , CaTiO3, CaSnO3 and CaZrO3. , . 3-3() , .. ( a, b, c V) CaTiO3, CaSnO3 CaZrO3 . (Buttner, Maslen, 1992; Koopmans et al., 1983; Vegas et al., 1986) 0.2% (. 3-4, ,,). K (Ross et al., 2002), 5%, .. 19%. ST GULP 300 ­ 1500 K. 0.2% 300 K (. 3-4, ,,). , (Yashima, Ali, 2009) , 1512±13 K Pnma CaTiO3 I4/mcm, 1635±2 K - Pm3m.

37


. 3-3 (). CaZrO3, CaTiO3 CaSnO3, . Ca2+-O1 Ti O
3.2+ .73(3).73(3)73(3)-

, 1340.18 770.02 790.2 766.2 22764.0

,å 0.321 0.3698 0.38096 0.364078 0.1490

C, ·å 0.0 0.0 0.0 0.0 43.0

6

Zr3.2+-O1

-O1.

Sn3.2+-O1
1.73(3)-

.73(3).73(3)-

-O1

. 3-3 (). CaZrO3, CaTiO3 CaSnO3, .. . Ca2+-O2 Zr4+-O2 Ti4+-O2 O -O
2-

, 1340.18 1150.869 840.2 1285.2 22764.0

,å 0.321 0.3750 0.3810 0.3611 0.1490

C, ·å 0.0 0.0 0.0 0.0 43.0

6

-

Sn4+-O2
2-

38


. 3-4 (). V a, b, c, K, E S
300

CaTiO3,

. CaTiO3 V, å3 a, å b, å c, å K, E, / S300 , /·K (Buttner, Maslen, 1992; Ross et al., 2002) 223.682 5.388 5.447 7.654 171(1) 93.64 ( .., 2012) 224.754 5.385 5.440 7.672 215 -14586.22 94.34 (Mather et al., 2007) 226.3 5.411 5.439 7.689 222.037 5.384439 5.403729 7.631177 170.122 -10672.40 93.49

39


. 3-4 (). V a, b, c, K, E S
300

CaSnO3,

. (Vegas et al., 1986; Ross et al., 2002) 248.4642 5.5320 5.6810 7.9060 163(1) ( .., 2012) 248.6584 5.5398 5.6406 7.9575 198 -14240.69 95.02

CaSnO3 V, å3 a, å b, å c, å K, E, / S
300

248.383967 5.544557 5.636276 7.948121 157.70204 -10384.40 98.89

,

/·K

40


. 3-4 (). V a, b, c, K, E S
300

CaZrO3,

. CaZrO3 V, å3 a, å b, å c, å K, E, / S
300

( .., 2012) 258.269 5.6011 5.7085 8.0775 184 -13981.11 96.3

(Davies et al., 2000) 253.678 5.608 5.665 7.985 258.242 5.411296 5.441571 7.677132 149.2348 -10217.65 97.81

(Koopmans et al., 1983; Ross et al., 2002) 258.265 5.5912 5.7616 8.0171 154(1) 96.4

,

/·K

: , , ( a, b V ) CaTiO3, CaSnO
3

CaZrO3.

K

. .., K . . . , CaTiO3 (Mather et al., 2007; Bassoli et al., 2008; .., 2012) CaZrO3 (Davies et al., 2000; .., 2012). V CaTiO3 and CaZrO3 , (Davies et al., 2000; Bassoli et al., 2008; .., 2012). , . 41


3.3 ABO3 (A=Ca; B=Zr, Ti, Sn)
( ) - , . 3-3. (. 3-5, ). , , TiO2, SnO2 (, 2008) ZrO2 (Khan et al., 1998) - , ­ CaO (Lide, 1994). . 3-5 , , , . , , Ca-O . CaZrO3 (Davies et al., 1999). 3-5 (). (, ), . Ca B O1 O2 Ca B O
' VA' ' VB' ''

CaSnO3 21.94 56.51 15.02 15.10 -12.18 -40.01
'' i

CaTiO 21.42 58.27 14.25 14.32 -9.88

3

CaZrO3 21.96 55.21 14.88 14.83 -11.30 -42.51 -7.43

VO1 VO2

Ca

i

B

i

-43.05 -6.87

O

-7.71

42


. 3-5 (). (, ), . A B O CaSnO3 CaTiO3 CaZrO3 (Davies et al., 1999) 4.21

Ca
B

A

' VA'

Ca
B

i

4.88

5.77

5.33

B

' VB'''

i

8.25
'' i

7.61

6.35

9.10

O Ca

O

VO B
B

O 3O
O

3.65

3.69

3.725

2.63

A

2V

'' A

V

'''' B

3VO

CaBO

3.19
3

2.38

3.11

2.22

, , . . CaZr1
xTixO3 -

, CaZr1-xSnxO3 and CaSn1-xTixO3 . 3-2

. , .

43


. 3-2. , .
CaTiO3 CaZrO SrZrO LaFeO
3

X 9 .1 0 1 1 .3 8 8 .5 7 8 .7 9 9 .1 9 1 1 .1 7 9 .5 4 1 1 .8 1 1 8 .2 7 .6 1 1 3 .0 2 1 1 .3 1 1 2 .3 5 7 .6 1 8 .2 5 6 .3 5

O 2 .6 3 4 .7 6 4 .2 5 4 .0 2 4 3 .5 4 .5 3 4 .4 8 1 0 .1 4 .3 0 4 .3 4 4 .3 1 4 .1 5 3 .6 9 3 .6 5 3.725

2 .4 9 2 .2 2 3 .5 1 3 .6 3 .4 8 3 .7 3 2 .9 4 3 .7 4 4 .5 7 4 .2 6 3 .5 5 4 .5 3 4 .0 2 2 .3 8 3 .1 9 3 .1 1

A-O 2 .9 2 1 .2 6 2 .6 8 3 .0 3 3 .2 3 .5 3 .9 3 .7 0 3 .4 2 4 .1 1 3 .5 0 -

B-O 3 .0 3 3 .0 9 4 .4 5 3 .7 3 .7 2 3 .9 4 5 .4 5 3 .2 1 3 .9 8 5 .1 7 4 .5 2 -

(Mather et al., 2007) (Davies et. al., 2000) (Davies et. al., 2000) (Jones, Islam, 2008) (Souza et. al, 1999) (Souza et. al, 1999) (Tealdi et.al, 2006) (Tealdi et.al, 2006) (Mather, Islam, 2005) (Thomas et al., 2005) (Beale et. al., 2009) (Kuklja, 2000) ( .., 2012) ( .., 2012) ( .., 2012)

' VA'

' VX'

''

VO1
1 9 .6 4 1 9 .9 9 1 1 .4 1 8 .8 9 2 0 .9 0 2 0 .2 6 2 0 .9 4 2 0 .0 7 1 4 .2 5 1 5 .0 2 14.88

VO2
1 9 .6 3 1 9 .9 8 2 0 .3 9 2 0 .9 8 2 0 .4 7 1 4 .3 2 1 5 .1 0 14.83

A
-

i

X
-

i

O
-

'' i

A 4 .2 1 6 .0 0 9 .7 9 1 0 .0 8 9 .2 5 1 1 .1 9 1 1 .2 9 5 .3 6 1 6 .5 7 .3 5 4 .9 8 4 .8 4 4 .0 4 5 .7 7 4 .8 8 5.33

2 2 .1 5 2 1 .2 3 1 8 .3 2 0 .9 2 4 8 .7 0 2 2 .6 0 2 3 .3 1 2 2 .9 4 2 1 .4 2 2 1 .9 4 21.96

8 2 .2 7 8 1 .5 8 4 1 .7 8 1 .1 6 5 2 .0 9 8 5 .5 6 8 4 .1 4 8 1 .8 2 5 8 .2 7 5 6 .5 1 55.21

3 3 3 3

LaMnO LaMnO NdCoO NdCoO SrCeO SrTiO SrTiO YAlO

3 3

3

-10.52 -1.8 -33.48 -

-57.95 -23.5 -37.40 -

-11.02 -1.3 -12.31 -

3 3

3 3 3

CaTiO

CaSnO CaZrO CaTiO

3 3 3

CaSnO CaZrO

3

44



- , - , . GULP. , , . - ABO3 (A=Ca; B=Zr, Ti, Sn). - . - .

45



1. . . // , . 21, 1976. . 249-255. 2. E.. , : - // , . . 2012. 23 . 3. E.. , , : // , . . 2008. 73 . 4. . . . .: . 1999. 394 .

. . . . ­ . . 228-266. 5. «-» (http://parallel.ru/cluster).

6. .. . .: . 1975. 335 . 7. . ., . . - . .: - . 1989. 8. . ., . . ( ). .: - . 1. 2004. 9. . ., . . . 37-44. 10. Alfredsson M., Cora F., Brodholt J. P., Parker S. C., Price G. D. Crystal morphology and surface structures of orthorhombic MgSiO3 in the presence of divalent impurity ions // Phys. Chem. Miner. 2005. V. 32. P. 379­387. 11. Basciano J.C., Peterson P.C., Roeder P.L. // Canad. Mineral. 1998. V. 36. P. 1203-1210. . . 2004. C. 4. . N. 5.

46


12. Bassoli M., Buscaglia M.T., Bottino C., Buscaglia V., Molinari M., Maglia F., Parravicini G., Dapiaggi M. Defect chemistry and dielectric properties of Yb3+: CaTiO3 perovskite // J. App. Phys. 2008. V. 103. 014104. P. 1-10. 13. Beale A. M., Paul M., Sankar G., Oldman R. J., Catlow C. R. A. French S., Fowles M. Combined experimental and computational modelling studies of the solubility of nickel in strontium titanate // J. Mater. Chem. 2009. V. 19. P. 4391­4400. 14. Berggren J. // Acta Chem. Scand. 1971. V. 25. P. 3616-3624. 15. Brich W.D., Pring A., Reller A., Schmalle H.W. // Amer. Mineral. 1993. V. 78. P. 827-834. 16. Buttner R.H., Maslen E.N. // Acta Cryst. C. 1992. V. 48 P. 644. 17. Cohen-Addad C. // Bull. Mineral. 1967. V. 90. P. 32-35. 18. Corgne A., Allan N. L., Wood B. J. Atomistic simulations of trace element incorporation into the large site of MgSiO3 and CaSiO3 perovskites // Phys. Earth Planet. Inter. 2003. V. 139 P. 113­127. 19. Davies R.A., Islam M.S., Gale J.D. Dopant and Proton Incorporation in Perovskite-Type Zirconates // Sol. St. Ionics. 1999. V. 126. No 4. P. 323­335. 20. Davies R.A., Islam M.S., Chadwick A.V., Rush G.E. Cation Dopant Sites in the CaZrO 2000. V. 130. No 2. P. 115­122. 21. De Souza R. A., M. Saiful Islam, Ivers-Tiffe E. Formation and migration of cation defects in the perovskite oxide LaMnO3 // J. Mater. Chem. 1999. V. 9. P. 1621­1627. 22. Gale J.D., Rohl A.L. The General Utility Lattice Program // Mol. Simul., 2003. V. 29. 5. P. 291-341. 23. Galuskin E.V., Gazeev V.M., Armbruster Th., Zadov A.E., Galuskina I.O., Pertsev N.N., Dzieranowski P., Kadiyski M., Gurbanov A.G., Wrzalik R., Winiarski A. Lakargiite CaZrO Russia // Amer. Mineral. 2008. V. 93, No 12. P. 1903­1910. 24. Glazer A. M. // Acta Cryst. A. 1972. V. 31, P. 756-762. 25. Glazer A.M., Mabud S.A. // Acta Cryst. B. 1978. V. 34. P. 1065-1070. 26. Horiuchi H., Ito E., Weidner D. Perovskite type MgSiO3: single crystal X-ray diffraction study // Am. Mineral. 1987. V. 72. P. 357­360. 27. Howard C. J., Stokes H.T. // Acta Cryst. B54, 1998, P. 782-789. 47
3 3

Proton Conductor: A Combined EXAFS and Computer Simulation Study // Sol. St. Ionics ­

- a new mineral of the perovskite group from the North Caucasus, Kabardino-Balkaria,


28. Hu X.Q., Xie G.F., Ma Y. A new optimization method for shell model interatomic potential parameters of perovskite ferroelectrics // Physica B. 2010. V. 405. P. 2577-2580. 29. Islam M. S. Ionic transport in ABO3 perovskite oxides: a computer modelling tour // J. Mater. Chem. 2000. V. 10. P. 1027-1038. 30. Islam M. S., Davies R. A. Atomistic study of dopant site-selectivity and defect association in the lanthanum gallate perovskite // J. Mater. Chem. 2004. V.14. P. 86 ­ 93. 31. Jones A., Islam M. S. Atomic-Scale Insight into LaFeO3 Perovskite: Defect Nanoclusters and Ion Migration // J. Phys. Chem. C. 2008. V. 112. P. 4455-4462 32. Khan M.S., Islam M.S., Bates D.R. Cation Doping and Oxygen Diffusion in Zirconia: A Combined Atomistic Simulation and Molecular Dynamics Study // J. Mater. Chem. 1998. V. 8. No 10. P. 2299­2307. 33. Koopmans H.J.A., van de Velde G.M.H., Gellings P.J. Powder neutron diffraction study of the perovskites CaTiO3 and CaZrO3 // Acta Crystallogr. C. 1983. V. 39. No 10. P. 1323­ 1325. 34. Krayzman V., Levin I., Woicik J.C., Yoder D., Fischer D.A. Effects of local atomic order on the pre-edge structure in the Ti K x-ray absorption spectra of perovskite CaTi Phys. Rev. B. 2006. V. 74. No 22. P. 224104­224131. 35. Krivovichev S.V., Chakhmoundian A.R. // Eur. J. Mineral. 2000. V. 12. P. 597-607. 36. Kuklja M. M. Defects in yttrium aluminium perovskite and garnet crystals: atomistic study // J. Phys.: Cond. Matt. 2000. V. 12. P. 2953­2967. 37. Levin I., Cockayne E., Lufaso M.W., Woicik J.C., Maslar J.E. Local Structures and Raman Spectra in the Ca(Zr,Ti)O3 Perovskite Solid Solutions // Chem. Mater. 2006. 18. No 3. P. 854­860. 38. Lufazo M.W., Woodward P.M. // Acta Cryst. B. 2001. V. 57, P. 725. 39. Marshall B.J., Pederson D.O., Dorris G.G. // J. Phys. Chem. Sol. 1967. V.28. 6. 40. Mather G. C., Islam M. S. Defect and Dopant Properties of the SrCeO3-Based Proton Conductor // Chem. Mater. 2005. V. 17, P. 1736-1744. 41. Mather G. C., Islam M. S., Figueiredo F. M. Atomistic Study of a CaTiO3-Based Mixed Conductor: Defects, Nanoscale Clusters, and Oxide-Ion Migration // Adv. Funct. Mater. 2007. V. 17, P. 905­912.
1-x

ZrxO3 //

48


42. Miller G., NEW5. Extended Hiickel Band Structure Calculation Program // Iowa State University, 1990. 43. Mitchell R.H. Perovskites: Modern and Ancient // Almaz Press Inc, Thunder Bay, 2002. 249 p. 44. Mitchell R.H., Choi J.B., Hawthorne F.C., McCommon C.A., Burns P.C. // Canad. Mineral. 1998. V. 36. P. 107-116. 45. Mitchell R.H., Chakhmouradian A.R. // Phys. Chem. Miner. 1999. V. 26. P. 396-405. 46. Mitchell R.H., Chakhmouradian A.R., Woodward P.M. // Phys. Chem. Miner. 2000. V. 27. P. 583-589. 47. Moore P.B., Smith J.V. // Ark. Mineral. Geol. 1967. V. 4. P. 395-399. 48. Morgenstern-Badarau I. J. // Solid State Chem. 1976. V. 17. P. 399-406. 49. Morgenstern-Badarau I., Michel A. J. // Inorg. Nuclear Chem., 1976. V. 38. P. 1400-1402. 50. Muhll R., Sadel A., Hagenmuller P. // J. Solid State Chem. 1984. V. 51, P. 176-182. 51. Pena M. A., Fierro J. L. G. Chemical Structures and Performance of Perovskite Oxides // Chem. Rev., 2001, V. 101. 52. Redhammer G. J., Tippelt G., Roth G., Amthauer G. // Amer. Mineral. 2004. V. 89. P. 405420. 53. Ross N.L., Angel R.J., Kung J., Chaplin T.D. Elastic Properties of Ca-perovskites. Mat. Res. Soc. Symp. Proc. 2002. V. 718. P. 115­119. 54. Ross K.C., Mitchell R.H. // J. Solid State Chem. 2003. V. 172. P. 95-101. 55. Rouse R.C. // Z. Kristallogr. 1971. V. 134. P. 69-80. 56. Schrewelius N. // Z. Anorg. Allgem. Chem. 1938. V. 238. P. 241-254. 57. Scott J.D. // Amer. Mineral. 1971. V. 56. P. 355. 58. Stokes S. J. Atomistic Modelling Studies of Fluorite-and Perovskite-Based Oxide Materials // PhD Thesis. 2010. University of Bath, Department of Chemistry. 59. Stokes S. J., Islam M. S. Defect chemistry and proton-dopant association in BaZrO3 and BaPrO3. J. Mater. Chem., 2010. V. 20. N. 30 P. 6258-6264. 60. Tealdi C., Malavasi L., Fisher C. A. J., M. S. Islam Disproportionation, Dopant Incorporation, and Defect Clustering in Perovskite-Structured NdCoO3 // J. Phys. Chem. B. 2006. V. 110. P. 5395-5402. 49


61. Thomas B.S., Marks N.A., Begg B.D. Developing pair potentials for simulating radiation damage in complex oxides, Nucl. Instr. Meth. Phys. Res. B. 2005. V. 228, P. 288-292. 62. Vegas A., Vallet-Reg M., Gonzales-Calbet J.M., Alario-Franco M.A. The ASnO3 (A=Ca,Sr) perovskites // Acta Crystallogr. B. 1986. V. 42, No 2. P. 167­172. 63. Wang Y., Weidner D.J., Guyot F. Thermal equation of state of CaSiO3 perovskite. // J. Geophys. Res. 1996. V. 101. P. 661­672. 64. Watson G W , Wall A., Parker S. C. Atomistic simulation of the effect of temperature and pressure on point defect formation in MgSiO3 perovskite and the stability of CaSiO3 perovskite // J. Phys.: Cond. Matt. 2000. V. 12. P. 8427­8438. 65. Woodward P.M. Octahedral Tilting in Perovskites II. Structure Stabilizing Forces // Acta Cryst. B. 1997. V. 53, P. 44-66. 66. Wu J., Davies R. A., M. S. Islam, Haile S. M. Atomistic Study of Doped BaCeO3: Dopant Site-Selectivity and Cation Nonstoichiometry // Chem. Mater., 2004. Vol. 17, No. 4, 846851. 67. Wyckoff R.W.G. // Crystal Structures. 1963. V. 3. 374 p. 68. Yang H., Ghose S., Hatch D.M. // Phys. Chem. Miner. 1993. V. 13. P. 528-544. 69. Yashima M., Ali R. Structural Phase Transition and Octahedral Tilting in the Calcium Tinanate Perovskite CaTiO3 // Sol. St. Ionics, 2009. V. 180. P. 120-126. 70. Zhao Y., Parise J.B., Wang Y., Kusava K., Vaughan M., Weidner D.J., Kikegawa T., Chen J., Shimomura O. // Amer. Mineral., 1994. V. 79. P. 615-621.

50