..

2007




() :
1. :
. ,
2. :

3. -:
""

,

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.




, ,

(, ),
(, , , ), (-., , ,
)

(, ), ()

(, , ),



!
:
1.

2.

3.

:
1.

( )

2.

3.

4.

5.

9
X-rays
K
Cu
1s

2s

2p
3s

Cr

0.22909 nm

Fe

0.19373 nm

Cu

0.15418 nm

Mo

0.07107 nm

Ag

0.05608 nm



. , ,
, c .

:
2d sin = n

(NH4)6(NiMo9O32)6H2O:
:
:

NaCl

d()
KCl

d()

2

,

TiO2

d()

TiO2

d()

TiO2

d()



:
2dhkl sin = n
h, k, l , ,
.
: 1/d2 = h2/a2 + k2/b2 + l2/c2
( 1/d2 = h2/a2)
: 1/d2 = (4/3)([h2 + k2 + hk]/a2) + l2/c2

.
.

 ?
NaBr
: 1/d2 = h2/a2

a = 5.9723 0.0005



(Sn24P19.3)I6Br2 a = 10.9141 0.0015
N

I/I0

104/d2(obs)

104/d2(calc)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31

16.24
18.19
19.93
23.06
25.83
28.34
29.52
30.65
32.84
33.88
37.79
38.75
40.5
41.38
42.23
44.71
50.15
50.16
51.64
55.85
56.57
57.26
58.57
59.22
61.89
62.55
65.04
67.58
68.86
69.42
70.02

5.4591
4.8781
4.4543
3.8570
3.4494
3.1493
3.0260
2.9167
2.7270
2.6458
2.3803
2.3237
2.2274
2.1820
2.1401
2.0267
1.8191
1.8187
1.7699
1.6462
1.6269
1.6089
1.5760
1.5601
1.4992
1.4850
1.4339
1.3861
1.3634
1.3538
1.3436

20
5
10
20
10
15
100
90
20
20
50
20
40
20
30
10
50
30
50
20
10
20
10
10
30
10
5
5
1
1
5

335.6
420.2
504.0
672.2
840.5
1008.3
1092.1
1175.5
1344.7
1428.5
1765.0
1852.0
2015.6
2100.3
2183.4
2434.6
3021.9
3023.3
3192.3
3690.1
3778.1
3863.2
4026.1
4108.6
4449.2
4534.7
4863.6
5204.9
5379.6
5456.2
5539.4

0
0
1
0
0
2
0
1
0
0
1
2
2
0
0
0
0
2
1
2
2
1
4
0
0
1
0
1
0
0
1

0
1
1
2
1
2
2
2
0
1
2
3
2
0
1
2
0
4
1
2
4
3
4
0
2
2
3
5
0
1
1

2
2
2
2
3
2
3
3
4
4
4
3
4
5
5
5
6
4
6
6
5
6
4
7
7
7
7
6
8
8
8

335.8
419.8
503.7
671.6
839.5
1007.4
1091.4
1175.3
1343.2
1427.2
1763.0
1846.9
2014.8
2098.8
2182.7
2434.6
3022.2
3022.2
3190.1
3693.8
3777.8
3861.7
4029.6
4113.6
4449.4
4533.3
4869.1
5204.9
5372.8
5456.8
5540.7

0.3
0.5
0.3
0.6
1.0
0.9
0.7
0.2
1.5
1.4
2.0
5.1
0.8
1.6
0.7
0
0.3
1.1
2.2
3.7
0.4
1.4
3.5
4.9
0.2
1.4
5.5
0
6.8
0.6
1.3

:
1.

2.

3.



1.

2.

,
H, Li, B

3.

1.

2.

,

, ,
M = H,

.
,

3R
______ T
=
NA

()

d-:

= n(n+2) = 4 S(S+1)
n ; S

d4

s obs

- ( 4d 5d)

TC
Co 1400 K
Fe 770 K
EuO 69 K

T
c

TN
CrO2 310 K
MnO 122 K


?
1) ,
0 < E1 < E2 < E3 <
2) Ei Ej
,
E = Ei Ej = h = hc/ = hc ~ = kT
h , 6.626 1034
(1, )
, 2.997 108 /
l (, , )
~
(1)
k , 1.381 10-23 /
()
3)


(-1 )
20

15

10

()
5

10

10

-5

10

-10

10

-15

10

400
700

 (-. )

.
?

, ,


[Ti(H2O)6]3+

E = ch~maxNA (/)

- [Cr(H2O)6]3+

17400

eg
24500

E
33300

t2g
15000

20000

25000

30000

35000

~
, -1
3 ?

 ()
1.

I 0

2.

, I >

3.

( )

- , :
1.

I>0

2.

3.

(
)


I > 0 2I + 1

I= -1/2
E
I=1/2

I= +1/2
, I =
I 1 .
I, .

 -

= 106 ( ref)/ ref

ref
( ..)
ref
ref (1H) = Si(CH3)4

ref (31P) = H3PO4 (85%)

< 0,
> 0,

, 1:
< 0 HCo(CO)4

> 0 H2SO4

- 1

M = 2nI + 1

- 2

- J ()

PF61-

JPF
708

31

PF61-

 (, )

() ( )
:
F:
F = kx
k , .

:
E ~ h = (h/2) (k )1/2
( )
40 4000 1
-

3N-6
3N-5

-1

1 = 3652 cm

3 = 3756 cm-1

-1

2 = 1595 cm

, . :
1) ..
2)

1 3

3600 - 3320

2 1650 - 1600

-
c -1
4000 3500 3000 2500 2000 1500 1000 500

CaSO42H2O

H2O

SO42-


- PtCl2(NH3)2

NH 3

Cl
Pt

NH 3

Cl

Cl

NH 3
Pt

Cl
600

500

400

cm-1

300

NH 3

:
Pt-Cl

300-350 -1

Pt-NH3 500-550 -1