40- XX . , (, ) , .
50- , .
(), . , .
, , , - .
. () . .
, , ( , , ), d - , . , (, ). H2O, NH3, CO , , .
(, [CoF6]-3 [Co(NH3)6]3+). - (+n) d - , (, F- NH3). (+n), , d - (.. ).
d - . d (z 2) d(2-2), , . , , , . , . .
d - d (xy), d (xz) d (yz), , . d - , d (xy), d (xz) d (yz)- .
, d - , , , d (xy), d (xz) d (yz), , d (z 2) d(2-2). d - d ε d γ:
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d (z 2) d(2-2)
d (xy), d (xz), d (yz)
d ε d γ Δ0:
E 2 E 1 = Δ0 ≈ 0
d ε d γ (d -) :
( 2 0) > ( 0 1).
- , , .. 0.
,
4( 2 0) = 6( 0 1),
4 6 d γ- d ε-. ,
( 2 0) / ( 0 1) = 3/2
( 2 1) / ( 0 1) = 5/2,
Δ0 / ( 0 1) = 5/2, ( 0 1) = 2/5Δ0.
d ε- () 2/5 Δ0.
, d γ- () 3/5 Δ0.
d ε- d γ- , ( ).
d - 1 6 , d ε-, .
d ε- .
, . , Δ0.
, , . , d ε- d γ-, Δ0 :
λ = c / ν; Δ0 = 2 1 = h ν = h (c / λ),
h 6,6260693 ∙ 10-34 ;
= 3 1010 /.
Δ0 , : -1, 12 /. , , .
, , , . Δ0 . , [Mn(H2O)6]2+ [Fe(H2O)6]2+ 7800 10400 -1, [Mn(H2O)6]3+ [Fe(H2O)6]+3 13700 21000 -1 . - Δ0 . (III) [Co(NH3)6]3+, (III) [Rh(NH3)6]3+, (III) [Ir(NH3)6]3+ (Z = 27, 45 77) , 22900, 34100 41000 -1.
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Δ0 . , -, , , Δ0 :
I > Br > Cl > NCS- ≈ NO3- > F- > OH- >H2O > H- > NH3 > NO2- > CN- > NO > CO.
, d - CN- , NO CO. d ε- d γ- . d ε- d γ- . d ε-:
dγ
dε
d - , . ( ) , d ε- d γ-; , d γ-.
dγ
dε
Δ0 d γ- ; d ε-.
dγ
dε
4 5 , . , d ε-, . , d γ-, ( d 6, d 7 d 8):
dγ
dε
dε -, , d γ-:
dγ
dε
, . :
dγ
dε
[Co(NH3)6]3+ [CoF6]-3. , NH3 , - F- . [CoF6]-3 F- (Δ0 = 13000 c-1), 3 d 6- d ε- d γ- - . , :
[Co(NH3)6]3+ NH3 (Δ0= 22900 -1), 3 d 6- d ε-. d ε- d γ- - . , :
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[Fe(H2O)6]2+ [Fe(CN)6]-4:
H2O ; d ε- d γ- , Fe+II. , .
, CN- d -, 33000 -1. , d ε-. , , , .
C , d - (4 sp 3 d 2), ― d - (3 d 24 sp 3).
, d - , ― d - . (). , , .
. . , , [Cu(NH3)4]2+, , [Ti(H2O)6]3+ , [Co(NH3)5H2O]2+ . , : ( , ); ( ); , ( , ).
, . (, ) , d ε-, d γ-. , , (III) [Ti(H2O)6]3+, - (20300 -1, λ=500 ). d ε- d γ-:
, [Ti(H2O)6]3+, ( -). [V(H2O)6]Cl3 . . , (III) 3 d 2, d ε-:
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d γ-: d γ-, . , , .
, , 400 (III). - -. d 0 d 10, d ε- d γ- - , - . , Sc(III) (3 d 0), Cu(I) (3 d 10), Zn(II) (3 d 10), Cd(II) (4 d 10) .., . , . , , , , , . , , (II) [Cu(H2O)4]2+, , (II) [Cu(NH3)4]2+ .