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1 I l + I [Ti(OH ) 6 ] + d Lambert-Beer I=I I=I exp(-cl - 4-8nm 4-49 nm nm nm nm 58-7 nm nm Ti (ground state) (exited state) e g h Ti + Ti 4+ + e- -CT) max = 5 nm / nm t g d-d
2 (R) (Y) (G) (B) (P) (YR) (GY) (BG) (PB) (RP) 55 5YBG 469
3 (Electron Configuration) F -s s p 5 Mn + - t g e g (Electronic State) (Mulliken ab AB e E t T
4 S+ SS=m si S+ X Y X=A,B,E,TY=g,g,g S + +/ S( S +) d e g e g t g t g T g E g -/ S=/ S+= S= S+= -S+S S+ - S+ A,B=, E=,T= E g x=4 T g x=6 T g x=9
5 A g T g E g A g
6 d () t g, t g e g, e g e g e g 4 e g g 4 C = 6 4 A g g E g A g g A g E g t g e g A g e g (4t g 64x6=4 =(x)+(x)+(x)=6 tt g g e g g T g g T g g T g g T g g t g 6 C = tt g g 5 6 T g g T g g E g A g g
7 d A g E g e g A g T g T g T g T g t g eg A g E g T g t g T g
8 d (Russell-Saunders) d n (L(S) S+ L J (L=l i L+ S+ J : J=L+S, L+S-, L-S J d L=l i =(i=) l i - - L= S P D F G H I L=S+= D
9 d () d () C 45 = PauliFund LL=l +l, l +l -,, l -l d L=4,,,, SS=s +s, s +s -,, s -s d S=, L=4(l =l =)S= l i G =9x=9 L=(l =l =)S= F =7x= L=(l =l =)S= D =5x=5 L=(l =l =)S= P =x=9 L=(l =l =)S= S =x= - - l i - - l i - - l i - - l i - -
10 d C = LL=5,4,,, SS=/,/ L=5(l =l =l =)S=/ H L=4(l =l =l =)S=/ G L=(l =l =l =)S=/ 4 F L=(l =l =l =)S=/ F L=(l =l =l =)S=/ D L=(l =l =l =)S=/ D L=(l =l =l =)S=/ P L=(l =l =l =-)S=/ 4 P
11 .. S.. L.. J L --S L + S d n d,d 9 d,d 8 d,d 7 d 4,d 6 d 5 D F, P, G, D, S 4 F, 4 P, H, G, F, Dx, P 5 D, H, G, Fx, D, Px, I, Gx, F, Dx, Sx 6 S, 4 G, 4 F, 4 D, 4 P, I, H, Gx, Fx, Dx, P, S
12 () () Si () Mn + () Rb (4) Co + S
13 S A g S O h A g G g T g P T u T g D F E g +T g A u +T u +T u 5(+) 7(++) P A g T u G H A g +E g +T g +T g E u +T u +T u 9(+++) (+x+) D E g T g I A g +A g +E g +T g +T g (++++x) d F, P, G, D, S F A u T u T u
14 d S G A E T A E A e (non-crossing rule) P D T A T E T T T T t e T F A T T A E T t T p. Free ion Weak filed Strong field Limited d g
15 La Porte s Rulel= O h )( u g; g u) d p; sp dd; sd S= T g A g Paporte T g T g [Ti(OH [Ti(OH ) ) 6 ] + 6 ] + d d-dlaporte ) d-dlaporte Laporte
16 - 4 6 d 5 [Mn(OH ) 6 ] + d 8 [Ni(OH ) 6 ] + [PdCl 4 ] - -CT acacp CT
17 Racah ABC () d E( S)= A + 4B + 7C E( G)= A + 4B + C E( D)= A -B + C E( P)= A + 7B E( F)= A -8B A C >5B F < P < D < G < S dc 4B B B [Co + ]: B = 97 cm - [Co(H O) 6 ] + d 7 B= 9 cm - [CoCl 4 ] - d 7 B= 77 cm - =.95 =.75, =B/B d
18 8 [V(H O) 6 ] + d B=86 cm - (V + ) A g E g 5 CT 57cm - T g T g 78cm - T g T g A g (e g ) S E / B G P D F T g T g T g T g (t g e g ) A g E g T g T g (t g ) 4 5 / Β / cm -. [V(H O) 6 ] + V + d. d-d. d T g 4. T g, T g, A g 5. =57/78= /B/B=9. 8. T g T g, T g T g B 4.5B. B6cm -. B(86cm - )7. CT
19 S E / B G P D F Ni + A g d 8 B=8 cm - (Ni + ) T g E g T g (t g 4 e g 4 ) T g T g T g T g (t g 5 e g ) A g E g A g (t 6 g ) 4 5 / Β.7. / nm [Ni(en) ] + [Ni(H O) 6 ] / cm - [Ni(H O) 6 ] +. 4/88=.7 o /B=. A g T g (E/B ), A g T g (E/B 8) E (88+857)=868. B/B =8% (B=868cm - ) 4. A g T g 5. A g E g ( T g E g A g E g [Ni(en) ] +. 5/=.8 o /B=.. 4. d-d
20 Charge transfer, CT :d-d CT LMCTligand-metal charge transfer MLCTmeta-ligand charge transfer LMCT CT d-d log(e/l mol - cm - ) 4 (5 cm - ) [CrCl(NH ) 5 ] +, Cr(III), d d-d 4 (5 cm - ) d-d 6 l/ nm (7 cm - )
21 No d B=766 cm - (V + ), cm - (Cr + ) A g 4 T g (t g e g ) 794cm cm - 74cm - 574cm - 74/794= A g 4 T g B=(74/4+794 /)/ =(5+55)=54 =B/B =54/=.5 E/B=4 E / B F 4 4 T g (t g e g ).7 E/B= T g. P H G 4 P T g E g : 4 A g 4 T g : 4 A g 4 T g : 4 A g T g ( 4 T g T g ) 4 F 4 A g (t g ) 4 5 / Β /B=
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