Agust,www,...januar09/Profun-110209ak.ppt. 1) 1) Ed(0), J´=0 – EVv´=8,J´=0 = 45.553 cm-1 3) 3)...
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Transcript of Agust,www,...januar09/Profun-110209ak.ppt. 1) 1) Ed(0), J´=0 – EVv´=8,J´=0 = 45.553 cm-1 3) 3)...
agust,www,...januar09/Profun-110209ak.ppt
84x103
83
82
81
2 h
[cm
-1]
g3-
(0+),v'=0
V1+
, v'=9
V1+
, v'=10
0
1
1
2
4f3
1(v´=0)
f3
2(v´=0)
f3
3(v´=0)
V1+
, v'=8
V1+
, v'=7
3
C1(v´=1)
D1(v´=0)
F1(v´=0)
d3(v´=0)
d3(v´=0)
g3-
(1),v'=0
E1+
,v'=0
1)
1) Ed(0), J´=0 – EVv´=8,J´=0 = 45.553 cm-1
3)
3) Ef(2), J´=5 – EVv´=8,J´=5 = 17.14 cm-12) EVv´=9, J´=5 – EDv´=0,J´=5 = 164.24 cm-1
2)
4)
4) EVv=10, J´=3 – Egv=0 J´=3 = 106.64 cm-1
agust,heima,...january09/Profun-080209ak.pxp <= agust, heima, ...january09Term values for triplet paper-080209kmak.xls
f3D1 (0)
82544.07
82585.60
82647.27
82729.51
82832.47
82956.54
83100.74
av term
82509.27
82548.29
82606.68
82684.29
82781.5
82896.94
83027.44
DE(f3D1-D1Pi1)
34.8
37.31
40.59
45.22
50.97
59.60
73.30
D11(v´=0)
J´
0
1
2
3
4
5
6
7
agust, heima, ...january09/Term values for triplet paper-110209kmak.xls
Termf3D1 (v=0)
82544,0782585,6082647,2782729,5182832,4782956,5483100,74
J'01234567
Termg3Sm0(0)
83088,083103,183133,583179,983242,583322,183418,1
DE(g3Sm0p-f3D1)
559,00547,91532,60513,03489,67461,60
=1 / heterogeneoustriplet triplet
Termf3D1 (0)
J'01 82544,072 82585,603 82647,274 82729,515 82832,476 82956,547 83100,74
av terms83288,27
8333183391,3783463,2783530,34
DE(g3Sm1-f3D1
744,20745,40744,10733,77697,87
g3Sm1
Term Termf3D1 (0) g3Sp1(v=0)
J' New StateDE(f3D1-g3Sp1)
0 Q
1 82544,07Q 82541,7 2,37
2 82585,60S 82582,3 3,30
3 82647,27S 82643,7 3,57
4 82729,51S 82725,7 3,81
5 82832,47S 82827,9 4,57
6 82956,54S 82950,2 6,34
7 83100,74S 83092,2 8,54
83253,1
=0 homogeneoustriplet singlet
=0 homogeneoustriplet triplet
=0 homogeneoustriplet triplet
Termf3D1 (0)
82544,0782585,6082647,2782729,5182832,4782956,5483100,74
J'01234567
TermV1S (9)
82839,7082847,1782861,8182883,2782911,6482946,1482986,7383029,23
DE(f3D1-Vv9)
-303,10-276,21-236,00-182,13-113,67-30,1971,51
=1 / heterogeneoustriplet singlet
Termg3Sp1(v=0)New StateQ
82541,7
82582,3
82643,7
82725,7
82827,9
82950,2
83092,2
83253,1
J'01234567
TermV1S (9)
82839,7082847,1782861,8182883,2782911,6482946,1482986,7383029,23
DE(g3Sp1(v=0)-Vv9)
-305,47
-279,51
-239,57
-185,94
-118,24
-36,53
62,97
84x103
83
82
81
2 h
[cm
-1]
g3-
(0+),v'=0
V1+
, v'=9
V1+
, v'=10
0
1
1
2
4
f3
1(v´=0)
f3
2(v´=0)
f3
3(v´=0)
V1+
, v'=8
V1+
, v'=7
3
C1(v´=1)
D1(v´=0)
F1(v´=0)
d3(v´=0)
d3(v´=0)
g3-
(1),v'=0
E1+
,v'=0
g3+
(1),v'=0
agust,heima,...january09/Profun-100209ak.pxp <= agust, heima, ...january09Term values for triplet paper-100209kmak.xls
84x103
83
82
81
2 h
[cm
-1]
g3-
(0+),v'=0
V1+
, v'=9
V1+
, v'=10
0
1
1
2
4
f3
1(v´=0)
f3
2(v´=0)
f3
3(v´=0)
V1+
, v'=8
V1+
, v'=7
3
C1(v´=1)
D1(v´=0)
F1(v´=0)
d3(v´=0)
d3(v´=0)
g3-
(1),v'=0
E1+
,v'=0
g3+
(1),v'=0
70
60
50
40
7654321
Ef31 – D11
J´
agust,heima,...january09/Profun-100209ak.pxp <= agust, heima, ...january09Term values for triplet paper-100209kmak.xls
84x103
83
82
81
2 h
[cm
-1]
g3-
(0+),v'=0
V1+
, v'=9
V1+
, v'=10
0
1
1
2
4
f3
1(v´=0)
f3
2(v´=0)
f3
3(v´=0)
V1+
, v'=8
V1+
, v'=7
3
C1(v´=1)
D1(v´=0)
F1(v´=0)
d3(v´=0)
d3(v´=0)
g3-
(1),v'=0
E1+
,v'=0
g3+
(1),v'=0
8
7
6
5
4
3
7654321
Ef31 – g3+
1
J´
agust,heima,...january09/Profun-100209ak.pxp <= agust, heima, ...january09Term values for triplet paper-100209kmak.xls
84x103
83
82
81
2 h
[cm
-1]
g3-
(0+),v'=0
V1+
, v'=9
V1+
, v'=10
0
1
1
2
4
f3
1(v´=0)
f3
2(v´=0)
f3
3(v´=0)
V1+
, v'=8
V1+
, v'=7
3
C1(v´=1)
D1(v´=0)
F1(v´=0)
d3(v´=0)
d3(v´=0)
g3-
(1),v'=0
E1+
,v'=0
g3+
(1),v'=0
300
250
200
150
100
50
0
7654321
Ef31 - V,v´=9
J´
agust,heima,...january09/Profun-100209ak.pxp <= agust, heima, ...january09Term values for triplet paper-100209kmak.xls
84x103
83
82
81
2 h
[cm
-1]
g3-
(0+),v'=0
V1+
, v'=9
V1+
, v'=10
0
1
1
2
4
f3
1(v´=0)
f3
2(v´=0)
f3
3(v´=0)
V1+
, v'=8
V1+
, v'=7
3
C1(v´=1)
D1(v´=0)
F1(v´=0)
d3(v´=0)
d3(v´=0)
g3-
(1),v'=0
E1+
,v'=0
g3+
(1),v'=0
Eg3
1 - V,v´=9
J´
agust,heima,...january09/Profun-110209ak.pxp <= agust, heima, ...january09Term values for triplet paper-110209kmak.xls
300
250
200
150
100
50
0
7654321
84x103
83
82
81
2 h
[cm
-1]
g3-
(0+),v'=0
V1+
, v'=9
V1+
, v'=10
0
1
1
2
4
f3
1(v´=0)
f3
2(v´=0)
f3
3(v´=0)
V1+
, v'=8
V1+
, v'=7
3
C1(v´=1)
D1(v´=0)
F1(v´=0)
d3(v´=0)
d3(v´=0)
g3-
(1),v'=0
E1+
,v'=0
g3+
(1),v'=0
540
520
500
480
654321
Ef31
- g3-0
J´
agust,heima,...january09/Profun-100209ak.pxp <= agust, heima, ...january09Term values for triplet paper-100209kmak.xls
84x103
83
82
81
2 h
[cm
-1]
g3-
(0+),v'=0
V1+
, v'=9
V1+
, v'=10
0
1
1
2
4
f3
1(v´=0)
f3
2(v´=0)
f3
3(v´=0)
V1+
, v'=8
V1+
, v'=7
3
C1(v´=1)
D1(v´=0)
F1(v´=0)
d3(v´=0)
d3(v´=0)
g3-
(1),v'=0
E1+
,v'=0
g3+
(1),v'=0
agust,heima,...january09/Profun-100209ak.pxp <= agust, heima, ...january09 / Term values for triplet paper-100209kmak.xls
740
730
720
710
700
54321
Ef31 - g3-
1
J´
The question arose whether the “New state” (assigned as g3+(1) from Q lines) could simply beQ lines for the f31 <-<-X1+ ???
Factors which favour that are:
1) Term values for “New state” (derived from Q lines;Term values for triplet paper-110209kmak.xls)are close to that for f31 derived from S lines (see slides 3, 7And 8 above) 2) B´s are similar: B´(“New state” ) 10.26 cm-1; B´(f31) = 10.293 cm-1
3) 0´s are similar:0(New state) = 82521.2 cm-1; f31) = 82523.65 cm-1
Arguments agains it (from KM):
1) Although difference in term values is small it is significant andsimultaneous simulation of line positions for Q lines in the “New state” spectrum and line positions for S lines in the f31 <-<-X1+ spectrum can not be done for a unique set of B´(and D´) values: Thus if the S lines are fitted the position of the Q lines will be at higher cm-1 and close to the Q line near 82523.65 cm-1 which Green et al assigned as the Q line peak for the f31 <-<-X1+ spectrum.
2) The single peak at 82523.65 cm-1 which Green et al. assigned as the Q line peak can not be assigned to any other nearby systemwhich favours the Greens assignment.
3) A single peak for a Q line serie is obtained for = 1 (i.e. For ´ = 1 (´´=0), whereas different shapes are obtained for = 0 and = 2, roughly:
=0 =1 =2 Hunds case c
=0 =1 =2 Hunds cas a-b
3+(1) assuming Hunds case (b)
3 (1) assuming Hunds case (c)
3 (1) assuming Hunds case (a)
3+(1) assuming Hunds case (c)
Most likely
a)
a) Shape closes to that observed for “new state”
4) Good fit was obtained for P and R lines using the otherset Of B´and D´values derived by Green et al.
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