2

2.1 Fluorescence
F

2.2 Phosphorescence
P

2.3 Chemiluminescence
C

2.1.1 2.1
2.1.1

2.1.2

2.1.3

2.1.4

M
2.1.5

2.1.6

Mg
2.1.7
00:00:49
2/23/2013

00:00:49

2.1 Fluorescence
2.1.1

: /

M=2S+1

S
S= 1 2 1 2 0
,

singlet state:

00:00:49

2.1.1
S0

S0

S1/ S2

S/T

Hund

S=
1 2 1 2 1

T1/T2

M=2S+1 3
triplet state
00:00:49


Mg

3p
3s

1
2

1
2

2S+1=1

1
2

1
2

1
2

1
2

1st

2S+1=1

J2S+1

(L+S),(L+S-1),,(|L-S|)

2S+1=3

MgS / S / T
0
1
1
S=
1
2

1
2

3p

state
1

2
3s

1st
2S+1=1
2S+1=3
2S+1=1

L=0

s
J2S+1:(L+S),(L+S-1),,(|L-S|)
1
2

1
2

1
2

L=

0 (S)

J=

1
2

1(P)
1

1
2, 1, 0

3p
1
2

1
2

1
2

1
2

3s

1
2

Mg
1
2

1st

2S+1=1

2S+1=1

3 S0

3 P1
n

2 S 1

2S+1=3
3

3 P2 3 P1 3 P0
LJ

2.1.1 6
(1) vibrational relaxation
: 10-15s <
10-14-10-12s

(2)

00:00:50

p136

S1 S0 : 10-9-10-7s

2.1.1

S
S1

(3) internal conversion

(S1S2)
10-13-10-11s

(4) intersystem corssing

: S1 T1
10-2-10-6s
00:00:50

2.1.1
(5)
T1 S0
10-2-10s

(6) external conversion

/
00:00:50

2.1.1

00:00:50

2.1.1
e

00:00:50

2.1.1
e

e
e

00:00:50

2.1.1

e
e

S1

S0

2.1.1 2.1
2.1.1

2.1.2

2.1.3

2.1.4

2.1.5

2.1.6

2.1.7
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2/23/2013

00:00:50

2.1.2

f/

kf
k f ki

kfki
f>0.1f1

00:00:50

2.1.1 2.1
2.1.1

2.1.2

2.1.3

2.1.4

2.1.5

2.1.6

2.1.7
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2/23/2013

00:00:50

2.1.3

>1

f=0.29f=310nm
f=0.46f=400nm

2.1.3

3+
pH5Al

f1.0

f0.2

BBR

2.1.3

//

-NH2 -OH
n-,

>C=O -NO2

10

18

10
20
0

2.1.3

p137

10

10

2.1.3
--

8-

::1:30:1000

CCl4
2.24
CHCl3
5.2
CH3CN
38.8

f/nm f
390 0.002
398 0.041
410 0.064

2.1.3
--

TT

-80f=100%

10 f3%

2.1.3
-- pH ( p140 )

()

--
f

()f

2.1.3

(1)

A lg( I 0 I )

M* +Q M+Q+
M* +Q M+Q*

2.1.3

(1)

A lg( I 0 I )

(3) /

2.1.1 2.1
2.1.1

2.1.2

2.1.3

2.1.4

2.1.5

2.1.6

2.1.7
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2/23/2013

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2.1.4

A lg( I 0 I )

I I 0 10
2

2!

3!

x e x 1 x x x ... 1 x
A lg( I 0 I )

x 1 e

I f f I a f ( I 0 I ) f I 0 (1 10 )
A

A=kbc

I f 2.30 f I 0 A 2.30 f I 0 kbc Kc

2.1.4

I f Kc

A<0.05
If

A lg( I 0 I )

IfA
Ac
0
0

0.1

0.2

0.3

2.1.1 2.1
2.1.1

2.1.2

2.1.3

2.1.4

2.1.5

2.1.6

2.1.7
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2/23/2013

00:00:50

2.1.5

f
I

ft

2.1.1 2.1
2.1.1

2.1.2

2.1.3

2.1.4

2.1.5

2.1.6

2.1.7
00:00:50
2/23/2013

00:00:50

2.1.6

00:00:50

2.1.6

,

IA

00:00:50

2.1.6

00:00:50

2.1.7
Th 0.01g
,

Ift

00:00:50

2.1.7

<15nm,
>60nm,

tyr

try

k /(10 mg

-1

L)

phe

2
1
0
260

00:00:50

310

360
/nm

410

460

2.1.7

70
Be Al B Ga Se Mg
F S Fe Ag
Cu Be Fe Os H2O2

00:00:50

2.1.7
200

150

n=1

exn

100

50

1000

4 mg/L
2 mg/L

0
phe
ex=257nm
250
270
290
310
330
350
/nm
n=1,2
1200

n=2

800
600

1000

400

800

200
4 mg/L
2 mg/L

600

400

250

200

350

450

ex=257nm

0
450

500

550
/nm

600

650

550

650

2.1.7
www.PerkinElmer.com

LS45
LS55

I p Kc

2.2 Phosphorescence
2.2.1
T1>S0
Ip

I p Kc
/

00:00:50

I p Kc

2.2.2
T1

///

D*
00:00:50

I p Kc

2.2.2

A*

D*
SA+hv

A*T
1

S1

e
A

e
T1
e
T1
(1)

(2)T1DT1
(3)1,4-
S0

S0

D
00:00:50

I p Kc

2.2.3
Ip:
()
internal heavy-atom
effect

()

-
S1>T1

00:00:50

I p Kc

2.2.4

:.

, p88.
,
00:00:50

I p Kc

2.2.4

2
00:00:50

I p Kc

2.2.4

//

:
, VK, VB6, VE
: .
,
00:00:50

I p Kc

2.3 Chemiluminescence

2.3.1

Cr3+10-9 g/L

56


00:00:50

I p Kc

2.3.2


A + B > C* + D
<0.01
C* > C + h

(Redox)

00:00:50

I p Kc

2.3.2
(3-)

max=425nm
10-9 mol/L H2O2
,
Co(II)/Cu(II)/Ni(II) 0.0140 g/ml
00:00:50

I p Kc

2.3.2
(3-)

AA O2 H2O2 NH3

00:00:50

I p Kc

2.3.2

NO O3 NO O 2
*
2

NO NO 2 h
*
2

600 875nm
1 ng/mlNOO3
NO2 (NO)
NH3 (NO2 )
NOx
00:00:50

I p Kc

2.3.2
NO

NO H HNO

HNO HNO h
*

max=690nm
NO2 NO, NOx

00:00:50