Chng 3: Ph hp th electron

3.0. M u:
Ph electron dng nghin cu c cc hp cht v c v hu c, trong v c ch
yu l nghin cu phc cht.
Phc cht ca kim loi chuyn tip thng c mu (vi cu hnh d
n
, n 10) do n
hp th nh sng. C ion trung tm v phi t u c th hp th nh sng, nhng m ca
phc cht ch yu c quyt nh bi ion trung tm, do ph electron dng nghin
cu ion trung tm l ch yu.
Phc cht hp th nh sng kch thch electron ca ion trung tm nhy ln mc
nng lng cao hn. V vy xt ph electron ca phc ph xt ph nng lng ca ion
trung tm.
Ion t do c trng i xng cu, cn ion nm trong phc chu s tc ng ca phi
t nn ph nng lng ca n khc vi ph nng lng ca ion t do. Cc ion nm trong
cu ni ca phc gi l ion nm trong trng tinh th. Trng tinh th lm tch cc s hng
nng lng.
3.1. Ph hp th electron v cu to ca cc phc cht kim loi chuyn tip:
3.1.1. Cc kiu chuyn mc c th xy ra trong phn t phc cht:
Trong thnh phn ca mt phn t phc cht c ion kim loi trung tm (cu hh d
n
),
phi t v c th c c ion cu ngoi, do trong trng hp chung nht ph hp th ca
phc s l mt tp hp ca ph hp th ca cc thnh phn ny. Ngoi ra, tu thuc vo tnh
oxi ho kh ca ion trung tm v phi t m trong ph ca cc phc cht cn c th c
thnh phn ph chuyn in tch. Trong 4 thnh phn ny th ph ca ion trung tm (thng
gi l ph chuyn d d) cho nhng thng tin v tnh i xng, ngha l cu trc hnh hc
phn t. Do , c th thu c nhng thng tin v cu to phn t t ph hp th electron,
iu quan trng l phi phn lp c cc di ph chuyn d d trong ph tp hp . Mun
vy cn phi bit cc phi t v ion cu ngoi no c th hp th nh sng v c im ca
ph hp th ca chng. Di y l mt s kiu chuyn mc electron xy ra trong phn t
phc cht (ngoi chuyn mc d d)

a) Cc chuyn mc trong ni b phi t:
- Chuyn mc n o*: Khi phi t l nhng phn t (ion, phn t) c cc cp electron
khng lin kt v khng c lin kt t th obitan c nng lng cao nht b chim bi
electron, k hiu l HOMO (vit tt ca t ting Anh: Highest occupied molecular
orbital) l MO cha cp electron khng lin kt n, cn obitan c nng lng thp
nht khng c electron LUMO (vit tt ca t ting Anh: Lowest unoccupied
molecular orbital) l obitan o*. S chuyn mc n o* xy ra khi hp th nh sng
trong vng trng thy hay t ngoi. Cc phi t thuc loi ny l H
2
O, NH
3
, amin,
ancol Nc c mt di hp th mnh vng 60.000cm
-1
(hay 167nm), CH
3
OH c
di hp th 54.500cm
-1
(hay 183nm)
- Chuyn mc n t*: S chuyn mc ny xy ra khi phi t c lin kt t ng thi
c cc cp electron khng lin kt. Phi t loi ny l cc anehit, xeton, gc axit
hu c, cc phi t cha cc nhm N=C; N=N; cc hp cht d vng Trong
trng hp ny HOMO l obitan n cn LUMO l t*. Cc chuyn mc ny cng
thng xy ra vng trng thy v t ngoi.
- Chuyn mc t t*: S chuyn mc ny xy ra cc phi c lin kt t nhng
khng c cc cp electron khng lin kt, v d etylen, benzen
b) Cc mc chuyn trong ion cu ngoi: Khi cu ni ca phc cht l cation th cu
ngoi c th l anion n hoc a nguyn t. Cc anion n nguyn t v mt s
anion a nguyn t nh ClO
4
-
, SO
4
2-
khng hp th nh sng trong vng UVVis nn
khng c ph ring, nhng mt s anion hp th nh sng mnh trong vng UVVis
nh MnO
4
-
, CrO
4
2-
, NO
3
-
, NO
2
-
trnh nh hng ca anion n ph ca phc
cht ngi ta thng s dng cc ion cu ngoi nh SO
4
2-
, ClO
4
-
, Cl
-

c) Ph chuyn in tch:
Ngoi hai loi chuyn mc trn (chuyn mc trong ni b phi t hoc trong ion cu
ngoi) cn c mt loi chuyn mc na khng thuc loi chuyn mc d d l chuyn mc
chuyn in tch (change transfer transitions).
Ph chuyn in tch xut hin do s chuyn electron gia ion kim loi trung tm
vi phi t. Ngi ta phn bit s chuyn in tch kim loi phi t, thng c k
hiu l chuyn M L, trong electron chuyn t obitan ca kim loi sang obitan trng
ca phi t v s chuyn in tch phi t kim loi, k hiu l chuyn L M, trong
electron chuyn t cc obitan ca phi t sang cc obitan trng ca kim loi.
S chuyn in tch M L xy ra khi kim loi d b oxi ho, ngha l c nhng
obitan cha electron c nng lng cao, cn phi t th c nhng obitan trng c nng
lng tng i thp. V d ca trng hp ny l cc phc cht ca cc kim loi mc oxi
ho thp v phi t c cc obitan t* trng nh piridin; 2,2 bipiridin; 1,10 phenantrolin.
S chuyn in tch L M xy ra trong trng hp ngc li, khi kim loi mc
oxi ho cao, c nhng obitan d trng c nng lng tng i thp, cn phi t c cc
obitan n c nng lng tng i cao. V d ca trng hp ny l cc phc cht ca Hg2+,
Ti
4+
, Co
3+
, Fe
3+
vi cc phi t nh I
-
, S
2-
, cc hp cht d vng, amin hoc trong cc
ion nh CrO
4
2-
, MnO
4
-

Da trn ph chuyn in tch ngi ta c th gii thch nhiu hin tng nh s
chuyn mu trong dy AgX: AgCl (khng mu)AgBr (vng nht)AgI (vng) hay mu ca
cc hp cht d
0
nh HgI
2
() hay cc sunfua thng c mu m hn cc oxit tng ng
Cc di ph chuyn in tch thng xut hin trong vng t ngoi v c cng
rt mnh.
Nh vy, khi bit thnh phn ca mt phc cht, da vo c im ca cc phi t
v ion cu ngoi ngi ta c th phn lp c cc di hp th ca chng v do xc nh
c cc di chuyn d d.
3.1.2. th Tanabe Sugano.
th Tanabe Sugano l th biu din s ph thuc ca cc mc nng lng ca
cc ion dn trong trng phi t bt din (xem cc th km theo). th c xy dng
da trn cc nguyn tc sau:
- Khi t trong trng phi t, nng lng ca cc s hng l hm ca 4 bin s: E =
f(A,B,C,A) trong A, B, C l cc thng s Racah, n xut hin khi tnh n tng tc gia
cc electron; A l thng s c trng cho tng tc ca trng phi t (nng lng tch).
- i vi mi cu hnh dn, phn ng gp ca A vo nng lng ca tt c cc s
hng l nh nhau, cn t l C/B bng mt gi tr xc nh ~ 4.
- Ph hp th electron l th hin tng tc gia cht nghin cu v cc photon:
electron hp th cc photon nhy ln mc nng lng cao hn, hiu hai mc nng lng
ny bng nng lng ca photon b hp th (iu kin tn s Borh)
V vy hiu gia cc mc nng lng quyt nhph ca cc cht (ch khng phi
nng lng tuyt i ca cc s hng). Do c th b qua phn ng gp ca A trong cc
s hng nng lng. Nu biu din C theo B th E/B (c trng cho nng lng ca cc s
hng) l hm ca A/B hay 10Dq/B (c trng cho lc trng phi t).
- S hng c bn trng vi trc honh.
Trn th ca cc cu hnh d
4
d
7
cc ng biu din nng lng c im gy khi
chuyn t trng yu sang trng mnh do ng vi cc cu hnh ny c sp xp cc
electron khc nhau trong trng yu v trng mnh, phn bn tri ca th ng vi
trng yu (P > A), phn bn phi ng vi trng mnh (P < A)
Bng: Cu hnh electron trong trng yu v trng mnh
Cu hnh
Trng yu Trng mnh
Bt din (O
h
) T din (T
d
) Bt din (O
h
) T din (T
d
)
d
1
T
2g
1
e
1
T
2g
1
e
1

d
2
T
2g
2
e
2
T
2g
2
e
2

d
3
T
2g
3
e
2
t
1
T
2g
3
e
3

d
4
T
2g
3
e
g
1
e
2
t
2
T
2g
4
e
4

d
5
T
2g
3
e
g
2
e
2
t
3
T
2g
5
e
4
t
1

d
6
T
2g
4
e
g
2
e
3
t
3
T
2g
6
e
4
t
2

d
7
T
2g
5
e
g
2
e
4
t
3
T
2g
6
e
g
1
e
4
t
3

d
8
T
2g
6
e
g
2
e
4
t
4
T
2g
6
e
g
2
e
4
t
4

d
9
T
2g
6
e
g
3
e
4
t
5
T
2g
6
e
g
3
e
4
t
5

d
10
T
2g
6
e
g
4
e
4
t
6
T
2g
6
e
g
4
e
4
t
6

Quy tc k hiu ca cc s hng:
+ S, P, D c k hiu theo moment ng lng obitan ton phn M
L
= Em
l
: Khi M
L

= 0k hiu S; M
L
= 1k hiu P; M
L
= 2k hiu D; M
L
= 3k hiu F; M
L
= 4k hiu G
+ S nh bn tri s hng ch bi spin ca trng thi: n = 2S 1. S nh bn
phi ch c im i xng ca s hng (s 1 ch trng thi i xng vi trc C
2
vung gc
vi C
n
; s 2 ch trng thi bt i xng vi trc C
2
vung gc vi trc C
n
)
+ Ch nh pha di bn phi ch nhm c tm i xng: ch g ch trng thi i
xng vi tm, ch u ch trng thi bt i xng i vi tm.
+ A, B, E, T ch suy bin ca s hng: Suy bin bc 1k hiu A,B (A-khi i
xng vi trc chnh; B-khi khng i xng vi trc chnh); bc 2-E; bc 3-T;
+ th Tanabe Sugano c th p dng cho cc trng i xng khc da trn
nguyn tc: Theo phng din tnh in th cu hnh d
n
v cu hnh d
10-n
l tng ng
nhau, ch khc nhau l nu n electron b y bi trng phi t th n v tr trng b ht bi
trng phi t, do c s tch cc s hng ca cu hnh d
n
, ngc vi cu hnh d
10-n
. Bng
l lun tng t ta c cu hnh d
5+n
tng t d
n
; d
5-n
tng t d
10-n
.

Hnh v: th Tanabe Sugano cho cc cu hnh.
V d 1: ion Cr
3+
, cc chuyn mc khng b cm l:
4
A
2g

4
T
2g

4
A
2g

4
T
1g

4
A
2g

4
T
1g
(P)
Ta ni trong trng hp ny c 3 chuyn mc cho php v spin. 3 chuyn mc ny
s hp th cc bc x vi cc tn s tho mn cc h thc:
hv
1
= E
(
4
T
2g
)
E
(
4
A
2g
)
.
hv
2
= E
(
4
T
1g
)
E
(
4
A
2g
)
.
hv
3
= E
(
4
T
1g
(P))
E
(
4
A
2g
)
.
Do ph ca cc phc cht bt din ca Cr
3+
s c 3 di hp th.
Tip theo, ta c th xc nh v tr ca cc di hp th, tc l cc gi tr ca v
1
, v
2
v
v
3
khi bit A i vi phi t tng ng.
Chng hn, i vi phc cht Cr(NH
3
)
6
3+
, phi t NH
3
c A = 21550cm
-1
(1cm
-1
=
11,963kJ/mol). V vi Cr
3+
c B = 1030cm
-1
nn A/B = 21550/1030 = 20,92 hay Dq/B =
2,092 (v A = 10Dq). Trn trc honh ca th Tanabe Sugano, t im trn trc honh
ng vi Dq/B = 2,092 v mt ng thng song song vi trc tung. ng thng ny s ct
cc ng biu din ca cc s hng
4
T
2g
,
4
T
1g
,
4
T
1g
(P) tng ng vi cc gi tr E/B =
20,03; 30 v 46,3. T suy ra s sng ca cc bc x b hp th l:

V d 2: D on cc c trng ca ph hp th electron ca cc phc cht [Fe(en)
3
]
2+
v
[Fe(CN)
6
]
4-
, bit A ca en v CN
-
tng ng bng 12.000 v 32.200cm
-1
.
Tr li: T th TanabeSugano vi cu hnh d
6
ca Fe
2+
ta thy i vi Fe
2+
c B =
1058cm
-1
, do i vi en th A/B = 11,34 v i vi CN
-
th A/B = 30,43. Nh vy, phc cht
[Fe(en)
3
]
2+
thuc trng hp trng yu cn [Fe(CN)
6
]
4-
thuc trng hp trng mnh.
i vi phc cht [Fe(en)
3
]
2+
, chuyn mc cho php v spin duy nht l:
5
T
2g

5
E
g

Do ph hp th electron ch c 1 di.
i vi phc cht [Fe(CN)
6
]
4-
cc chuyn mc cho php v spin l:
1
A
1g

1
T
1g

1
A
1g

1
T
2g

1
A
1g

1
E
g

1
A
1g

1
A
2g
1
A
1g

1
A
1g
(
1
F)
T cc im ng vi honh c Dq/B = 1,134 v 3,043 v cc ng thng song song
vi trc tung v bng phng php tng t nh v d 1 trn ta s xc nh c v tr cc
di hp th tng ng.
Nh vy, da vo quy tc cm v spin ta xc nh c s lng v v tr ca cc di
hp th.
b) Xc nh cng ca cc di hp th.
Vic xc nh cng ca cc di hp th da trn quy tc Laporte. Theo quy tc
ny mi s chuyn mc gia cc trng thi c cng tnh chn l u b cm. Quy tc ny
thng c din t di dng c th hn l trong cc phc cht c tm i xng mi s
chuyn mc u b cm.
Nh vy, trong cc phc cht i xng bt din (O
h
), c tm i xng, mi s
chuyn mc u b cm theo quy tc Laporte, cn trong cc phc cht t din (T
d
) khng c
tm i xng cc mc chuyn l c php theo quy tc Laporte.
c) Nhn xt chung:
T hai quy tc chn lc xt trn c th nhn xt rng nu cc quy tc ny hon
ton nghim ngt th cc phc cht bt din ca cc kim loi chuyn tip u khng mu v
khng hp th nh sng. c bit l trng hp ca cc phc cht bt din ca Mn
2+
, v d
Mn(H
2
O)
6
2+
cc chuyn mc va b cm v spin va b cm theo quy tc Laporte, do cc
phc cht ny s hon ton khng hp th nh sng. Tuy nhin thc t cho thy rng cc
phc cht bt din ca cc kim loi chuyn tip u c mu, ngay c phc cht Mn(H
2
O)
6
2+
cng hp th nh sng, tuy rt yu. iu ny ni ln rng s cm theo quy tc trn l khng
trit , mt s chuyn mc b cm theo quy tc ny hay quy tc kia nhng trong thc t
vn c th xy ra, d xc sut b.
3.2. Ph hp th electron v mu ca phc cht:
Nu cht hp th cc photon thuc vng trng thy (400 750nm) th cht c mu,
nu cht khng hp th cc photon trong vng nhn thy th n c mu trng, cn nu n
hp th tt c cc photon trong vng nhn thy th n khng mu.
Mu ca cht m ta quan st c khng phi l mu ca nh sng b hp th m l
mu ca ca nh sng phn x ra t cht. Khi chiu nh sng trn ln mt vt th mt s
bc sng thnh phn b hp th, phn cn li c phn chiu li. Mt ta quan st c
nh sng phn chiu nh l mu ca phn b ca mu b hp th. Gia mu ca nh sng
b hp th bi hp cht v mu ca hp cht c mi quan h vi nhau nh sau:

V d: Cc hp cht ca MnO
4
-
c mu tm do n c hai di chuyn in tch nt*
520nm v 545nm (thuc vng mu vng). Cc hp cht ca Cr
2
O
7
2-
c mu da cam do n c
mt di chuyn in tch nt* 440nm (thuc vng mu xanh).
3.3. Mt s ch dn khi chn iu kin ghi ph:
3.3.1. Chn dung mi:
Chn dung mi ghi ph l yu t rt quan trng , dung mi c chn phi p
ng hai yu cu sau:
- Dung mi khng hp th trong vng ang nghin cu;
- Dung mi khng nh hng n dng ph. Khi ph thu c s l tng ph ca
dung mi v cht nghin cu.
Cc dung mi khng phn cc khng to lin kt hidro vi cht tan nn ph ca dung
dch cht tan gn ging vi ph ca n dng kh nn vic nghin cu cu trc ca cht thng
thun li. Dung mi phn cc thng to lin kt hidro vi cht tan nn vic nghin cu cu
trc kh khn. Sau y l mt s dung mi v
max
ca n:
Bng : Mt s dung mi v
max
ca n
Dung mi
max
(nm) Dung mi
max
(nm)
Axetonitril 190 Etanol 205
CHCl
3
240 Metanol 205
xiclohexan 195 Isooctan 195
n - hexan 210 H
2
O 190
1,4 dioxan 215 Trimetylphotphat 210
3.3.2. Mt s nguyn nhn lm sai lch nh lut Lambe Bia:
C nhiu nguyn nhn khc nhau nh my mc, thit b v cc nguyn nhn ho l.
Sau y l mt s nguyn nhn ho l thng gp:
- H s hp th phn t c: trong mt chng mc no c th ph thuc vo nng
ca cht. nh lut Lambe Bia ch hon ton ng i vi mi trng ch c mt trung
tm hp th. Nu khi ho tan cht m bn cht ca cht hp th thay i, v d do xy ra qu
trnh phn li hoc kt hp khi thay i nng ca cht th h s hp th phn t s khng
c nh i vi cc nng khc nhau ca cht. V vy trc khi tin hnh phn tch bao
gi cng phi kim tra xem nh lut c c thc hin hay khng v c thc hin trong
khong nng no.
- S chuyn dch cn bng gia cc cu t ca cht tan, v d s chuyn dch gia
CrO
4
2-
v Cr
2
O
7
2-
. khc phc iu ny cn phi kim tra cht ch pH ca dung dch.
- Ph hp th cng c th b thay i do s oxi ho cht nghin cu, khi dung dch tc
dng vi khng kh hoc nh sng. khc phc iu ny cn phi ghi ph trong khong thi
gian m cht cha b bin i di tc dng ca mi trng.
3.4. ng dng ca ph hp th electron:
3.4.1. Xc nh cu to ca phc cht:
Khi xc nh c cc di chuyn mc d d trong ph c th suy on c cu
hnh ca phc cht.
3.4.2. Xc nh thnh phn ca phc cht trong dung dch:
Bng phng php dy ng phn t gam c th xc nh c thnh phn v hng
s bn ca phc cht trong dung dch.
3.4.3. Phn tch nh lng:
Da vo nh lut Lambe Bia c th xc nh nng ca cc cht trong dung
dch, t c th nh lng c hp cht.