TNG HP CC CU HI QUANG PH RAMAN TRN LP CAO

HC QUANG IN T K18, I HC KHOA HC T NHIN

TP.HCM (THEO GIO TRNH Introductory Raman spectroscopy ca
John R.Ferraro)
CHNG I
1. im khc nhau c bn nht v bn cht ca ph Raman v ph Hng ngoi (IR) l g?
+ Bn cht ca ph Raman l do s thay i ca phn cc (polarizability) ca phn t trong
sut qu trnh dao ng. Ph Raman l ph tn x.
+ Bn cht ca ph Hng ngoi (IR) l do d thay i moment lng cc (dipole moment) ca
phn t trong sut qu trnh dao ng. Ph Hng ngoi l ph hp thu.
2. Gii thch v sao dao ng Raman l mnh nu l lin kt cng ha tr, dao ng hng ngoi l mnh
nu l lin kt ion?
+ Trong lin kt ion, phn t b phn cc hon ton thnh mt u mang in tch dng v
mt u mang in tch m, v vy phn t ng vai tr nh mt lng cc (dipole). Khi phn t dao
ng, trong phn t xut hin moment lng cc, do , dao ng ca phn t l dao ng hng ngoi.
+ Trong lin kt cng ha tr, phn t lin kt vi nhau bng cch dng chung cp in t ha
tr, khng c s phn cc r rng m ch c s khc nhau trong phn b in t, tc l c mt phn
cc nht nh. Khi phn t dao ng, phn cc ca phn t thay i, do , dao ng ca phn t l
dao ng Raman.
3. Gii thch v sao c th dng Raman cng hng nghin cu cc nhm mang mu?
Cc nhm mang mu trong mt hp cht thng c nng nh. Nu ch dng cc k thut
chp ph thng thng th kh m ghi nhn c ph ca nhm mang mu v chng c cng rt
b. Vi Raman cng hng, cc nhm mang mu c kch thch pht ra vi cng ln, c
th ghi nhn.
4. Cho bit ngha ca t s kh phn cc?
T s kh phn cc ca ph Raman cung cp thng tin quan trng v s i xng ca dao
ng, n khng th thiu trong vic gii on cc di ph.
Cng nhiu thng tin cng thun li cho vic nghin cu ph, t s phn cc l mt trong
nhng thng tin .
5. Trong biu thc tnh t s kh phn cc vi tn x Raman thng, con s no l quan trng nht?
Cho bit ngha ca chng.
T s kh phn cc c tnh theo cng thc:
0
3 5
10 4
s a
p s
g g
g g

+
(*)
Trong :
1
( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
2
0
2 2
2
2 2
2
2 2
2
1
3
1
3
1
2
1
2
xx yy zz
s
xx yy yy zz zz xx
xy yx yz zy xz zx
a
xy yz xz zx yz zy
g
g
g




+ +
1
+ +
1
]
1
+ + + + + +
1
]
1
+ +
1
]
Trong tn x Raman thng, g
a
= 0 v tensor phn cc l i xng. V vy, (*) tr thnh:
0
3
10 4
s
p s
g
g g

+
Con s quan trng nht trong tn x Raman thng l
4
3
+ i vi dao ng i xng hon ton, g
0
> 0 v g
s
0, v vy 0
p
<
3
4
(b phn cc).
Phn t ng hng (Phng dao ng song song vi phng in trng):
p
= 0
+ i vi dao ng i xng mt phn, g
0
= 0 v g
s
> 0, v vy
p
=
4
3
(b kh phn cc)
Trong tn x Raman cng hng (g
a
0), c th c
p
>
3
4
.
Khi
p
: phn cc d thng hay nghch (anomalous or inverse polarization) (vit tt l ap
hay ip).
6. Hy trnh by v cc vng ph v ngun gc ca chng
2
7. Ti sao khi gii thch c ch pht ph Raman hay Hng ngoi, ngi ta hay cp n s hot ng
ca phn t hai nguyn t?
Trc ht, hot ng ca phn t gm 2 nguyn t tng i n gin kho st hn l phn
t gm nhiu nguyn t. Vi phn t gm 2 nguyn t c th xy ra 3 loi dch chuyn sau: dch
chuyn gia cc mc quay, dch chuyn gia cc mc dao ng v dch chuyn gia cc mc in t,
mi dch chuyn ny s cho mt loi ph nht nh. V d dch chuyn gia cc mc dao ng s cho
ph Raman hay Hng ngoi ty thuc vo nng lng kch thch. T hot ng ca phn t gm 2
nguyn t, ngi ta s tip tc xy dng m hnh hot ng ca phn t gm nhiu nguyn t vn
phc tp hn rt nhiu.
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8. M hnh phn t 2 nguyn t s dng m hnh g trong c hc lng t?
M hnh dao ng t iu ha.
9. Cho bit dng biu thc ca th nng Morse. Ti sao trong m hnh phn t hai nguyn t, ngi ta
li s dng th Morse?
Biu thc ca th nng Morse c dng:
( )
( )
[ ]
2 1
2 1
2
.
2
2
1
0
m m
m m
D
e D r U
e
r r
e
+

Trong : D
e
l nng lng phn ly phn t; l tn s dao ng; l khi lng rt gn ca
phn t
Ban u, khi kho st m hnh phn t hai nguyn t, ngi ta s dng th nng iu ha:
( ) ( )
2
0
2
1
r r k r U
(*)
Trong : r
0
l khong cch gia hai nguyn t khi chng v tr cn bng
Khi so snh m hnh l thuyt vi th nng iu ha v cc kt qu thc nghim, ngi ta thy
c mt s iu cha hp l nh sau:
4
+ Theo thc nghim, khi khong cch gia 2 nguyn t cng ln (tc r ), th U(r) s tin
n mt gi tr xc nh no . Cn theo l thuyt, biu thc (*) cho thy khi r th U(r) .
+ Khi a biu thc th nng iu ha vo phng trnh sng Schrodinger, ngi ta thu c
biu thc tnh nng lng ca dao ng t trn mi mc dao ng c dng:

,
_

+
2
1
h E
v
Tc l khong cch gia 2 mc nng lng lin tip l mt lng h khng i, ni cch khc
cc mc nng lng dao ng cch u nhau. Tuy nhin, iu ny li khng ng vi thc nghim, v
t vic ghi ph, ngi ta thy rng khong cch gia cc mc dao ng hon ton khng cch u
nhau. Hn na, vi biu thc th nng iu ha, ngi ta cng khng th gii thch c s xut hin
trong ph ghi c cc ha tn bc 2, bc 3.
Th nng Morse c a ra gii quyt c nhng iu cha hp l .
+ Ta thy rng, vi biu thc th nng Morse, khi khong cch gia 2 nguyn t cng ln (tc r
), th U(r) s tin n D
e
. iu ny tng i ph hp vi thc nghim
+ Mt khc, khi thay th nng Morse vo phng trnh Schrodinger, biu thc tnh nng lng
ca dao ng t trn mi mc dao ng c dng:
2
2 2
2
1
4 2
1

,
_

+
,
_

e
v
D
h
v h E
Tc l cng ln cao, khong cch gia cc mc nng lng cng hp. iu ny ph hp vi
ph thc nghim v cng gii thch c s xut hin ca cc ha tn bc 2, bc 3.
ng cong th nng ca mt phn t gm 2 nguyn t. ng lin nt tng ng vi
th Morse (gn ging thc t). ng t nt l th dao ng iu ha (c dng parabol).
De l nng lng phn ly l thuyt v D0 l nng lng phn ly quang ph.
10. Trong phn tch quang ph, khi xc nh cc nh ph, ti sao ngi ta thng biu din
0
1
ln
I
I

theo (tc l biu din thng qua mi tng quan gia 2 nh ph) thay v biu din n gin l I()?
Nu biu din trc tip I theo th sai s xut hin s rt ln v cng vch quang ph ph
thuc rt nhiu vo cc yu t bn ngoi v gn nh l lun bin ng, iu ny dn n vic o c v
phn tch rt kh chnh xc. Do vy, ngi ta thng tin hnh lp t s cng gia 2 nh ph
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hn ch ti a sai s pht sinh v t s ny gn nh c nh, t ph thuc vo cc yu t bn ngoi.
Ngoi ra, ngi ta cn ly thm ln ca t s cng , mc ch l n gin ha vic tnh ton v
xut pht t nh lut Lambert-Beer: I
t
= I
0
e
-d
, ly ln s gip trit tiu hm e m.
11. Nu mi quan h gia ph Raman v ch s iot
S hin din ca cc lin kt i trong cc axit bo cha bo ha cung cp thng tin xc nh
cha bo ha. Khi x l vi iod, hai nguyn t iod gn vo trn mi lin kt i ca axit bo cha bo
ha. T s phn t gam c o vi cc lin kt ny c gi l ch s iod. Ch s ny cho bit mc
cha bo ha ca cc sn phm cha cht bo. Gi tr ch s iod cng cao th cha bo ha ca cc
sn phm cng ln. Khi ch s iod tng th t s cng cng tng, n chnh l s tng cc axit bo
trong cc cht c nghin cu. Ghi ph FT Raman bit c t s cng gia 2 nh ph, t
suy ra ch s iod v bit c nng axit bo trong mu."
12. Gii thch ti sao trong cc ngnh cng nghip sn, thc phm, thuc, nhum, du ha, ngi ta
khng dng ph Hng ngoi kho st m dng ph Raman?
Cc sn phm ca cng nghip sn, thc phm, thuc, nhum, du ha u l nhng hp cht
cha nc. Ta bit rng, nc l cht tn x Raman yu nhng li cht hp th hng ngoi mnh. V
vy, dng ph Raman kho st cc sn phm ny s loi b c nh hng ca nc ln ph ca
cc sn phm, gip nhn c thng tin chnh xc v sn phm.
13. Cho bit i tng nghin cu ca l thuyt v Nhm i xng im v Nhm i xng khng
gian?
+ i tng nghin cu ca l thuyt v Nhm i xng im (Point Group Symmetry) l cc
phn t c lp, ring l.
+ i tng nghin cu ca l thuyt v Nhm i xng khng gian (Space Group Symmetry)
l mng tinh th, tc l tp hp c trt t ca cc phn t.
14. Cho bit nhng im khc nhau trong l thuyt v h dao ng gia c hc c in v c hc
lng t
+ Theo quan im c in th nng lng E = 0 khi v = 0. Trong c hc lng t trng thi
nng lng thp nht (v = 0) c nng lng l hv (nng lng im 0), y l kt qu ca nguyn l
bt nh Heisenberg
+ Nng lng ca mt dao ng t iu ha c th thay i mt cch lin tc trong c hc c
in. Trong c hc lng t, nng lng ch c th thay i theo n v hv.
+ Trong c hc c in, s dao ng ch gii hn trong parabol v ng nng s m khi |q| > |
q
0
|. Trong c hc lng t, xc sut tm thy q bn ngoi parabol l khc 0 (do hiu ng ng ngm).
Gin th nng ca mt dao ng t iu ha
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15. C th s dng ph Raman nghin cu cc mc quay trong phn t khng?
Theo gin nng lng trong phn t, mc quay l nhng mc nm gia hai mc dao ng,
cn mc dao ng l nhng mc nm gia hai mc in t. V nguyn tc, c th dng ph Raman
nghin cu cc mc quay trong phn t v ngoi tn x dao ng thng thng, chng ta vn c tn x
quay. Tuy nhin, khong cch gia cc mc quay rt nh, chu nh hng ln ca mi trng, c bit
l nhit , v vy, nhit thng rt kh thu c mc quay (nn ph cao). Do , vic kho st
cc mc quay cn tin hnh nhit cc thp.
16. Cho bit 2 yu t chnh thc y k thut Quang ph Raman pht trin.
K thut Quang ph Raman ch c pht trin khi:
+ Ngun kch thch pht trin. Hin tng tn x Raman c Chandrasekhra Venkata Raman
pht hin vo nm 1928 nhng mi n nm 1960, khi ngun sng laser ra i, n mi c quan tm
vo pht trin. Khi s dng nh sng laser lm ngun kch thch, tn x Raman pht ra c cng ln
c th ghi nhn c. Mt khc, vi kch thch bng laser, hin tng hunh quang do cc dch
chuyn in t (chng che ph Raman) c loi tr ng k.
+ My n sc, detector v my tnh in t pht trin. Cng vi s pht trin ca ngun sng
kch thch, s pht trin ca cc thit b khc trong h o quang cng ng gp mt phn khng nh
vo s pht trin ca k thut Quang ph Raman. My n sc quyt nh phn gii ca ph. B
phn chnh ca my n sc l cch t. Cch t c mt vch cng ln th cho phn gii cng cao.
Detector cho php ghi nhn tn hiu quang v chuyn i tn hiu thnh tn hiu in. nhy ca
detector cng cao cho php tn hiu nhng tn hiu quang cng nh. Cui cng, my tnh in t cng
l mt b phn quan trng, gip x l, hin th ph cng nh cc thao tc ty chn khc, gip cho vic
phn tch ph d dng, nhanh chng.
17. Khi bn chn mua mt my o Quang ph Raman, tiu ch u tin ca bn l g?
Tiu ch u tin khi chn mua mt my o Quang ph Raman l phn gii ca my, tc l
khong cch nh nht gia hai nh ph gn nhau nht m my cn c th phn bit c. phn
gii ca my do b phn cch t ca my quyt nh. Cch t c mt khe cng ln th s cho
phn gii cng cao.
18. Ta bit cch t c mt khe cng ln th s cho phn gii cng cao. Vy b rng ca khe c
gy nh hng g n ph thu c hay khng?
C. B rng khe cng nh th s cho phn gii ph cng tt nhng b li cng ph s
cng nh. Cn nu b rng khe cng ln th s cho cng ph cng ln nhng phn gii ph s
cng nh. Trong qu trnh ch to cch t, ngi ta lun quan tm n 2 yu t ny v ty vo tng
ng dng c th, ngi ta s c nhng thng s ch to ti u.
19. Ph quang hc ca mt my quang ph bt k thay i th no khi nhit mi trng thay i?
Khi nhit mi trng thay i, chng hn khi nhit tng, ni chung, mu vt v cc thit
b trong my quang ph u b gin n, v vy, ph ghi nhn c cng s b thay i. C th l ton
b ph s b dch chuyn v pha bc sng di.
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