I HC QUC GIA THNH PH H CH MINH

TRNG I HC KHOA HC T NHI N

KHOA VT L
B MN VT L NG DNG

SEMINAR: QUANG PH NG DNG

QUANG PH RAMAN

GVHD:PGS-TS DNG I PHNG

TS NGUYN VN NH
SVTH: TRNG VN THNH
MSSV:0413018
THNH PH H CH MINH 4/2007

1.LCH S QUANG PH HC RAMAN:

Nm 1928 ,chandrasekhra venkata Raman kh m ph ra hin tng m sau ny n
mang tn ng bng nhng dng c o ph rt th s . ng s dng nh sng mt tri lm
ngun sng v knh vin vng lm c-lec-t thu nhn nh sng tn x ,cn de-tec-t l
i mt ca ng .Ngy nay chng ta gi l hin tng tn x Raman .
Theo pht trin ca khoa hc k thut ,ngi ta tp trung nghin c pht trin cho
cc ngun kch thch . Trc tin ,ngi ta s dng cc loi n ca cc nguyn t nh
helium,bismuth,ch ,km lm ngun kch thch ,nhng thc t khng p ng c
yu cu v cng qu yu .Vo nhng nm 1930 , ngi ta bt u s dng cc n
thu ngn cho ph Raman .V d ngi ta thit k mt h thng kch thch gm bn n
thu ngn bao quanh ng Raman .
Vi s pht minh ra Laser (nm 1962), ngi ta nghin c s dng mt s loi
Laser khc nhau lm ngun kch thch cho tn x Raman . Cc loi Laser c ng
dng ph bin thi l : laser Ar+(351,1-514,5 nm),Kr +(337,4-676,4 nm) v gn y
nht l laser rn Nd-YAG,(1.064 nm).Vi ngun kch thch bng laser Nd-YAG ,hin
tng hunh quang do cc dch chuyn in t (m n c th che ph Raman) s c
loi tr mt cch ng k .
Khi u ghi nhn ph Raman ngi ta dng cc knh nh ,sau vo u nhng
nm 1950 ngi ta dng nhn quang in . Hin nay , trong cc thit b FT-IR v FTRaman hin i ngi ta s dng mt trong hai loi de-tec-t ch yu l DTGS v MTC.
e-tec-t loi DTGS hot ng nhit phng ,c khong tn s hot ng rng ,n
c s dng rng ri hn loi MTC. De-tec-t loi MTC p ng nhanh hn v c
nhy cao hn loi DTGS ,nhng n ch hot ng nhit nit lng v b gii hn v
tn s hot ng .Do ngi ta ch s dng n vo nhng mc ch c bit m thi .
Vo nhng nm 1960,vic nghin c h thng quang hc cho quang ph Raman bt
u c ch trng . Ngi ta s dng my n sc i cho cc thit b ph Raman bi
v n c kh nng loi tr nh sng nhiu mnh hn my n sc rt nhiu ln . Sau ny ,
tng cng hn na hiu sut loi tr nhiu ngi ta cn s dng my n sc
ba.Cng vo nhng nm ny ,cch t ton k cng c s dng tng hiu sut thu
nhn nh sng tn x Raman trong cc thit b Raman .
Ngy nay ,vi s pht trin vt bc ca khoa hc k thut , ngi ta c th thu c ph
Raman bng phng php bin i FT-Raman .Cc thit b FT-Raman c sn xut lp
ghp vi thit b FT-IR hay hot ng c lp nh mt thit b FT-Raman chuyn dng.

2 .DAO NG CA PHN T 2 NGUY N T :

Dao ng ca phn t l s dch chuyn v tr tng i gia cc ht nhn nguyn t
trong phn t i vi nhau .

Trong c hc lng t ,s dao ng ca phn t 2 nguyn t c xem nh chuyn ng

ca 1 ht c khi lng (dao ng iu ho ).
Phng trnh schrodinger ca mt h thng nh th c dng :

d 2
8 2
1

(E
k q 2 )
2
2
dq
h
2

gii phng trnh sng vi iu kin phi n tr ,h hn ,lin tc ,ta c :

-Nng lng dao ng
1
1
Ev hv (v ) hcv (v )
2
2
- Tn s dao ng :
1 k
1
k
v s sng v
v
2
2 c
v l s lng t dao ng , v=0,1,2,3,
- s hng dao ng :
1
Gv v (v )
2
- quy tc lc la : v 1
suy ra s sng ng vi chuyn di hai mc dao ng : v ' G (v ') G (v ") v
vy tn s hp th hoc bc x ca phn t dao ng ng bng tn s ca dao ng t .

3. HIU NG RAMAN :
Khi chiu bc x in t hv vo mt phn t , nng lng c th b hp thu hoc pht x .
- Tn x Rayleigh xut hin l do tng tc ca nh sng vi nguyn t .
- Tn x Raman xut hin l do tng tc ca nh sng ti vi lin kt trong phn
t .
Dng my quang ph ghi nhn ph tn x ngi ta thy :
- Tn x Rayleigh c tn s photon tn x tng ng vi tn s photon ti v c
cng mnh nht .
- Tn x Raman c tn s tn x khc vi tn s photon ti v c cng yu hn
.
Tn x Raman l mt loi ph pht x th cp v chia lm hai thnh phn : vch
stoke v vch phn stoke , trong vch stoke c cng mnh hn nhiu ln vch
phn stoke.
Ngi ta gii thch ph tn x Raman theo thuyt c in v thuyt c hc lng t .
Theo thuyt lng t
1
Nng lng dao ng ca phn t c lng t ho theo h thc Ev hv (v )
2
Mt bc x c tn s v0 chiu bc x mt phn t ,nng lng c th b hp th hoc
pht x .Khi nhn c nng lng ,phn t s b kch thch t trng thi c bn ln mc

kch thch dao ng cao hn (mc o),mc nng lng ny khng n nh ,do phn t
lp tc mt nng v quay v mc dao ng c bn ng thi pht ra photon tn x
.Photon ny c nng lng v tn s ging vi photon ti . y l tn x Rayleigh l s
va chm n hi gia phn t v photon ti ;l kt qu ca s chuyn di m trong
mc nng lng cui cng ca phn t chnh l trng thi nng lng ban u .
Tuy nhin ,c mt s phn t nhy v mc nng lng cao hn (mc kch thch)khng
phi l mc c bn m l mc v =1 .Photon tn x trong trng hp ny c nng lng
nh hn photon kch thch v cho mt vch stoke trong ph Raman .
Theo c hc lng t , s thay i cho php trong s lng t dao ng vi s chuyn
tip Raman l v 1 i vi mt dao ng iu ho .
Ngoi ra , khi phn t khi u trng thi kch thch v =1 ,hp th nng lng photon
ti v nhy ln mc nng lng khng n nh cao hn . Khi phn t tr v trng thi c
bn v =0 , pht ra mt photon tn x lm xut hin vch Anti stoke trong ph Raman.
Nh vy, tn x Raman l kt qu ca s va chm khng n hi gia cc phn t v
photon ti , m hu qu chuyn di l pht ra cc bc x c tn s (v0 vv ) c xc nh
bi quy tc lc la trong c hc lng t ( v 1 ). Tn x stoke l kt qu ca chuyn
di m trng thi nng lng cui cng cao hn trng thi nng lng ban u mt lng
Ev (l hiu nng lng gia hai mc dao ng ca phn t ) v do tn s ca vch
stoke l v0-vv .Ngc li ,nu trng thi cui cng ca phn tch kch thch thp hn trng
thi nng lng ban u mt lng Ev cho vch phn stoke vi tn s v0+vv .

Stoke

phn
Stoke

Rayleigh

d ch chuyn in t
(pht nh sng hunh quang)

hnh 1:s chuyn di cc mc nng l ng

HP TH

TN X
Khng n hi

n hi

Ev 0

Khng n hi

v1 v0 vv

v1 v0

V=1
hvo
hvv

Ev 0

Ev 0

v1 v0 vv

hv0
hv1

hv1
hv0

V=o

Hnh 2 : m hnh tm tt s chuyn di cc mc nng lng dao ng

gii thch cng vch stoke mnh hn nhiu ln cng vch anti-stoke ( nhit
bnh thng ), ngi ta da vo nh lut phn b Boltzmann Maxwell.
E
N N 0 exp( v )
KT
Biu thc trn cho thy hu ht cc phn t u trng thi c bn (trng thi nng
lng cp khng)mt s t phn t trng thi nng lng cao hn .
T , ngi ta thit lp c t l chnh xc cng gia 2 vch l :

I Anti stoke
v vv 4
E
(
) exp( v )
I Stoke
v vv
KT

4. SO SNH GIA PH HNG NGOI (IR)V RAMAN

Quang ph Raman v hng ngoi u da trn tn s dao ng ,song c hai k thut u
c nhng u khuyt im khc nhau .
Cc quy tc lc la khc nhau r rt gia hai loi ph .mt dao ng c th l hot
ng Raman hay hng ngoi hoc c hai .Cc dao ng i xng ton phn (hoc phn t
c i xng tm ) lun l hot ng Raman .
Mt s dao ng yu trong quang ph hng ngoi nhng li mnh trong Raman v
ngc li .Tr mt s cht c bit thng thng :
-Dao ng mnh trong ph Raman nu lin kt cng ho tr .
- Dao ng mnh trong IR nu lin kt ion .

Cc php o t l phn cc trong ph Raman cho thng tin v i xng trong mt dao
ng thng trong dung dch Quang ph hng ngoi khng c c tnh ny .
Trong quang ph Raman ch cn mt mu din tch nh l c th nhn c ph . y
l mt thun li rt ln so vi quang ph hng ngoi
Quang ph Raman rt thun li khi kho st cc mu phn tch trong nc ,v nc c
tn x Raman rt yu ,trong khi nc cho ph hng ngoi mnh .
i vi cc hp cht ht m v cc hp cht nhy khng kh ,cho vo ng thu tinh nt
kn ri thu ph Raman ,trong ph hng ngoi th ng thu tinh hp th bc x hng
ngoi.

5. MT VI NHC IM CA PH RAMAN
quan st c ph tn x Raman ,ngi ta phi s dng ngun laser cng sut ln .
iu ny c th to nn s nng cc b (lm chy mu )v s quang phn ly , c bit
vi ph Raman cng hng m tn s laser c iu chnh vo vng hp thu ca
phn t .
Mt s hp cht pht hunh quang khi chiu bng bc x laser .
Thu ph quay v ph dao ng quay vi phn gii cao trong ph Raman kh hn
trong ph hng ngoi .L do l ph Raman c quan st trong vng t ngaoa ,kh kin
m nhng vng ny rt kh thu c ph c phn gii cao .Trong nhng nm gn
y ,ngi ta bt u s dng cc cc loi laser hng ngoi (hoc cn hng ngoi )lm
ngun kch thch tn x Raman .
Thit b quang ph Raman t tin hn ph hng ngoi .

6. Hin tng hunh quang

Khi hiu ng Raman c khm ph ,ph Raman c nghin c pht trin thnh
php phn tch quan trng . Nhng thc t ,mu phn tch (hoc tp cht )c th hp thu
chm laser v pht ra nh sng hunh quang xut hin trong ph v ph Raman s b mt
di hunh quang rng v mnh che khut .
cng ca n c th ln hn 104 ln tn hiu Raman ,c th lm phng ph Raman cao
hn bnh thng .
Hin tng hunh quang xy ra khi c s chuyn di cc mc nng lng in t .

E2
E E2 E1

v0
E1

Hnh 3 : m hnh chuyn di mc nng lng in t

khc phc vn ny ,ngi ta a ra nhiu phng php khc nhau trong nhiu
trng hp :
Nu hunh quang do tp cht trong mu hoc mang mu sm ,dng ngun laser cng
sut ln ,chiu vo mu trong thi gian di c th loi b cc tp cht pht hunh quang
(nn ph c h xung ).
N t thn mu vt pht hunh quang , khi c s hp th ngun kch thch laser v
pht ra nh sng hunh quang .Lc ,ngi ta thay i bc sng ngun kch thch
thay i dch chuyn tn s .
c bit , hin nay ngi ta dng php bin i FT-Raman . Vi phng php ny ,s
dng ngun kch thch laser hng ngoi . Trong vng bc sng ny t xy ra s chuyn
di mc nng lng in t , tc l t xy ra hin tng hunh quang .

7.Quang ph FT-Raman
Gii thiu
i vi ph Raman thng c 3 vn :
- Ph Raman b che lp bi ph hunh quang .
- chnh xc v tn s rt km .
- phn gii khng cao.
khc phc cc vn trn ,ngi ta a ra phng php FT-Raman . Dng ngun
laser rn Nd :YAG lm ngun kch thch ph Raman v thc hin c giao tip vi cc
b phn Raman vi cc thit b ca ph FT-IR . K thut ny c Chantry v Gebbie
a ra ln u tin vo nm 1964 , nhng do thiu s pht trin v k thut nn 20 nm
sau k thut ny mi c p dng rng ri .
Cc hng ni ting trn th gii ch to cc my FT-Raman nh :
Bomem,Bruker,Digilab,Nicolet,Perkin -Elmer c nhng phn mm hin i tng ng

Nguyn tc :
Trong ph Raman thng , cng nh sng ph thuc theo tn s hoc bc sng .

Trong ph FT-Raman o cng nh sng ng thi ti nhiu bc sng c ngha l ta

xem nh ph ph thuc vo thi gian .Ph ny sau c bin i thnh ph Raman
nh vo php bin i Fourier c lp trnh trn my tnh .
Vi k thut FT-Raman , ta c th quan st c cng mt lc ton b ph .Trong trng
hp ny , phn gii , chnh xc v tn s v c bit nh hng ca hunh quang
c ci thin rt nhiu so vi ph Raman tn sc thng thng.

u khuyt im ca FT-Raman:
u im
-

Gim hoc loi tr nh sng hunh

quang
phn gii cao
Hiu sut cao.
Kh nng linh ng trong thc
nghim.
Cc vch stoke v phn stoke c
thu nhn mt cch ng thi .
Kh nng cung cp thng tin tn
s thp .
s dng cho IR v Raman trn cng
mt thit b
L tng cho cc cht hu c .
D s dng.

khuyt im :
-

Hp thu trong vng cn hng ngoi

nhy thp
Khng th pht hin c tp cht
hm lng thp bng php tr ph .
cng kch thch ph thuc vo
v4 .
Kh khn trong vic nghin cu
mu nhit cao hn 1500C v
khi mu b bao ph bi mt lp
en do nhit .

Thit b
Ph FT-Raman ca phn t c o bng quang ph k EQUINOX 55 c kt ni vi
b phn Raman FRA-106/S ca hng Bruker M ti phng phn tch trung tm ca
trng i Hc Khoa Hc T Nhin Thnh Ph H Ch Minh . Thit b ny khng dng
b phn cch t m s dng h thng giao thoa k Michelson vi cc hm bin i ton
hc Fourier x l ph .
Ngun sng kch thch l loi laser lin tc Nd :YAG c bc sng 1.064 nm , cng sut
0-2000mW . Vi ngun laser cn hng ngoi ny lm tn hiu Raman gim 16 ln so vi
laser kh kin c bc sng 514,5nm , v tit din tn x t l vi v4 . Dng bc sng
ny (cn hng ngoi )c u im l c th khc phc c hin tng hunh quang do
dch chuyn in t lm che khut ph tn x Raman cn kho st .
Detect c s dng trong thit b l loi DTGS .
Mt b phn lc quang hc trong thit b FT-Raman lc nh sng nhiu t ngun laser
, ng thi lm gim mnh vch Rayleigh (c cng bng 106 ln cng vch
stoke ).

Phng php ghi ph :

Quang ph k FT-Raman c iu khin bng my vi tnh nh vo cc chng trnh
dc lp trnh sn trn my , qua phn mm OPUS version 3.0 . Sau khi t mu vo gi
trong bung mu , ph ca mu ang quan st c hin th trn mn hnh vi tnh .

Mt thit b ngoi vi gn lin vi ph k cho php iu khin v tr ca mu sao cho cc

mi ph ti u nht .
Chm tia laser ngun ti bung cha mu v hi t li trn mu . nh sng tn x Raman
t mu c gng parabol thu nhn v i qua mt module lc , sau i vo giao thoa
k Michelson .
Ngun bc x sau khi i qua cng vo vng hng ngoi v hng ti b tch chm .
Trong trng hp l tng , ngun bc x ny s truyn mt na bc x v phn x na
cn li . Na phn x sau khi i qua mt khong L , s n gng c nh M , sau tr
v b tch chm mt ln na . Na bc x chuyn tip cng i qua mt qung L .tuy
nhin gng M2 ca giao thoa k c th dch chuyn dc theo trc quang . Sau chng
c ti kt hp li b tch chm . Chm tia ny c iu bin bng s dch chuyn
ca gng , sau hi t hon ton trn detect .
Nh vy , cng I(x) c th o c nh l mt hm s ca s dch chuyn x ca s
dch chuyn gng M2 khong cch (L) . S bin i ton hc Fourier c thc hin
trn my vi tnh . Cc ph o c lu vo my tnh di dng s s dng .

S khi ca quang ph k EQUINOX 55