Luận án Ứng dụng tin học trong phân tích phổ raman

-.D ~ 2 3 4 500 1000 1500 2000 2500 3000 3500 b -1Wavenum er, cm lfmh3.14.Ph6FT-Ramancuacaemiiug6Bc;tchd~mVi~tnamxii'19 Bang3.15.Di~ntkh caedinh1600cm-lvoi thaigianxii'19khacMali. 'Ph6sO'0ahinh3.12a,b. Ph6 Thai gian Din tkh dinh1600cm-l xii'19(phut) Thong NewZealand Bc;tchdm Vit nam aT 0 0,04134 0,02244 1 15 0,01667 0,00673 2 30 0,01124 0,00543 3 60 0,00801 0,00480 4 120 0,00634 0,00336 5 180 0,00275 0,00213 6 240 0,00124 0,00101 ChU(fnJ!3: Kef qua va blnh luan Luan anTie'nsf VatIf 101 800 N 0 'D 600 '3 (tJ ,q ~ 400 a; C t: (tJ E (tJ ~ 200 0 600 800 1000 1200 1400 1600 1800 Wavenumber,cm-1 Hlnh 3.15.Ph6Micro-Ramancuag6thongNew Zealand Bang3.15trlnhbaydi~ntichcuadinhph6d~ctninglignin1600 cm-lcuag6thongradiatavag6b~chdanVi~tnam0 cacthaigianxU'19 khacMall. Vi~ctinhdi~ntichdinhph6bi ch6ngch~pvoi nhau(Cl,!the haidinhV16vaV16')du<;jcthlfchi~ntheocacbuocnhusail : - VI hai dinh nay bi ch6ngch~pnhau,nen truoctienphai tach ch~p(deconvolute)hai dinhnay.Vi~cTach ch~phai dinhph6naydu<;jc thvchi~n b~ng cong Cl,!"Fit curves" voi thu~t toan Levenberg- Marquardtrenph'anmSmOPUS 3.0 [36]du<;jccai d~ttheoquangph6 kSEQUINOX55/FRA-106/S. - Sailkhi tachch~p,cacdinhriengIe V16va V16'du<;jctinhd~ntich b~ngcongCl,!"Intergration"cling thuQcph'anmSmtren theophudng thlicB. Di~ntichtinhtheophudngthucB nayla di~ntichcuavunggioi Chztanz3:Kefquavablnhluan LuananTie'nsfVatly 102 h~nboiduangGongph6,duangnSnvahaiduangth~ngsongsongvdi tr\lctungdu<;1cxacdinhboihaigiatribienla"ytkhphan. Sai s6 cila cac ke'tqua tinhdit$ntkh theophudngphapnayphv thuQcvaodQchinhxaccilathie'thi. Hinh3.16a,b la cacduangGongbiSu di(§nslj phVthuQccila dit$n tkhdinh1600cm-ltheothaigianxii'ly cilahai lo~ig6khaosat.Quacac ke'tquatren, taGgiaco nh~nxetnhusau: - Tri s6dit$ntkh dinh1600cm-lgiamra"tnhanhtrongkhoangthai gianxii'ly ill'0 - 50phtitva saudogiamch~md'an.Dit$ntkh dinh 1600 em-lcilab~chdaTInh6hdncila thong(0 clingthaigianxii'ly) va t6cdQ giamtheothaigiaxii'ly clingnhanhhdn. - Cacdinhvung 1600cm-lcilacacm~uxii'ly vdi thaigianill'180 phuttrodih'aunhuma"th~n,nhungtri s6dit$ntichtrenbang3.15v~ncon khackhong.Nguyennhanladotinhit$unhi(§ut~ivi tridinhkhaosat.BS kh~cphvcvin dSn'ay,phaitangs61'anquet(scan)khi ghiph6. - Ph6 FT-Ramancila g6 thongva b~chdaTIsau thai gianxii' ly kh6ngco g'ikhacbit$tvdi ph6 cila m~ubQtgia"ydu<;1csanxua"t~iNew Zealand,ngo~itru Quangn'enco Qo~nhdi dangcao,nguyennhfmla do cacm~ukhao satchuadu<;1ctiy tr~nglien phatsinhhit$ntliQnghuynh quang.PhVIvc B4so sanhph6FT-Ramancila B~chdaTIVit$tnamdff10~i he'tligninvdiph6cilabQtgia"yNewZealand(GRADE NBKP). Cac ke'tqua ph6 FT-Ramanthudu<;1cmQtl'annua co thSkh~ng dinhphudngphapFT-Ramanvungh6ngngo~ig'an(NIR) co l<;1ithe'ra"t nhi~usovdi phudngphapRamantans~c0 vungkhakiSnla h~nchS .... Chrtanf!3: Ke'tqua va binh [win Luanan Tie'nsi Vat[2.103 duQct6idahi~ntu'dnghuynhquangkhi khaosatnhunghQpch(t hUllcd, hQpchfftmangmall,cacpolymer,... 0.025 0.015 a-G6thongNew Zealand 0.020 'E 0.010 u 0 0 0.005I.D ~ 0.000 CLI 0 c... 0.025 ...c u '.;:: 0.020c: <CLI' 0 0.015 50 100 150 200 250 0.010 b-G6 B<}.chclanVi~tnam 0.005 0.000 0 50 100 150 200 250 Thaigianxu 19(phut) II'mh3.16.51fph\!thuQcdi~ntkh dinh1600cm-IvaothaigianxU'If. Tren cd so di~ntkh dinhph6d~ctn/figph6FT-Ramancualignin (1600cm-I),c6 th€ theod6i duQCquatrlnhtachchie'tcellulose(1o~ibo lignin)tUg6va tUd6xacdinhduQcthaigianxU'If t6iUu.Tit hlnh3.16a, bcoth€ suyra r~ngthaigiannayla khmlng180phutchocahai lo~ig6 thongvab~chdan. Ty l~thanhph'anlignintrongg6b~chdaDth(p hdntrongg6thong vathaigianxU'If (1o~ibohe'tlignin)clingnhohdn. mm Chztcmf!3: Ke'tquavablnhluan Luan an Tie'nsi Vat11.104 3.5.KmO SAT pHUc THE SIEU DANFULLERENE- MERCURIC IODIDE (C6O,HgIz) PhantU'fullereneC60(saudaygQiHitla C60)co tinhd6ixungcao, thuQcnhomd6i xungIh(hinh1.9ph'ant6ngquail).Tinh tmlnb~ng19 thuye"tnhom [7] d6i voi mQtC60co l~pcho ke"tqua la 174modedao I dQngehudntdedu<;JcbiSudi~nnhusan: fvib(Ih)=2Ag+3FIg+4F2g+6Gg+8Hg+Au+4FIu+5F2u+6Gu+7Hu. (3.3) Ke"th<;JpbiSudi~n(3.3)voi bangd~cbiSucuanhomIh,co thStha'y r~ngchi co 42 modela hoc;ltdQngRaman(2Ag,8Hg)va 12modela hoc;lt dQngIR (4FuI)[62].Nhuv~y,co thSdl1dmlntrongph6RamancuaC6o phaixua'thi~n10dinhph6baag6m2dinhkhongsuybie"nAl va8dinh suybie"nb~cnam Hg. Trongph'anay,truoctienchungWisekhaosatph6micro-Raman cuaC6o,ke'th<;Jpvoi tinhtoanab initiodS giai doanph6 va quyke"td6i xung.San do se nghienCUllsl1"xen" (intercalation)cua phantii'HgI2 VaGca'utrUccua phan tU'C60,tilc la sl1tc;lothanhphuc thS (C60,Hgh). 3.5.1.Chuftnhi mfiu. Phuc thS (C6o,HgI2)co thSdu<;Jcdi~uche"b~ng2 phudngphap: Phu'dngphapbay hdi va phudngphapfiling.Ca hai phudngphapdi~u chSnayd~udu<;Jcthl1chi~ntc;liphongthlnghi~mHoa 19phantU',Bc;lihQc BordeauxI , CQngboaPhap. '::hztlJnf?3: Kit quavabinhluan Luan an TieTzsf Vat ly-'105 3.5.1.1.Phudngphapbayhdi. Cho C6Ova Hgh voi luQngthkh hQpcungboa tantrongdungmoi ::::S2.Sando chobayhdihS'tdungmoi (trong10gia), chungWi thuduQc nhungh~ttinhthenhoC6oco s11"xen" cuapMintUHgh vaoca'utrUccua [10. 3.5.1.2.PhudngphapDung. Can mQtluQngm~uthkh hQpC6ova Hgh, sando d~tC60vaomQt fauva HgI2vao mQtd'aucon l~icua 6ng silica voi duangkinh 5 mm, K ;hi'eudai 50rom.OngduQcrutchankhongWi khoang10mmHgvahall inl~ib~ngdengas.Trongquatrinhhutchankhongvahall,c'and~td'au ~ngsilicacochuaHghvaobinhDewarcochuaNitdlongdeh~nchS's11 dehdicuaHgh. OngduQcfilingtrong100 nhi~tdQ205°c (nhohdn Inhi~tdQnongchaycuaHgI2,259°C)trongthaigian48 gia.M~uC60Iffy rasanthaigiann'aydil co s11xen vaocua Hgh nhutrongphudngphap tren. 3.5.2.Ghi ph6micro-Raman. Ph6 Raman duQcghi b~ngquangph6 kS' micro-RamanDilor LABRAMnhudil sad\lng0 ph'antren.De tranhchom~ukhoibi pha huy,chungWi ghiph6Ramancuacacm~u0 congStittlaserra'ttha'p (9 ~W),thaigian do vila phai (90 s), GQtkh l\llon (90 l'an). 3.5.3.TfnhtoaDluQngtitabinitio va quyke"t061xung. Nhucacph'antrudc,bell c~nhvi~cdo ph6th11cnghi~m,chungtoi da:thvchi~nvi~ctinh loan luQngtii'ab initio b~ngbQ chudngtrinh Gaussian98vdi maGly thuyetHF vah~hamca siJ la STO-3G. Daylah~ . ~- ~ ,.-=- ChUClnf!3: Ktt (IUdva binh luan LuananTitnsfVatIi. 106 hamcd sdthuQc10~iddngian.Ly dophaisadl,mgh~hamcdsdnay1avi phantii'C6O1aphantii'khaIon (60nguyentii'),ne'usad~ngh~hamcd so Ionthi t6nrfftnhi'euthaigiOdShoantfftvi~ctinhtoan(hdn2 tu'an1<S). M~cdii ddngian,nhungh?hamcdsanayv~ndambaaduQcdQchinh xacc'anthi6t.Phl,lll,lcC21achudngtrinhchovi~ctinhtoanvuanentren b~ngbQph'anm'emGaussian98.Tu ke'ttinh toannay, c6 thSdl,l'doan du'Qcac dinh ph6, kh~ngdinh cac k6t qua tinh toanb~ng1ythuye'td tren. Bang3.16.K6t quatinhtoan1uQngtii'chophantii'C60. Caemode daodQng 1-5 18-22 23 57-61 71-74 105-109 121-125 148-152 153 170-174 T~ns6 (em-I) 269 453 493 746 791 1151 1332 1480 1502 1707 Cu'ongdQ (a.u) s6modeI DQkhii" D6lxung ;: Ktanso phanet;le 12.40 2.33 5 5 Hg Hg 0.75 0.75 73.29 1.77 0.00 0.75 1 5 Ag Hg 6.24 14.40 0.75 0.75 5 5 Hg Hg 31.17 5.65 5 5 Hg Hg 0.75 0.75 646.60 42.45 0.00 0.75 1 5 Ag Hg BS so sanh,chungtoi ding th\fchi~nmophongph6Ramanb~ng ,thudngtrinhmophongnhudfin6i tren(phl,ll,lcC1)chophiintii'C6OtU ~acd111i~utinh toan. - ChLttYnJ!.3: Kef clUd va binh Luiin Luiin an Tie'nsf ViitLf 107 Bang3.16trinhbayke'tquatlnhloanabinitiocaefans6ho'.ltdQng RamanehophantiYC6o.Tii' bangke'quanay,chungtoi co ffiQtsO'nh~n xetsan: I T6ngsO'modeho'.ltdQngRamanla 42(t6ngeuaeQtthli4).Ke't IquanayphilhQpvdi tlnhloan19thuye'tatren. I Hai modedao dQng thli 23 va thli 153(theothli t1!euake'qua tinmhloanabinitio-Gaussian98)d~ucodQkhii'phanevep =0, tilela phanevehoanloanva co eu'ongdQm'.lnhnha't.Do do,co th~kh~ngdinh ngayr~ng2 modedao dQngnay thuQed6i xling Ag vdi fan sO'Raman tUdngling la 493em-Iva 1502em-I. Ta't ea 8 fan sO'con l'.li 269, 453, 746, 791, 1151, 1332,1480, 1707em-\ m6i fan sO'd~uco sO'modedaodQngnQitu'dngling Ia 5(cQt4), haynoi eachkhae,caefansO'daodQngnayco dQsuybie'nb~c 5.M~tkhae,ta'teachungh~sO'khii'phanevep =0.75=% (eQtthli 5), nhu'v~y,daodQngnayeh~e h~nsethuQev~d6ixungHg. Nhu'v~y,de'nday,co th~ehor~ngke'tqua tlnh loanab initio Ia philhQpvdi ke'tquatlnhloanb~ngphu'dngphap19thuye'tnhomatren (bieudiSn3.3). 3.5.4.Ph6 micro-RamancuafullereneC6O. Cae dinh ph6 cd ban euaC6od~un~mtrongvung tU 250 -1600 cm-I(hinh 3.17a).d vungn'ayco 2 dinhm'.lnhla 1464em-Iva 491cm-I. Sosanhvdi ph6 mo phong(hinh3.18),co th~tha'yngaydug haidinh naytu'dngling tu'ant1!vdidinh1504cm-Iva 493em-I,dodo,co th~cho r~nghai dinhnay la hai dinhthuQedaodQnghoanloand6i xlingthong mybie'nAg. ChuanJ!3: Kit quavaQlnhluan LuananTiin sfVatIf 108 20 ..".'"' ..". ~ ::J 0 15 ~ c- o;;; c: Q) :s 10 c: co E co c.::: 5 0 200 400 600 800 1000 1200 1400 1600 1800 b -1Wavenum er, em Hinh3.17a.Ph6micro-RamaneuaC6Ovung250-1600em-I Dinh 1464em-Ila daodQnghoatri eualien k€t C=C.Chli Y r~ng, dinhnay, 1464em-I,tha"phdnkha nhi~usovdi fans6d~etru'ngeuadao dQnghoatrieualien k€t d6iC=Cbinhthu'ongmanoco fans6n~mtrong vung1660em-I.Di~unaynoi len d~etru'nglien k€t d6i co tinhddneua caelien k€t CC trongC6O.K€t quatinhtoan1u'<;5ngtU'dffkh&ngdinhnh~n xettren,cv thSla theotinhtoanabinitiodQdai lien k€t ling n6id6iC=C 0 cuahinhngugiaela 1.4628A vaeuahinhIvegiaela 0 1.3760A, trong 0 khidon6id6iC=Cbinhthu'ongcodQdai1.3300A [17,20].Ngu'oitagQi n6id6i co tinhddn naytrongC6Qla n6i 1.8boi VI di~ntti'phanb6 tren to~lllquadiu, kh6ngt~ptrung0 n6id6idosl!co m~teuanhiYngm~tngu giac[62]. "- 0 "- 0\ 0\ 0\ ;; 0 "- 0 '"' coN "- "- - ..". '"' ..". ..". N 0 0\ - + - N '"' + + ..". lr\- - r- \ Chl1anf!3:Ktt Quavabinhiuan i LuananTitnsfVatif. 109 Cacdinhph6khacnoichungcocu'ongdQra'tye'u,trongd6dinh 267cm-l (d6ixungHg)cothedu'QCsli'd\lnglamdinhd~ctru'ngchovi~c phantich. 50 "- ... co N "-'"'"N '3 <1i40 C;- °;:;:; CI.) E 30 c: <I) E <I) 0::: b) ..."-'" N '"M'"N co... M20 10 0 2200 2400 2600 2800 3000 3200 3400 b -1Wavenumer,em II'mh3.17b.Ph6micro-Ramancua C60vung2600-3250cm-l Vung2600-3250cm-l(hlnh3.17b, cu'ongdQda:du'Qcnhanlen 50 fan)lavungph6cuacacdinhph6doho~fanvacacdinhph6dost!ke't hqpcuacacdaodQngcdbanke ca nhungdaodQngkhongxua'thi~n trongvung cd ban. Vung n'ay du'QcgQi la vung lu'Bngphonon (bi-phonon).Bi'eunayco thekh~ngdinhdt!atrenke'tquatlnhtoanlu'Qng ill'ab initio, VI r~ngcac fan sO'cd ban chi xua'thi~ntrong vung tU 269cm-lde'n1707cm-l(bang3.16). DS dangnh~ntha'yr~ng,trongvungcd banxua'thi~nhdn10dinh ph6theenhu'tlnhtoanly thuye'tnhomva dt!deanb~ngtinhtoanlu'Qng Ch~(cmJl3: Ke'tCluavablnh[win LuananTie'nsfVat[f 110 ill'ab initio d tren.Co thStha'yding, bell qmh OOungdiOOcd ban,xua't hi~nmQts6diOO000,C\lthSla diOO707cm-Iva dinh1689cm-I.Nguyen nha.nco thSla do st!d6ixlingc'aukhanghoantoancuaC6ohayco thSla dohQat'anhaydo st!kt h<;1pcuacacdaodQngt'ans6tha'p.Ktt quatinh loanhi<;1ngtU'ab initio khang co cac diOOnay. N a U"\ a co .... M M U"\~ "" '" ~~ " " + + U"\ N M M \ "a" 400 600 1400 1600 1800800 1000 1200 Wavenumber,cm-1 mnh 3.18.Ph6RamanmaphongcuaphantU'C60 Trong ph6 Ramancua C60khangco dinh nao tu'dngling vdi C70 ch~ngh:;lnnhli 1568,1226,1180,260 cm-I [41,46,62],do do co thS kh~ngdiOOdingC60dangkhaosatla tiOOkhitt, khangl~nC7o. 3.5.5.Tac dl;mgtlidngh6giuaC6OvaHglz. ? d d:;lngtt!do, phantii'Hglz g6m3 nguyentU'thfinghang,thuQc nhomd6i xling D.XJh.Theo tinhtmincuaK. Nakamoto[86]va tinhtmin 0.14 0.12 '5' 0.10 ttI....... 0.08 "Ci) c: Q) 'E 0.06 c: ttI E 0.04 ttI 0.02 '"N I 0.00 , 200 ChU:(/nf!3: Kef Cluava blnh luan LuananTitnsfVatly 111 hi<;1ngtU'ab initio (mr1cly thuyetHF, h~hamC(jsiJ LANL2DZ i) phantU' n'ayc6 badaDdOngcdban,trongd6c6hai daDdOngkhongsur bi€n Lg, L.umOtdaDdOngsur bi€n b~chai TIu.Theo nguyenuk, phantU'nay thuQcnh6md6i xungDoohnenchi c6 VI(Lg)xua"thi~ntrongph6Raman. Nhlingthvct€, khi 0 thSra:nhay thSlong, ca 3 fansO'VI(Lg),V2(TIu)va V3(Lu)d~uxua"thi~ntrongph<5Ramanboi VI 0 hai thSn'ay,m6iphantU' n~mc~nhk~cac phantU'khac do d6 c6 xay ra tacdOngdipole-dipole gaynensv thayd6i Hnhd6i xung. A. Loewenschuss[78] da:ghi ph6 RamancuaHgI2trongmatrixkhf trd,trongkhi d6chungWi ghiathSra:n. Hinh3.19la ph6 RamancuaHgh 0 thSra:n.Cack€t quadu'<;1cli~tke trongbang3.17. Bang3.17.Cact'ansO'cdbancuaHgh (cm-I). Binh V2n~mavungt'ansO'tha"p,khongthSghidu'<;1cb~ngthi€t bi Ramanay,nhu'ngvdiHnhtoanabinitiochungtac6du'<;1cV2=46cm-I. Binh 105cm-I (hlnh3.19)la do plasmacuakhf Argon tronglaser 'chthich. Ph6Ramancuam~udu'<;1cdi~uch€ b~nghaiphu'dngphapn6itren hlnh3.20),c6 nhi~uthayd6i so vdi ph6cua C6otinhkhi€t (hlnh3.17), H~hamcdsO'naythichh<;1pvdi caenguyentii'n~ngtuchuky 4 c1iabangphanlo~ituiinhoan. VI(Lg) V2(TIu) V3(Lu) Ref. 158 63 237 [69] 156 - 235 Do tronglun annay 149(Raman) 46(IR) 224(IR) Tfnhtoanabinitio Chl(l1n~3: Kit qua va binh Luan LuananTiin SlVatLx112 d~ebi~td vungdaodQngboa triod do,ngoaidinh1467em-I,conthffy xuffthi~nthemdinh1458em-I.Cu'ongdQtu'dngd6igilia2 dinhn'aykhae nhaumy theo h~tm~udu'Qedo (sau khi du'Qedi~uehe').Tren cd sd nhungdli ki~nn'ay,chungtoico th6suydoannhu'sail : Slfthayd6iph6noitrencoth6labi6uhi~ncuaphanlingtu'dngh6 giuaC6ova HgIz. ~ U) U) M N 100 150 200 Wavenumber, cm-1 250 300 Hlnh3.19.Ph6micro-RamaneuaHgIz Slf thayd6ieu'ongdQtu'dngd6igiliahai v~chn'aymy theoh~tm~u du'Qcdo,chungtom~udi~uche'khongdu'Qcd6ngnhfft. T'ansO'daodQngcualienk6tCC giamxu6ng,tUdocoth6suyra r~ng,mQtph'andi~ntti'dffchuy6ntUlienke'tCC quaphantti'HgIz.BdiVI khichuy6ndi~ntU'di thl h~ngsO'Ilfc se giamva tfftnhient'ans6dao dQngsegiam[6].Clingvlly dodo va doslf tu'dngquailgilia t'ans6dao 6 I .,., 5 ..-.. :J 4 ro........>....... 'w 3 c: Q.)...... c: c: 2 ro E ro 0::: 1 0 ChU{fflJ?3: Ke'tQUQva binh fwin Luanan Tie'nSI VatIi. 113 dQngboatrivadQdailienktt CC, chungtoichodings11tu'dngtacgiua C6ovaHghdillamchodQdailienktt CC tanglenmQtit. 60 co'" "-- '".... /' '" N .... ....'"'" N'".... 800 1000 1200 Wavenumber,cm-1 lI'mh3.20.Ph6micro-Ramancuaphucthe(C6o,Hgh) 400 600 1400 1600 trongvung200-1600cm-I Khi khaosatph6cuaphucthe0vungfans6thffp(HInh3.20),co thethffycomQtvaithayd6inho,d~cbi~tbellqmhdinhph6267cm-Ico xua'thi~nmQtdinhnho0 fans6 251cm-I.DiSu n'ayco thelienquailde'"n tu'dngtacgiuahai phanhi'.Tuy nhiende kh~ngdinhdiSun'ayc'ankhao satky hdnvungph6thffpnoi tren. Nhu'v~y,mQtl'annua,ktt hQp19thuyttnhomvoi phu'dngthuctlnh toanhiQngtti'ab initiora rangco thedl!dondu'Qcs6dinhph6,cu'ongdQ vaquyke'"td6i xungchocacdinhph6Ramanco khanangxua'thi~ncho C60,hi do lamcdso chovi~cnghienCUllcacphucthecuano. 50 ......... ::J 40CtI'-" >.-- .00 30c: Q)-- c: c: 20CtI E CtI 0::: 10 1 \ 0 ---,- 200 Chl((/nZ 3: Kef quavablnhiuan Luanan Tie'nsi Valif 114 B~ngHnhloanabinitiocoth€ dt!doandu'9Ccacdinhph6fans6 tha"pdo daodQngcuacacnguyentti'n~ngt~olienmakhongth€ phat hi~ndu'9cb~ngquangph6ke'micro-R_amanthongthu'ong.Trongtru'ong h<;1plu~nannayla phantU'Hglz. ChungWi mu6ndiSuche'va nghienCUllst!ph6ih9P giuaC6ova HgIz.Ph6Ramancuam~ucha'tdiSuche'co st!thayd6i,st!thayd6inay lienquailde'nst!com~tcuaphucth€ (C6o,Hglz).St!giamfans6boatri cualienk6tCC chophepchungWisuyracost!tangdQdailienk6tboa hQCcuaCC dok6tquacuast!chuy€n doi di~ntU'tUphantU'C60d6nphan to'Hglz.DiSu nay tu'dngtt!vdi ke'quacua Haddonva cQngst![54]khi khaosatph6RamancuaC6odu'9cphat~pvdiRb. Tren ph6 cua phuc th€ (C6o,HgIz), ph6 rieng cua HgIz khong hi~n f6,coIe chinhVIph6Ramancuanora'tye'usovdiph6cuaC6o. mm ChU(JfU?3: Ke'tqua va blnh luan Luanan Tie'nsi Vatly'115 ? , '" ? ,,' 3.6.KHAO SAT PHO MICRO-RAMAN CUA H(1P CHAT PM T QUANG GADOLINIUM PHOSPHATE. B€ khaosatph6Ramancuah~th6ng(Gd2O3-P20S),trudch6t chungWiphantfch,giaidminph6RamancuaGdPO4(1:1)dt!atrenHnh "tUdngquan"cuacacnhomdi€m va trenk6tquaHnhloanb~ngphtidng thucltiQngtii'abinitiotheomohinh"phantii'nQiti6p". Gadoliniumphosphate(GdPO4)la mQtlo(;liorthophosphateda't hie'mthtiongdtiQcdi"euch€ b~ngphtidngphapdongnhi~tdQcao [45]. Theak€t quado nhieuX(;ltiaX thl GdPO4thuQch~ddnta co ca'utrue monazite,tUdi~nPO4hdi bj bi6n d(;lng,nhomkhonggian la P21/n(14) 0 0 0 voicaethongs6m(;lng: a=6,6546A; b=6,8486A; c =6,3372A va ~=103,50[27]. Ph6daodQngnoi chungva ph6Ramannoi riengcuaGdPO4dtiQc thShi~nchuy6ula ph6cuacacnhomPO4.Ph6daodQnglien quaild6n Gdxua'thi~nafans6ra'tha'pvacoctiongdQra'ty6u.Dodo,trtidclien chUngtoi se HnhloancacdaodQngcdbancuaion PO~-t1fdo va trong m~ngtinhth€ GdPO4.Cack6tquatinhloansedtiQcdunglamcdsokhao satph6Ramantht!cnghi~mcuaGdPO4.Ion PO~-t1fdoco d(;lngXY 4ca'u trUetUdi~nsemantheod6ixungTd[3].Trongkhi doXY 4tUdi~ntrong tinhthecoth€ khongcond6i xungTdm1a.Trongtht!ct6,Hnhd6i xung cilachungsecokhananggiamdi,thongthtiongsebi€n thanhnhomcon kh6ngfamthtiongcuaTd[83]. :hl((JllZ3: Kit quavabinhiuan LuananTiensfVatif 116 61 a.;I: hK ~... leuc e mau. Cacphakhacnhaucuah~tho'ng(Gd2O3-P2OS)du<;icdi~uche'b~ng hudngphapphanlingtrongphar~n0 nhi~tdQ 700-1450°c saukhi cac fmhph'andu<;icboa tantrongaxitnitricd~md~cva bayhdi chokho. achoachfftband'auIa NH4H2PO4(99%minimum)cuahangMERCK; d2O3(99,999%)cuahangJOHNSONMATTHEY; Y2O3(99,999%)cua angRHODIA va Eu203(99,99%)cuahangACROS. Toan bQquatrlnh i~ucht naydu<;icchungtoi thl!chi~nt~iPhongthinghi~mHoahQcv~t ~ucod~c,CNRS, 33608Bordeaux-Pessac,CQngboaPhap. .6.2.Chiph8micro-Raman. BuQc g~n voi mQt kinh bien vi quang hQc, quang ph6 k€ 'cro-Ramanco thekhaosatdu<;icnhungm~unhovoi kich thuocco 1/.l. °do,d6ivoinhungm~ukhongthu'anhfft,cothekichthichtrennhung lingmyyc'ankhao sat[58].Cac ph6Ramantrongph'annayduQcghi fenDILOR LABRA1\1 (Trung Him Khoa hQcV~t li~u,Nghla do, TiI iem,Ha nQi)voi ngu6nlaserkich thichla He-Ne buocsong632,8nm o~tdQng0 15 mW va detectorCCD; va trenquangph6k€ micro- amanOMARS 89(thuQcPhongthinghi~mHoa-Ly phantU',B~ihQc ordeauxI, Phap)voingu6nlaserionArgonSpectra-Physics2061buoc song514,5nmva laserHe-Nebliocsong632,8nmho~tdQng0 cong sua't400mWva voi detectorCCD. BQphangiaicahaimayla 3cm-I. 3.6.3.Mo hlnhtlnh toaD. DekhaosatcffutruchlnhhQcvacacye'uto'do'ixlingcuamQtphan nrho~cffiQtion tli di~n0 cacdi~uki~nkhacnhau,chungWi sadl,mgmo ChU:lJnf! 3: Ktt CluavablnhLuan LuananTitnsfVatLi 117 hlnhma0 donodu'Qcd~tnQitie'ptronghlnhl~pphu'dng.Ne'ud6ixung cuachunggiamtitTdxu6ngD2d,thltacothexemphantU'(ho~cion)nQi tie'ptrongmQthlnh l~pphu'dngbi lambie'nd~ngdo slfnenVaGva gHin racuahlnh l~pphu'dngtheotrvc Z. Hlnh 3.21trlnh bay ma hlnh cua chungWidu'aradekhaosation PO~-. Theomahlnhnay,khihlnhngo~itie'pIa l~pphu'dngthlnhomd6i xungcuaphantU'sela Tdvakhino la hlnhkh6ichITnh~t(bigianho~c nen)thlnhomd6ixungcuaphantU'baygio sela D2d.. Z(S4,C2) :~5 @ :0 . :P y(C2) x(C2) dy 3- Hlnh3.21.Ma hlnhtinhtminchoionP04 3.6.4.Ph6 RamancuaGdPO4(1:1). 3.6.4.1.Ph6RamancuaionPO~-tl1do. N6u0 tr~ngthaitlfdo,ion PO~-secod6ixungTd[3,83].Trong tnionghQpnay, sa dvngphu'dngphaptlnh toan19thuye'tnhom[5,38] thotha"yding ion tlf do nayco 9 modedaodQngehudntdethuantheo biSudi~n: ChllcJnJ! 3: Ktt CluavablnhLuan Luanan Titn si VatLx118 r vib(Td)=At +E +2F2 (3.4) I Nhu v~y,thco (3.4) ion PO:- tI! do c6 b6n dlnh phil Ramancd ban. Bang 3.18 trlnh bay fan s6 cua cac dinh ph6 Raman quail sat th1;lc nghit?m[86]va ke'tquatinhtoanb~ngphu'dngphaplu'qngt1Yab initio0 milcHF (Hartree-Fock)vahamcdso6-31++G(d)choiontt;tdonay.Hai da'ucQng(+)0 hamcd soco nghlala hamcd so 6-31G(d)du'qcQng themvao hai hamkhuechtan,mQthamchocacnguyent1Yn~ngva mQt hamcho cacnguyent1Yhydro.Ht?hamcd so nhu'the'nayrfftthkh hqp chocacanion,cacht?th6ngcotkh dit?nam,...[49].Chliyr~ngphaicho giatri -3 (dit?ntkh cuaion PO~-)va 1(dQbQispin)vao0 dulit?uvao "Charge& spinmultiplicity". B6ndaodQngcdbannoi trendu'qcmotanhu'tronghinh3.22du'di day[58,86]. vL v\(A\) v2(E) v3(F2) v4(F2) Irmh 3.22.CacdaodQngchugntAccuaion PO~-tt;tdo. D6i vdi ion phosphatett;tdo,dinhVt=938cm-l la daodQnghoa tricualienketP-O vacocu'ongdQm~nhnha't.Benc~nhdo,theoket quatinh toanab initio chi ra r~ngdao dQngnay ht?sO'khli'phanc1;lc p=0, tilc la daodQngnaybi phanc1;lchoantoan.Do do,co th€ ketlu~n Ch"'(JnJ!3: Kef quavabinhIuan Luanan Tie'nsf VatIi. 119 dayla daDdQnghoantoand6iKungAI. Binh V3=1064cm-I1adaDdQng ,cogianba"td6i Kung.Con cacdinhV2=420cm-Iva V4=567cm-lacac ~odedaDdQngbie'nd~nggoc.Dlfatrenke'tquatlnhtoanabinitioco the ~€ dangquyke't d6iKungchocacdaDdQngcdbanV2,V3,V4nay(nhu'0 !llVC3.1).Ke'tquadu'QCtrlnhbaytrongbang3.18. JIang3.18.T'anso'Raman(cm-I)cuaionphosphatetlfdo. Blnh ThQ.'cnghi~m[24] Tinhtmln Dol ph6 Tans6 Cu'ongoQ Tans6 Cu'ongoQ xUng V2 938 420 rm y 903 404 17.90 0.90 AlVI E y 987 578 16.35 0.32 F2 F2V4 1017 567 mV3 nn:ra'tm:;mh;m:m~nh;y :ye'u. 3.6.4.2.Ph6RamancuaionPO~-trongm~ngtinhth~. ~Tinhtmlnblingtvthuy~tnh6m. Khi 0 trong m~ngtinh the, ch~ngh~nnhu'cac orthophosphate GdPO4,EuPO4,YPO4 thlion PO~-seco d6iKungD2d[24,83].Tinh toan st!phanb6 cacmodedaDdQngb~ngh~congiliuc Herzberg(ph\ll\lcA3) nhu'0 cac ph'antren,chi ra r~ngtrongtru'onghQpnay ion PO~-co 9 modedaodQngco bieudi€n : r vib(D2d)=2AI+ Bl +2B2+2E (3.5) Nhu'v~y,theo(3.5)va ke'thQpvdibangd~cbieucuanhomD2d,co th6dlf doandng trongph6 Ramancuacac tinhthe orthophosphatese --- --- ChLtlJnf!3: Ke'tQuava binh iuan LuananTie'nsfVatif 120 xuffthi~nbaydinhcdbancuaion PO~-(haidinhAI, rnQtdinhBI, hai dinhB2va hai dinh suybie'nb~chai E) thayVI b6nnhu'0 tren.Nguyen nhanla co sv tachdinhph6dod6iKunggiarntUnhornTdxu6ngnhorn D2d[83].Dvavaotinhcha"ttu'dngquail(correlation)ginacacnhorn,trong trlionghQpnay la nhornTdva nhornD2d,co th€ xac dinhdu'Qcphu'dng thUGcua sv tachdinh ph6 do sv giarnd6i Kung.Bang tu'dngquaild6i xungTd-D2d[44,46,94]chiradingkhi d6iKunggiarntUTd xu6ngD2dthl daodQngAl cua Tdgin khong d6i; ciaodQngE cua Tdtach thanhAl + BI;daodQngF2cua TdtachthanhB2+E. Ne'u0 ph6 h6ng ngo~ti,thl trong ph6 se xua"thi~n4 dinh cd ban cuaionPO~-baog6rn2 dinhB2va2 dinhE. ~TfnhtoaDtheome)hlnh"nOitit})". Sv tachdinhph6do giarnd6i Kungnhu'dad~c~pco th€ du'Qc khingdinhthongquatinhtoaDIu'Qngtii'abinitiotrencdsornohinhdu'Qc Ixaydvngnhu'0 tren. E)~sa dl,lngrnohinh tren,chungtoi gia thie'td.ng ion phosphate chibinenhaygian dQctheotrl,lcZkhi 0 trongrn~ngtinhth€. Bi~unay ICOnghiala chi co c~nhdzbi thayd6i, con cac c~nhdxva dydu'Qcgin ongd6i(xernhinh3.21). TrudctieD, chungtOitie'nhanhtinhtoaDb~ngphu'dngphapIu'Qng '.abinitiod€ xac dinhcacthongsO'ungvdi tru'onghQpion phosphate o~-tVdo.Ke'tquadu'QCtrlnhbaytrongbang3.19(0hangdu'9ctoden). 0 rangtruonghQpnay dz=dy=dz= 1.81A. ChU:(/nf!3: Kef Cluava blnh luan LuananTitnsfVatly 111 hi<;1ngtU'ab initio (mr1cly thuyetHF, h~hamC(jsiJ LANL2DZ i) phantU' n'ayc6 badaDdOngcdban,trongd6c6hai daDdOngkhongsur bi€n Lg, L.umOtdaDdOngsur bi€n b~chai TIu.Theo nguyenuk, phantU'nay thuQcnh6md6i xungDoohnenchi c6 VI(Lg)xua"thi~ntrongph6Raman. Nhlingthvct€, khi 0 thSra:nhay thSlong, ca 3 fansO'VI(Lg),V2(TIu)va V3(Lu)d~uxua"thi~ntrongph<5Ramanboi VI 0 hai thSn'ay,m6iphantU' n~mc~nhk~cac phantU'khac do d6 c6 xay ra tacdOngdipole-dipole gaynensv thayd6i Hnhd6i xung. A. Loewenschuss[78] da:ghi ph6 RamancuaHgI2trongmatrixkhf trd,trongkhi d6chungWi ghiathSra:n. Hinh3.19la ph6 RamancuaHgh 0 thSra:n.Cack€t quadu'<;1cli~tke trongbang3.17. Bang3.17.Cact'ansO'cdbancuaHgh (cm-I). Binh V2n~mavungt'ansO'tha"p,khongthSghidu'<;1cb~ngthi€t bi Ramanay,nhu'ngvdiHnhtoanabinitiochungtac6du'<;1cV2=46cm-I. Binh 105cm-I (hlnh3.19)la do plasmacuakhf Argon tronglaser 'chthich. Ph6Ramancuam~udu'<;1cdi~uch€ b~nghaiphu'dngphapn6itren hlnh3.20),c6 nhi~uthayd6i so vdi ph6cua C6otinhkhi€t (hlnh3.17), H~hamcdsO'naythichh<;1pvdi caenguyentii'n~ngtuchuky 4 c1iabangphanlo~ituiinhoan. VI(Lg) V2(TIu) V3(Lu) Ref. 158 63 237 [69] 156 - 235 Do tronglun annay 149(Raman) 46(IR) 224(IR) Tfnhtoanabinitio Chl(l1n~3: Kit qua va binh Luan LuananTiin SlVatLx112 d~ebi~td vungdaodQngboa triod do,ngoaidinh1467em-I,conthffy xuffthi~nthemdinh1458em-I.Cu'ongdQtu'dngd6igilia2 dinhn'aykhae nhaumy theo h~tm~udu'Qedo (sau khi du'Qedi~uehe').Tren cd sd nhungdli ki~nn'ay,chungtoico th6suydoannhu'sail : Slfthayd6iph6noitrencoth6labi6uhi~ncuaphanlingtu'dngh6 giuaC6ova HgIz. ~ U) U) M N 100 150 200 Wavenumber, cm-1 250 300 Hlnh3.19.Ph6micro-RamaneuaHgIz Slf thayd6ieu'ongdQtu'dngd6igiliahai v~chn'aymy theoh~tm~u du'Qcdo,chungtom~udi~uche'khongdu'Qcd6ngnhfft. T'ansO'daodQngcualienk6tCC giamxu6ng,tUdocoth6suyra r~ng,mQtph'andi~ntti'dffchuy6ntUlienke'tCC quaphantti'HgIz.BdiVI khichuy6ndi~ntU'di thl h~ngsO'Ilfc se giamva tfftnhient'ans6dao dQngsegiam[6].Clingvlly dodo va doslf tu'dngquailgilia t'ans6dao 6 I .,., 5 ..-.. :J 4 ro........>....... 'w 3 c: Q.)...... c: c: 2 ro E ro 0::: 1 0 ChU{fflJ?3: Ke'tQUQva binh fwin Luanan Tie'nSI VatIi. 113 dQngboatrivadQdailienktt CC, chungtoichodings11tu'dngtacgiua C6ovaHghdillamchodQdailienktt CC tanglenmQtit. 60 co'" "-- '".... /' '" N .... ....'"'" N'".... 800 1000 1200 Wavenumber,cm-1 lI'mh3.20.Ph6micro-Ramancuaphucthe(C6o,Hgh) 400 600 1400 1600 trongvung200-1600cm-I Khi khaosatph6cuaphucthe0vungfans6thffp(HInh3.20),co thethffycomQtvaithayd6inho,d~cbi~tbellqmhdinhph6267cm-Ico xua'thi~nmQtdinhnho0 fans6 251cm-I.DiSu n'ayco thelienquailde'"n tu'dngtacgiuahai phanhi'.Tuy nhiende kh~ngdinhdiSun'ayc'ankhao satky hdnvungph6thffpnoi tren. Nhu'v~y,mQtl'annua,ktt hQp19thuyttnhomvoi phu'dngthuctlnh toanhiQngtti'ab initiora rangco thedl!dondu'Qcs6dinhph6,cu'ongdQ vaquyke'"td6i xungchocacdinhph6Ramanco khanangxua'thi~ncho C60,hi do lamcdso chovi~cnghienCUllcacphucthecuano. 50 ......... ::J 40CtI'-" >.-- .00 30c: Q)-- c: c: 20CtI E CtI 0::: 10 1 \ 0 ---,- 200 Chl((/nZ 3: Kef quavablnhiuan Luanan Tie'nsi Valif 114 B~ngHnhloanabinitiocoth€ dt!doandu'9Ccacdinhph6fans6 tha"pdo daodQngcuacacnguyentti'n~ngt~olienmakhongth€ phat hi~ndu'9cb~ngquangph6ke'micro-R_amanthongthu'ong.Trongtru'ong h<;1plu~nannayla phantU'Hglz. ChungWi mu6ndiSuche'va nghienCUllst!ph6ih9P giuaC6ova HgIz.Ph6Ramancuam~ucha'tdiSuche'co st!thayd6i,st!thayd6inay lienquailde'nst!com~tcuaphucth€ (C6o,Hglz).St!giamfans6boatri cualienk6tCC chophepchungWisuyracost!tangdQdailienk6tboa hQCcuaCC dok6tquacuast!chuy€n doi di~ntU'tUphantU'C60d6nphan to'Hglz.DiSu nay tu'dngtt!vdi ke'quacua Haddonva cQngst![54]khi khaosatph6RamancuaC6odu'9cphat~pvdiRb. Tren ph6 cua phuc th€ (C6o,HgIz), ph6 rieng cua HgIz khong hi~n f6,coIe chinhVIph6Ramancuanora'tye'usovdiph6cuaC6o. mm ChU(JfU?3: Ke'tqua va blnh luan Luanan Tie'nsi Vatly'115 ? , '" ? ,,' 3.6.KHAO SAT PHO MICRO-RAMAN CUA H(1P CHAT PM T QUANG GADOLINIUM PHOSPHATE. B€ khaosatph6Ramancuah~th6ng(Gd2O3-P20S),trudch6t chungWiphantfch,giaidminph6RamancuaGdPO4(1:1)dt!atrenHnh "tUdngquan"cuacacnhomdi€m va trenk6tquaHnhloanb~ngphtidng thucltiQngtii'abinitiotheomohinh"phantii'nQiti6p". Gadoliniumphosphate(GdPO4)la mQtlo(;liorthophosphateda't hie'mthtiongdtiQcdi"euch€ b~ngphtidngphapdongnhi~tdQcao [45]. Theak€t quado nhieuX(;ltiaX thl GdPO4thuQch~ddnta co ca'utrue monazite,tUdi~nPO4hdi bj bi6n d(;lng,nhomkhonggian la P21/n(14) 0 0 0 voicaethongs6m(;lng: a=6,6546A; b=6,8486A; c =6,3372A va ~=103,50[27]. Ph6daodQngnoi chungva ph6Ramannoi riengcuaGdPO4dtiQc thShi~nchuy6ula ph6cuacacnhomPO4.Ph6daodQnglien quaild6n Gdxua'thi~nafans6ra'tha'pvacoctiongdQra'ty6u.Dodo,trtidclien chUngtoi se HnhloancacdaodQngcdbancuaion PO~-t1fdo va trong m~ngtinhth€ GdPO4.Cack6tquatinhloansedtiQcdunglamcdsokhao satph6Ramantht!cnghi~mcuaGdPO4.Ion PO~-t1fdoco d(;lngXY 4ca'u trUetUdi~nsemantheod6ixungTd[3].Trongkhi doXY 4tUdi~ntrong tinhthecoth€ khongcond6i xungTdm1a.Trongtht!ct6,Hnhd6i xung cilachungsecokhananggiamdi,thongthtiongsebi€n thanhnhomcon kh6ngfamthtiongcuaTd[83]. :hl((JllZ3: Kit quavabinhiuan LuananTiensfVatif 116 61 a.;I: hK ~... leuc e mau. Cacphakhacnhaucuah~tho'ng(Gd2O3-P2OS)du<;icdi~uche'b~ng hudngphapphanlingtrongphar~n0 nhi~tdQ 700-1450°c saukhi cac fmhph'andu<;icboa tantrongaxitnitricd~md~cva bayhdi chokho. achoachfftband'auIa NH4H2PO4(99%minimum)cuahangMERCK; d2O3(99,999%)cuahangJOHNSONMATTHEY; Y2O3(99,999%)cua angRHODIA va Eu203(99,99%)cuahangACROS. Toan bQquatrlnh i~ucht naydu<;icchungtoi thl!chi~nt~iPhongthinghi~mHoahQcv~t ~ucod~c,CNRS, 33608Bordeaux-Pessac,CQngboaPhap. .6.2.Chiph8micro-Raman. BuQc g~n voi mQt kinh bien vi quang hQc, quang ph6 k€ 'cro-Ramanco thekhaosatdu<;icnhungm~unhovoi kich thuocco 1/.l. °do,d6ivoinhungm~ukhongthu'anhfft,cothekichthichtrennhung lingmyyc'ankhao sat[58].Cac ph6Ramantrongph'annayduQcghi fenDILOR LABRA1\1 (Trung Him Khoa hQcV~t li~u,Nghla do, TiI iem,Ha nQi)voi ngu6nlaserkich thichla He-Ne buocsong632,8nm o~tdQng0 15 mW va detectorCCD; va trenquangph6k€ micro- amanOMARS 89(thuQcPhongthinghi~mHoa-Ly phantU',B~ihQc ordeauxI, Phap)voingu6nlaserionArgonSpectra-Physics2061buoc song514,5nmva laserHe-Nebliocsong632,8nmho~tdQng0 cong sua't400mWva voi detectorCCD. BQphangiaicahaimayla 3cm-I. 3.6.3.Mo hlnhtlnh toaD. DekhaosatcffutruchlnhhQcvacacye'uto'do'ixlingcuamQtphan nrho~cffiQtion tli di~n0 cacdi~uki~nkhacnhau,chungWi sadl,mgmo ChU:lJnf! 3: Ktt CluavablnhLuan LuananTitnsfVatLi 117 hlnhma0 donodu'Qcd~tnQitie'ptronghlnhl~pphu'dng.Ne'ud6ixung cuachunggiamtitTdxu6ngD2d,thltacothexemphantU'(ho~cion)nQi tie'ptrongmQthlnh l~pphu'dngbi lambie'nd~ngdo slfnenVaGva gHin racuahlnh l~pphu'dngtheotrvc Z. Hlnh 3.21trlnh bay ma hlnh cua chungWidu'aradekhaosation PO~-. Theomahlnhnay,khihlnhngo~itie'pIa l~pphu'dngthlnhomd6i xungcuaphantU'sela Tdvakhino la hlnhkh6ichITnh~t(bigianho~c nen)thlnhomd6ixungcuaphantU'baygio sela D2d.. Z(S4,C2) :~5 @ :0 . :P y(C2) x(C2) dy 3- Hlnh3.21.Ma hlnhtinhtminchoionP04 3.6.4.Ph6 RamancuaGdPO4(1:1). 3.6.4.1.Ph6RamancuaionPO~-tl1do. N6u0 tr~ngthaitlfdo,ion PO~-secod6ixungTd[3,83].Trong tnionghQpnay, sa dvngphu'dngphaptlnh toan19thuye'tnhom[5,38] thotha"yding ion tlf do nayco 9 modedaodQngehudntdethuantheo biSudi~n: ChllcJnJ! 3: Ktt CluavablnhLuan Luanan Titn si VatLx118 r vib(Td)=At +E +2F2 (3.4) I Nhu v~y,thco (3.4) ion PO:- tI! do c6 b6n dlnh phil Ramancd ban. Bang 3.18 trlnh bay fan s6 cua cac dinh ph6 Raman quail sat th1;lc nghit?m[86]va ke'tquatinhtoanb~ngphu'dngphaplu'qngt1Yab initio0 milcHF (Hartree-Fock)vahamcdso6-31++G(d)choiontt;tdonay.Hai da'ucQng(+)0 hamcd soco nghlala hamcd so 6-31G(d)du'qcQng themvao hai hamkhuechtan,mQthamchocacnguyent1Yn~ngva mQt hamcho cacnguyent1Yhydro.Ht?hamcd so nhu'the'nayrfftthkh hqp chocacanion,cacht?th6ngcotkh dit?nam,...[49].Chliyr~ngphaicho giatri -3 (dit?ntkh cuaion PO~-)va 1(dQbQispin)vao0 dulit?uvao "Charge& spinmultiplicity". B6ndaodQngcdbannoi trendu'qcmotanhu'tronghinh3.22du'di day[58,86]. vL v\(A\) v2(E) v3(F2) v4(F2) Irmh 3.22.CacdaodQngchugntAccuaion PO~-tt;tdo. D6i vdi ion phosphatett;tdo,dinhVt=938cm-l la daodQnghoa tricualienketP-O vacocu'ongdQm~nhnha't.Benc~nhdo,theoket quatinh toanab initio chi ra r~ngdao dQngnay ht?sO'khli'phanc1;lc p=0, tilc la daodQngnaybi phanc1;lchoantoan.Do do,co th€ ketlu~n Ch"'(JnJ!3: Kef quavabinhIuan Luanan Tie'nsf VatIi. 119 dayla daDdQnghoantoand6iKungAI. Binh V3=1064cm-I1adaDdQng ,cogianba"td6i Kung.Con cacdinhV2=420cm-Iva V4=567cm-lacac ~odedaDdQngbie'nd~nggoc.Dlfatrenke'tquatlnhtoanabinitioco the ~€ dangquyke't d6iKungchocacdaDdQngcdbanV2,V3,V4nay(nhu'0 !llVC3.1).Ke'tquadu'QCtrlnhbaytrongbang3.18. JIang3.18.T'anso'Raman(cm-I)cuaionphosphatetlfdo. Blnh ThQ.'cnghi~m[24] Tinhtmln Dol ph6 Tans6 Cu'ongoQ Tans6 Cu'ongoQ xUng V2 938 420 rm y 903 404 17.90 0.90 AlVI E y 987 578 16.35 0.32 F2 F2V4 1017 567 mV3 nn:ra'tm:;mh;m:m~nh;y :ye'u. 3.6.4.2.Ph6RamancuaionPO~-trongm~ngtinhth~. ~Tinhtmlnblingtvthuy~tnh6m. Khi 0 trong m~ngtinh the, ch~ngh~nnhu'cac orthophosphate GdPO4,EuPO4,YPO4 thlion PO~-seco d6iKungD2d[24,83].Tinh toan st!phanb6 cacmodedaDdQngb~ngh~congiliuc Herzberg(ph\ll\lcA3) nhu'0 cac ph'antren,chi ra r~ngtrongtru'onghQpnay ion PO~-co 9 modedaodQngco bieudi€n : r vib(D2d)=2AI+ Bl +2B2+2E (3.5) Nhu'v~y,theo(3.5)va ke'thQpvdibangd~cbieucuanhomD2d,co th6dlf doandng trongph6 Ramancuacac tinhthe orthophosphatese --- --- ChLtlJnf!3: Ke'tQuava binh iuan LuananTie'nsfVatif 120 xuffthi~nbaydinhcdbancuaion PO~-(haidinhAI, rnQtdinhBI, hai dinhB2va hai dinh suybie'nb~chai E) thayVI b6nnhu'0 tren.Nguyen nhanla co sv tachdinhph6dod6iKunggiarntUnhornTdxu6ngnhorn D2d[83].Dvavaotinhcha"ttu'dngquail(correlation)ginacacnhorn,trong trlionghQpnay la nhornTdva nhornD2d,co th€ xac dinhdu'Qcphu'dng thUGcua sv tachdinh ph6 do sv giarnd6i Kung.Bang tu'dngquaild6i xungTd-D2d[44,46,94]chiradingkhi d6iKunggiarntUTd xu6ngD2dthl daodQngAl cua Tdgin khong d6i; ciaodQngE cua Tdtach thanhAl + BI;daodQngF2cua TdtachthanhB2+E. Ne'u0 ph6 h6ng ngo~ti,thl trong ph6 se xua"thi~n4 dinh cd ban cuaionPO~-baog6rn2 dinhB2va2 dinhE. ~TfnhtoaDtheome)hlnh"nOitit})". Sv tachdinhph6do giarnd6i Kungnhu'dad~c~pco th€ du'Qc khingdinhthongquatinhtoaDIu'Qngtii'abinitiotrencdsornohinhdu'Qc Ixaydvngnhu'0 tren. E)~sa dl,lngrnohinh tren,chungtoi gia thie'td.ng ion phosphate chibinenhaygian dQctheotrl,lcZkhi 0 trongrn~ngtinhth€. Bi~unay ICOnghiala chi co c~nhdzbi thayd6i, con cac c~nhdxva dydu'Qcgin ongd6i(xernhinh3.21). TrudctieD, chungtOitie'nhanhtinhtoaDb~ngphu'dngphapIu'Qng '.abinitiod€ xac dinhcacthongsO'ungvdi tru'onghQpion phosphate o~-tVdo.Ke'tquadu'QCtrlnhbaytrongbang3.19(0hangdu'9ctoden). 0 rangtruonghQpnay dz=dy=dz= 1.81A. C;U({JnJ!3: Klttquavablnhluan LuananTiln sfVatlY 121 moo 3.21(cacnguyentlYduQcdaOOs6nguyentlYtheotiOOloanab initio)chota: R =R(1,2) =R(1,3)=R(1,4)=R(1,5) Al =A(2,1,3)=A3=A(2,1,5) A2=A(2,1,4)=As=A(3,1,5) 0 B~ngcachthayd6idQdaicuadzxungquaOOgiatrt1.81A trong 0 khoangtU 1.0de'n2.5 A va tiOOloancac dQdai lien ke't,goc giiia cac lienk6ttlidngling vdi m6igia tri dzsaochoca"utrucluonduQcdambao laD2d.D€ c6 diOOcacdQdai lien ke't,cacgocgiiia caclien ke'tc'anphai t5iuu boa trongdi'euki~nt6i uu boa tUngph'an,tilc la cho tU khoa Opt=ModRedundant (ph\1l\1cD3).Cac ke'tquatiOOloancacthongs6 c[utniclingvdi cacgiatridzkhacOOauduQctr'inhbaytrongbang3.19. K6 do, th\!,chi~nHnhloanab initiocho ion phosphatetu'ant1!vdi caegiadz,dQdai lien k6t,gocgiiia caclien ke'ttheoOOubang3.19.Ke't quatinhloant'ans6duQctrlOObaytrongbang3.20. TItk6tquatinhloanlIen, co th€ rutramQts6OO~nxetsailday: 0 +Khi dz=1.81A, ion PO~-co d6ixlingTd.Hai mode1va2 thuQc lo~idaodQngsuybie'nb~chai E; Cac mode3,4, 5 thuQclo~idaodQng suybie"nb~cbaF2;Mode 6 thuQclo~idaodQngkhongsuybie'nAI; Cac mode7,8,9 thuQclo~idaodQngsuybi6nb~cbaF2.TIt do, so sanht'an 0quansatth\!'cnghi~mva t'ans6 tinhloan,ro dl.llgco thSquykStd6i lingehocacdiOOph6cuaionphosphatet1!do (bang3.18). +Khi ionbi nen(dzgiam)th'ico s\!,tachcacdinhph6.DaodQngE 404em-I) tachthanhhai daodQngAl (mode1)va Bl (mode2); Dao rhl1anJ!3: Ke't(llul va binh luan LuananTiensfVatIf 122 QngF2thunha't(578em-I) tachthanhhaidaodQngB2(mode3)va dao :QngE (mode4 va mode5); Oao dQngAl (mode 6) v~ngill nguyen; ~aodQngF2thuhai (987em-I) tachthanhhai daodQngB2(mode7) va ~aodQngE (mode8vamode9). 0 +Khi ionbi nenquanhi'eu(dz~1.0A) thlktt quatinhtmlneho [node1cofans6am,haycongQila fans6ao.Bi'eunaychungtodayla [nQtea'utruebitn d6i,khong6n dinh,la ea'utruetrunggianeuahai ea'u trUecanb~ngnaodo[49].Nhu'v~y,khinendtn mQtgiatrigioih~nnao ~6thlea'utruecod6ixung02dsekhongt'Ont~imaseehuyensangmQt d~ngea'utruekhaenaodo. IBang3.19.K€t quatinhroancaethongs6ea'utrueehoion PO~-. 0 dz(A ) 2.50 0 R(A) 1.7910 2.00 1.95 1.6265 1.6112 1.90 1.81 1.5962 1.5717 1.70 1.65 1.5388 1.5150 1.50 1.00 1.4859 1.3767 Al (dQ) 119.15 112.21 111.48 110.75 109.47 107.76 107.02 104.76 97.58 As(dQ) Ohi ehu 91.48 104.12 :;t:02d 105.52 106.95 109.47 112.94 114.51 119.37 137.41 VI <0 +Khi ion bi gian(dztang)thl sl,itachdinhph6clingxay ra tu'dng ~nhlitru'ongh<;5pnen.Tuy nhienco.mQtvai khaebi<%t,e\l thela mode1 Chu{JnJ!3: Kit quavablnhluan LuananTiin sfVatIx 123 13.daodQngE (404cm-I) tachhai daodQngBI (mode1)va Al (mode 2); DaodQngF2thunha"t(578cm-I) tachthanhhaidaodQngE (mode3, mode4) va B2(mode5); Dao dQngAl (mode6) v'angill nguyen;Dao dQngF2thuhai (987cm-I) tachthanhhaidaodQngvadaodQngE (mode 7, mode8)va B2(mode9).Tuy co khacbi~t, nhungv§:ntuantuantheo 0 tinhttidngquailTd-D2d.Nhungkhi gianquanhiSu(dz~2.0 A) thl d6i xungD2dbi phavo, b~ngchungla Sl}tachcacdinhph6khongcontuan theoquylu~tnhutrennua(phV Ivc D3). Bang3.20. Ke'tqua tinhtoant'ans6dao dQng(cm-I)cho ion PO~-vdi caethongsO'ca"utruckhacMall. Modedao dQng 1.5 1 2 300 460 3 4 537 586 5 6 586 1158 7 8 1215 1309 1 l 9 1309 1.65 359 429 562 584 584 1065 1144 1186 1186 0 DQ dai qlllh dz(A ) 1.70 378 421 570 584 584 994 1073 1099 1099 1.81 1.90 .404 392 404 417 578 578 578 903 987 987 987 568 568 580 837 910 910 922 1.95 385 423 560 560 580 799 868 868 884 2.0 379 427 548 548 578 761 828 828 845 +Mode6 (ttidngdudngvdiVI trongbang3.18)thuQclo~id6ixung Alvagill khongd6i khi ion giamd6i xungtu Tdxu6ngD2d.No Ia dao dQngeogHind6i xunglien ke'tP-O, co cuongdQm~nhnha"t.Hinh3.23 Van~3: Kef Qua_vabinh [win Luanan Tiensf Vat[1.124 tast!ph\!thuQcuafans6Ramancuamodenaytheodz.Til hinhnay hSnh~ntha'ydingtklns6Ramancangtangkhiionbinencangnhi€u. 1200 1000 HF/6-31++G(d) 1100 5 a ! 900 ) . I i. T 800 y 700 1.451.501.551.601.651.701.751.801.851.901.952.002.05 dz,A mnh 3.23.st!ph\!thuQccua VI VaGdz I Ph6 micro-Ramancua GdPO4(hinh 3.24)cho ta VI =979 cm-I. 0 'V~LOd'Othi trenhinh3.23,co thSxac dinhduQcdz=1.6933A. Til dlfaVaGhinh 3.21,vdi mQtvai pheptfnhhinhhQcco th€ xac dinh 0 ~dQdaicualien k€t P-O la Rp-o=1.5369A . K€t quanayphlihQpt6t 0 ~nhtoancuaMooney[83]laRp-o=1.54A. Ta'tnhien,tUgiatricua Inay,cacgia tri cuacacgoclienkStcuaionnaytrongtinhthSse !HnhmQtcach d€ dangb~ngmQts6 phep tinh toanhinh hQCva ggiac: Al =A(2,1,3)=A3=A(2,1,5)=107.67(dQ) A2 =A(2,1,4) =As = A(3,1,5)=113.15(dQ) ,... ChUGnfl3: Kef Clua va binh luan LuananTiensiVatli \15 20 GdPO4 '""'" 15 '3 t"C ,f' ~ 10 ~c: c: t"C E t"C a::: 5 .... ..., 0 '" "CO ...,"'- ....M.... .... N ..., It\ ~ co M 00 - 0 200 400 600 800 1000 Wavenumber(em-') Hinh 3.24.Ph6micro-RamancuaGdPO4 3.6.4.3.Ph6 Raman ciia GdPO4(1:1). Hinh 3.24 la ph6 micro-Raman cua GdPO4 trong vung 150- 1200cm-l. Trong vung 350-1200cm-l hi<%ndi<%n8 dinhph6 co cu'ongdQtU trungblnh den m~nh.Cac dinh nay co ngu6ng6c tUion Po~-.Vungtren1200cm-lh'aunhukhongco dinhph6nao.Trong8dinh nay,ngoaiVI,Saildinhbaag6m397,418,469,624,1034va 1064cm-l du'Qchlnhthanhtli's1jtachdoi cuabadinhph6, mQtdinh suybienb~c haiE va hai dinh suybien b~cba F2do s1jgiamd6i xungtUTdxu6ng D2d.Binh1085cm-lco thSla doho~t'anhays1jketketh<;1pcuadaodQng cdbanco t'ansO'tha"p.Co thSkh~ngdinhV2=418cm-l thuQcd6i xungAl vaV3=397cm-l thuQcd6i xungB1,boi Ie, khi so sanhph6 Ramancua GdPO4do chung Wi ghi (hlnh 3.24) va ph6 hang ngo~icua Agrawal [24] chotha"yr~nghai dinh ph6 nay chi xua"thi<%ntrongph6 Ramannhung thlianJ!3:Kittquavablnhluan Luan anTiitnsi Vatly 126 [hongxua'thi~ntrongph6 h'Ongngo~i.E>i'eunay phil hQpvdi ke'tqua tmln19thuye'tnhomd tren,d ch6Al va BI d'eubi ca'mtrongh'Ong :go~i.Caedinhtrongvilngph6fan86tha'p200-350cm-Ilien quailde'n '~ntu'qngt~oc'aun6iGd-O [83]. ang3.21.Sv tachdinhph6dogiamd6iKungTd- D2d PO~-ttfdo [24] VI(AI) =938 v4(F2)=567 v2(E)=420 v3(F2)=1017 20 YPO4 <C'"'" 15 <C'" 0 ::I <Ii ~ .~10 Q) C <C'"Nc ra Era ~5- 300 400 500 600 700 0 800 900 1000 1100 b -1Wavenum er, em H'mh 3.25.Ph6 micro-Ramanr.i~::IVP(). PO- trong GdPO4 PO- trong YPO4 VI (AI) =979 VI (AI) =998 v2(AI) =418 v2(AI) =484 v3(B1)=397 v3(B1) =340 vs(B2)=1064 vs(B2)=1058 v7(E)=1034 v7(E)=1025 V4(B2)=624 V4(B2)=660 v6(E)=469 v6(E)=580 ..... Luanan Tie'ns'iVatIV 127 Phantichtu'dngtv'clio ph6RamancuaYPO4 (hinh3.25).Cac ke't aphantichtrenclioGdPO4vaYPO4du'QCtrinhbaytrongbang3.21. 3.6.4.4.Ph6RamancuaGdPO4: Ell 3+. 15 -.&J "- '" "" :J ro 10 "-" Gd PO4:Eu3+(5%) >-- 'in c OJ- C C (\! 5 E (\! 0::: 0 -.&J 0 N ~ '" '" "" 0 0 0 200 400 600 800 1000 Wavenumber,cm-1 Hinh 3.26.Ph6 micro-Ramancua Gd PO4:Eu3+(5%) . Hinh3.26la ph6 micro-Ramancua GdPO4 tang ho:;tt5% EU3+.So ph6nay voi ph6 cua GdPO4khong tang ho:;tt(hinh 3.24) clio thffy gdtrongvung150-1200cm-lhaiph6nayla gi6ngnhaucav'evi trf cllongdQtu'dngdO'icuacacdinhph6. Tlnhtr:;tngclingtu'dngtv nhu'the'khi GdPO4du'Qctangho:;ttvoi 1% 10% Eu3+(phvlvc B6).Boi vi khi du'Qctangho:;tt,seco mQtsO'ion sethaythe'Gd3+trongm:;tngtinhthe,nhu'ngdo kich thu'occuaion a It-vaionEU3+khac nhaurfft it, C\l the Ia rGd=1,066A va fEu= 1,053 ~2],Dodo,h'aunhu'khongcosvkhacnhaugiuaph6cuaGdPO4du'Qc ho~tvaGdPO4khongtangho:;tt. ChuanJ!3 ..Ke'tCluavablnhluan Luan an Tie'nsf Vat 12.128 3.6.5.Ph6 Raman cuaGdZP4O13(1:2) Ph6 Ramancua cacgadoliniumphosphatethayd6i rfftnhi~utuy thuQcvao ty 1<%gilia GdZO3va PzOs.MQts6dli li<%uv~cffutruccuacac nh6mPO4trongcacgadoliniumphosphatevaphosphatecuanguyent6 da'thiSmkhacc6clingcffutrucdu<;1ctrinhbaytrongbang3.22,3.23(ph\! l\lC~). 35000 30000 Gd2P4013 1182 25000 --- ~ ~ 20000 >- I- Cf) 15000 Z W I- Z 10000 5000 689 0 500 1000 1500 WAVENUMBER(cm-1) Hinh 3.27.Ph6micro-RamancuaGdZP4013 Cffutructinhth€ cuaGdZP4013la chuadu<;1cbitt. HInh 3.27la ph6 Ramancuan6.Do slfkh6khancuavi<%cdi~uchSmfiunay[25],liencon comQtit lU<;1ngdu GdPO4,b~ngchungla slfhi<%ndi<%nhai dinh954va 1071em-I.C6th€ thffyr~nge6mQts6dinhm<;lnhxuffthi<%n.Dod6ixung ciiatUdi<%nbi phavo,eachgQitencaedaodQngVI va V3trongionPO4la khongcongiatri nlia.CaedaodQngmoixuffthi<%nla VsvaVaehocae c~uPOP, la euanh6mPOl [53,77]vatu'ant1f0 0 689va 1004cm-Ieho caeciaodQngPOP va 01182va 1231em-Iehopaz.CacgiatriVsvaVa Ch!tanf!3: Ktt quavabinh[win Luanan Titn sf Vat[y 129 nayduQekhiingdtnhbftngk~t,\uatinhtoanluQngt\1abinitio(bang3.24, phVIlJe~) trencd so mohinhehu6iphosphatevoi cacthongea'utrue0 bang3.23(phl;lll;le~). d dayv~nslYdl;lngmue19thuy€t HF va h~ham cdso6-31++G(d) ehovi~cHnhloan.Chu'dngtrinhHnhloanva k€t qua dU9Ctrinhbay trongphl;lIl;lCD4. 3.6.6.Ph6Ramancua GdP309(1:3)d~ngddntit. TrangcaemetaphosphateddntaGdP3O9(1:3)cactUdi~nPO4t~o nencaeehu6i(PO)ndo slJ'chiaxe caenguyentU'oxy (hinh3.28).Cac tU di~nnaybj bi€n d~ngm~nh.D9 dai lienk€t giiIa cacnguyentU'ph6tpho (P)vacaenguyentU'oxy e'aun6i (Obr)la dai hdn giuanguyentd P va oxy0dinh(Oap)(bang2 phl;lll;lcA3).Caeg6cOap-P-Oapla Ionhdnm9t eachdangkg sovoi caeg6c°br-P-Obr' Trangph6RamaneuaGdP3O9(hinh3.29),cacdaad9ngtu'dngung vdiVsvaVacuacaenh6mpaz va caedaod9ngVsva Vaeuacaee'aun6i POPg'annhu'khongd6i soyoi GdZP4O13.Di'eunayclingdehigun€u thua nh~nr~ngtrangcahaica'utruccaetUdi~nPO4 d'eudu'Qcn6ihaibell voi caeph'antU'Ian c~n. If'mh3.28.Chu6iphosphate Nh6mP-O-P Nh6mPO2tt0 0 0 0 0 0 I I I Ip p p p p p ...// o! all all o! 00 ... 0 0 0 0 0 Chl({fnJ!3 .. Kit quavabinhiuan Luan an TieTtSI Vat if 130 25000 1200 20000 GdP309 ~ 15000 t1I'-' 1233 >--'iij c: 10000 Q) 'E 677 0 379 5000 500 1000 Wavenumber (cm-1) 1500 Ifmh3.29.Ph6 micro-Ramancua GdP3Ogd~ngddn ta. 3.6.7.Ph6Raman cua GdPSO14(1:5). TrangGdPSO14(1:5) cac tUdi~nchungnhau cac g6c cua chungdS ~othanhnhungc~pchu6i mQtchi'eulien ke'tngangvoi nhau bdi nguyen ti( P [60].Ph6Ramancua GdPSO14c6 khac so voi ph6 cua GdPO4 va Gd2P4O13(hlnh3.30). Trangph6 cua GdPSO14,cac dao dQngVsva Vacua cac nh6m PO2 djchchuySnnhi'euv'ephla fan s6 cao, tu'antl! la 1268va 1302cm-l, trong khido,cac dao dQng Vsva Vacua nh6m nh6m O-P-O trongchu6i la h'au nhu'khongd6i. C6 thS giai thkh di'eunay nhu'sail : cac nh6m PO2bi anh hu'dngnhi'eudo bie'nd~ngca'utruc va do tu'dngtac ion-ion [66-67]hdn caenhom O-P-O n~mbell trong chu6i va do d6 n6 du'Qc"bao v~" ky hdn.Bang 3.23 (ph\! l\!c ~) chi ra r~ng cac tU di~n cua cac pentaphasphatevoi hai oxy c'aun6i la bi bie'nd~ngnhi'euhdn trangcac metaphasphate. ~u'O'nJ! 3 ..Ke'tQuava bznhiuan LuananTiensfVatif 131 35000 30000 GdPSO14 1302 25000 ..-.. ::I iii 20000 ......... 674 >-;t: ~ 15000 Q)- c:- 10000 1175126 721 5000 0 500 1000 Wavenumber(cm-1) 1500 mnh 3.30.Ph6micro-RamancuaGdPSO14 6.8.Ph6RamaneuaGdP309(1:3)d~ngtritegiao. MetaphosphateGdP3Ogcohaid~ngddntavatn;!cgiao,tuythuQc laodi'euki~ndi'euchS[25,27].D~ngd'autiendadu'Qckhaosata mvc .6.6.TrongGdP3Ogd~ngtrq'cgiao,cac1:11di~nPO4t~onenchu6i(PO)3 ~ngxo~n[42,60].Sanphgnthudu'Qcoph6Ramamkhacbi~tsovoi IPh6 cuaGdP3PO9d:;tngddntava cuaGdPSO14(hlnh3.31).Cac daodQng VsvaVacuacacnhomPO2xu~thi~nt:;ti1200va 1275cm-l.Haitans6 nayn~mgiuahait'ans6cuaGdP3PO9d:;tngddntavacuaGdPSO14(bang 3.24,phvlvc~). Til k6tquaphantkhdinhlu'Qnga bang3.24chotha'y r~ngca'utruccuano ra'tg'anvoi ca'utruccuapha(1:3)va tu'dngling voi congthlic GdP3Og. Chu yr~ngd6i voi Gd2PO13va GdP3Ogd:;tngddnta, khongcosl,ithayd6idangkS dosl,ithayd6ichi'eudaicuachu6i.Vdi pha mdinayma chungt6i da tlm th~yla GdP3Ogd:;tngtrl,icgiao,sl,itang m~nhfans6 Vacua nhomPO2co thSdu'Qcgiai thkh bdi sl,i"ep ch~t" ChU:(Jnf!.3 ..Kef qua va binh iuan LuananTieTzSlVatif 132 (constrain)nhomPOxvao chu6iph~nghdn so voi cac nhomPOxtrong GdP3O9d~ngddnta. 25000 1200 PhaX 20000 ........ :J ~ 15000 >-- '00 c:: 2 10000c:: 694 1275 1093 5000 0 500 1000 Wavenumber(cm-1) 1500 Hlnh 3.31.Ph6micro-RamancuaGdP3O9d~ngtrvcgiao(phaX). 3.6.9.811tlidngquangiii'atans6vaUQdailienke't. Khi dQdaicaclienktt tangdoca'utructhayd6i,ch~ngh~nnhusv xua"thi<%ncuad6i xungtrvcgiaohaysvt~oYang,co thetha'yr~ngchu6i rangdaithl fans6daodQngba'td6ixungVacuacacnhomPO2cangtang (Bang3.24phl,ll,lc~). Bi'eunaycotheduqcgiiii thkhla dosvngi1ndi cualienktt P-O dosvpolimerboahaysvt~oyangcolienquailWitinh d6ixungtUdi<%ncuacacmonomer[66-67]. Tmh tr~ngtu'dngtVvoi cacphosphateyttrium,m~cdli cacfans6 daDdQngcua chungla hdi nh~yhdn d6i voi sv tangchien dai chu6i (Mng3.25phl,lll,lc~). ChLlClnJ! 3 ..Ke'tqua va blnh iuan LuananTie'nsi Vatif 133 3.6.10.Anh h1idngeuasl1lamngheophosphatelen ph6Ramaneua caephosphategadolinium. lI'mh3.32.Ph6micro-RamancuaGdgP2O17 Khi tyIt%Gd2O3tang,co the tha"yd.ng ph6 Ramancua cac san ph~mthudU9CGdgP2O17(4:1)va Gd3PO7(3:1)co slfxua"thit%ncacdinh m~nhd vungfans6 tha"p.Co thedayla cacdaodQnglien quande'n gadolinium(hinh3.32,3.33). St!khong xua"thit%ncac dinhph6 d vung 680-700cm-Iva vung 1200-1300cm-Idokhongco slfpolimeboacacnhomPO4.Ngu9ch;li,co mQts6dinhmdi xua"thit%ntrongvung900-1100cm-I.Nguyennhanco thela do daodQngboatri cua cacnhomPO4bi bie'nd~ngbdi slfhit%n di~ncuacacnhomco kh6ilu9ngIOn(GdOy).Chungclingco theIa dost! ~othanhtUcac ho~dinhay st!ke'th9Pcua cacphonontlidnglingvdi Icae adnvi GdOy. 14000f- 915 12000 GdgPzO17 I 347 473 10000I- bn II976 ,-.... ::J <U 8000'-' 31 I \ / \ 11.1\111075(/)c: 6000 (1)- c: 4000 2000 0 500 1000 1500 Wavenumber (cm-1) Chttmtf! 3 ..Ke'tquavabinh1uan Luan anTie'nsf Vat12.134 344 970 Gd3PO7 0 500 1000 Wavenumber (cm-1) 1500 I1mh3.33.Ph6micro-RamancuaGd3PO7 Chungtaconh~nxetla cacdinhcdbantlidnglingydicacnhom IGdOybi marQngtrongph6cuaGdSP2O17.BiSu nayco thed~nd€n dl! .doanr~ngtrongphanayco sl!ma"tr~tVnaodoKayfa. 3.6.11.Anh hu'dngcuadi~uki~ndi~uche'mfiuleDtinhcha'tcuad~ng GdP309. Bagieu-Beucherya Tran Qui [28]da:chi ra r~ngco hai d~ngd6i voih<;1pcha"tGdP3O9.MQt Ia du<;1ct~othanhag'annhi~tdQ800°Cseco d'ongca"utrucydi cac metaphosphatecuaLa d€n Eu (theothli tV trong bangphanlo~itu'anhoan), hai la du<;1ct~othanhag'annhi~tdQ850°C secod'Ongca"utrucydi cacmetaphosphatecuaTb d€n Lu. Ca hai thu duQcdosl!phanly GdPSO14ydi sl!bayhdicuaP2Os. ChungWi da:kiem tracac diSuki~nt~othanhb~ngsl! t6ngh<;1p lr\ictier.Cacthinghi~mdu<;1cthl!chi~na diSuki~nmQitruongkh6ng khi.Trongthinghi~m,apsua"thdicuaP2OsduQcduytr}b~ngcachd~t 12000 10000 8000 .--. :::J ca'-' >- 6000;!::: (/) c Q)- 4000.s L 195 2000 482 910 I 367 320 III I I " "1038 ""I ! 1072524I ,. 39 ChUC1nf!3 ..Kit quavabinh[win Luanan Tiin si VatLV135 IDQtchen b~ngkim lo(;lichuad'ayNH4HzPO4bell C(;lnhchen chuacac hoa cha"tband'au. Trong truongh<;1pthunha't,filing (1nhit$tdQ(1800°Ctrong2 giOvdi tys6nguyentUGd/P=1/3se t(;lothanhGdP3O9d(;lngddn ta. Ph6 Raman cuanoda:du<;1cgidi thi<$u(1hinh3.29. Khi filingsanph§:mnay(1nhi<$tdQ 900°Ctrongsudt20 giO,thlph6Ramancuanoh'aunhukhongd6i,ngo(;li trumQtvai dinhye'uco thela dosvphan1ykhongdangke GdP309thanh GdPO4(hinh3.34b). Truong h<;1pnhi<$tdQ xli' 19(1800°Ctrong sudt20 giO, thl ph6 Ramankhongthayd6i,co nghla1aGdP3O9khongbi thayd6i.Do do, chungWi phaike't1u~ntraivdi Bagieuva cQngsv r~ngkhongco sv chuyenphatrongd~nsua"tGdP3O9. Trong truongh<;1pco mQt1u<;1ngnhoPzos trongdng 10filingcQng vdichenchuaNH4HzPO4va filing (1nhi<$tdQ900°Ctrongsu6t15gio, chungtase thudu<;1cGdP3O9d(;lngtrvcgiao (hinh3.34a).D(;lngnhuthe' clingco thethudu<;1c(1760°Ctrongdi~ukit$nmoitruonggiauPzOs(1cac ty 1<$kh(1i d'au Gd/P 1a 1:3; 1:4; 1:5. Vdi ty 1<$Gd/P =1:4, ph6 Raman clingnhuph6nhi€u X(;ltiaX da:chungtor~ngsanph§:m1aGdP3O9d:;lllg tn,tcgiaotinhkhie't(hinh3.34c). Khi chungtachosanph§:md(;lngtrvcgiaoda:thudu<;1c(1900°Cxu 19ddi~uki<$nmdi trong20gio (1800°Ctrongkh6ngkhi, thlph6Raman thanhphgmchotha'yr~ngco Svbie'nd6isangd(;lngddnta. Co theke't1u~nr~ng,trongta"tca cacthi nghi<$ma(1do co hdi P20Sduytrltrong10filing,thlGdP3O9d:;mgtrvcgiaosedu<;1chinhthanh. JIll""' 15000 691 10000 ,...... :J ro ........ :E- rn c Q) "E 5000 0 500 -- LuananTie'nSlVatlV136 1200 1273 23 (a) (b) (c) 1000 Wavenumber(cm-1) 1500 lfmh3.34.Ph6micro-RamanGdP309(a)900oC/15g/02/locochua as;(b)8000C/2g-9000C/20g(GdP3Ogddnta; GdPO4);(c)760oC/15g1 apsua'thdiP2Os(tnfcgiao) Theok€t quaphantkh dinhlu'Qng,thlca'utrUcdu'Qctlmtha'yla ra't yoipha (1:3)voi congthucGdP3Og.Nhu'v~y,0 day chungtoi qua 0satda:xacdinhdu'QcmQtphamoimachu'atacgianaGtru'ocdayd'e de-no rum