Cỏc trang th loi Húa hc lng t Mc lc Cu hỡnh electron 1.1 S lng t v lp 1.2 in electron vo cỏc lp 1.3 Liờn h n bng tun hon 1.4 Cu hỡnh electron ca mt s nguyờn t 1.4.1 Khớ him 1.4.2 Z t 11 n 17 1.4.3 Z t 21 n 31 1.4.4 Z t 39 n 49 1.5 Xem thờm 1.6 am kho Chm lng t 2.1 S giam gi lng t cht bỏn dn 2.2 Sn xut 2.2.1 Keo tng hp 2.2.2 Ch to 2.2.3 Lp rỏp 2.2.4 in húa lp rỏp 2.2.5 Bulk-manufacture 2.2.6 Chm lng t phi kim loi nng 2.3 Tỏc ng mụi trng 2.4 Tớnh cht quang 2.5 ng dng 2.5.1 Computing 2.5.2 Sinh hc 2.5.3 it b quang in 10 2.5.4 Light emiing devices 10 2.5.5 Photodetector devices 10 Mụ hỡnh lý thuyt 10 2.6.1 C hc lng t 10 2.6.2 bỏn c in 10 2.6.3 Classical Mechanics 11 2.6 i ii MC LC 2.7 Chỳ thớch 11 2.8 Liờn kt ngoi 13 in li 14 3.1 Nguyờn nhõn 14 3.2 in li 14 3.3 mnh yu 3.4 14 3.3.1 Cỏc cht in li mnh 14 3.3.2 Cỏc cht in li trung bỡnh v yu 14 am kho 15 in Mt Tri 16 4.1 Tng quan 16 4.2 S phỏt trin hin ti 17 4.3 Tng lng ó lp t ton th gii 17 4.4 ng dng 17 4.4.1 Trm phỏt in 17 4.4.2 Trong nh 18 4.4.3 Trong giao thụng 18 4.4.4 Trong cỏc thit b ri 18 4.5 Xem thờm 18 4.6 am kho 18 4.7 Liờn kt ngoi 19 Hiu ng lỏ n 20 5.1 Nguyờn nhõn 20 5.2 am kho 20 5.3 Xem thờm 20 5.4 am kho 20 Húa hc lng t 21 6.1 Xem thờm 21 6.2 am kho 21 6.3 Liờn kt ngoi 21 Lai húa (húa hc) 22 7.1 Khỏi nim 22 7.2 Lai húa gia obitan 2s v obitan 2p 22 7.3 Lai húa sp3 22 7.4 Lai húa sp2 23 7.5 Lai húa sp 23 7.6 am kho 24 Liờn kt húa hc 25 MC LC iii 8.1 Xem thờm 25 8.2 am kho 25 Lý thuyt VSEPR 26 9.1 Lch s i 26 9.2 Lun im chớnh 26 9.3 y tc thuyt sc y 26 9.4 í ngha 26 9.5 am kho 26 9.6 Liờn kt ngoi 26 10 Nng lng ion húa 27 10.1 am kho 11 Orbital nguyờn t 27 28 11.1 Cỏc tờn orbital 29 11.2 nh ngha chớnh ca c hc lng t 29 11.3 S lng t 29 11.4 Liờn h n h thc bt nh 29 11.5 Cỏc hỡnh dng ca orbital 29 11.6 Mc nng lng orbital 30 11.7 Xem thờm 30 11.8 Chỳ thớch 30 11.9 Liờn kt ngoi 30 12 y tc Hund th nht 31 12.1 Ni dung chi tit 31 12.2 Ngoi l 31 12.3 Xem thờm 31 12.4 Liờn kt ngoi 31 12.5 Chỳ thớch 31 13 y tc Slater 32 13.1 Ni dung ca quy tcSlater 32 13.2 Vớ d 32 13.3 Mc ớch 32 13.4 Chỳ thớch 33 14 Sai s ng t v trớ b c s 34 14.1 Sai s chng cht v trớ b c s (BSSE) 34 14.2 am kho 35 15 S lng t ớnh 15.1 am kho 36 36 iv MC LC 16 uyt FMO 37 16.1 Lch s 37 16.2 Hc thuyt 37 16.3 ng dng 37 16.3.1 Cng vũng 16.3.2 Phn ng chuyn v sigma 37 38 16.3.3 Phn ng nhit 39 16.4 Chỳ thớch 17 Toỏn t Hamilton 39 40 17.0.1 Phng trỡnh Schrửdinger v toỏn t Hamilton 40 17.0.2 Xem thờm 40 17.1 am kho 40 18 Tng tỏc trao i 41 18.1 Mụ hỡnh tng tỏc trao i 41 18.2 Tng tỏc trao i v tiờu chun st t 42 18.3 Tng tỏc trao i giỏn tip 42 18.4 Xem thờm 42 18.5 am kho 42 19 Vt lý bỏn c in 43 19.1 Sỏch tham kho 43 19.2 am kho 43 19.3 Ngun, ngi úng gúp, v giy phộp cho bn v hỡnh nh 44 19.3.1 Vn bn 44 19.3.2 Hỡnh nh 45 19.3.3 Giy phộp ni dung 47 Chng Cu hỡnh electron 47: Silber Lp electron ngoi cựng (lp húa tr) ca cỏc nguyờn t cha cỏc electron húa tr, cỏc electron ny quyt nh cỏc tớnh cht húa hc cng nh tớnh cht vt lý ca chỳng 2,8,18,18,1 1.2 in electron vo cỏc lp Ag 1K2 s 2L8 s p 3M18 s p d 4N32 s p d f 5O50 s p d f g 6P72 s p d f g h 7Q98 s p d f g h s p 10 d 1s 2p 14 f 18 g 4f i 22 h 3d 26 i s-s p-p p-p 10 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s2885f 14 1026d1127p118 2 Phõn b electron nguyờn t bc 10 12 18 20 10 30 36 38 10 48 54 56 14 70 10 80 86 Th t in electron vo cỏc lp theo cỏc mc nng lng khỏc Cu hỡnh electron, hay cu hỡnh in t, nguyờn t cho bit s phõn b cỏc electron lp v nguyờn t cỏc trng thỏi nng lng khỏc hay cỏc Cỏc electron s in theo th t vo cỏc lp cú nng lng t thp n cao, bt u l lp 1s Ngoi theo vựng hin din ca chỳng quy tc Hund, cỏc lp electron cú cựng mc nng lng thỡ ban u c in n, cho s electron c thõn l ln nht, sau y mi c in ụi 1.1 S lng t v lp S in electron vo cỏc lp khụng ch ph thuc vo v trớ hay khong cỏch ca chỳng n ht nhõn m cũn Trng thỏi ca mi electron lp v cú th c ph thuc vo mc nng lng ca cỏc lp biu din qua s lng t (c mụ hỡnh nguyờn t Bohr Vớ d: titan cú Z = 22, cu hỡnh theo th t cỏc lp 1s2 v orbital): 2s2 2p6 3s2 3p6 3d4 4s0 nhng nng lng ca lp 4s eo nguyờn lý Pauli, s lng t ca tng cp thp hn lp 3d nờn electron cũn li s in y vo electron nguyờn t khụng c trựng nhau, gii lp 4s (2) trc, sau y mi n lp 3d (2), cu hỡnh thớch cho s phõn b ca chỳng cỏc lp khỏc ỳng ca titan l 1s2 2s2 2p6 3s2 3p6 3d2 4s2 iu ny cng cú ngha l, trờn cựng mt phõn lp, khụng cú electron cú chiu t quay ging Ngoi l: S lng t chớnh n hỡnh thnh nờn cỏc lp chớnh, mi lp chớnh cú n phõn lp Cỏc electron trờn cựng mt lp thỡ cú mc nng lng xp x nhau, v trờn cựng mt phõn lp thỡ cú nng lng bng Tng s electron mi lp chớnh ph thuc vo b s lng t n, l, m v s nhng ti a l 2n2 electron Nguyờn t lantan, Z = 57 lp ngoi cựng 6s2 4f1 , electron t cui cựng in vo 5d trc vo 4f, tng t nguyờn t Ac thỡ 6d trc 5f Trong nguyờn t Cr v Cu mt electron lp cú nng lng thp 4s in vo lp cú nng lng CHNG CU HèNH ELECTRON cao hn 3d, chỳng cú cu hỡnh lp ngoi cựng l 3d5 4s1 v 3d10 4s1 Cỏc trng hp ngoi l khỏc Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ir, Pt, Au, Gd, cỏc actini t Ac n Np v Cm 1.3 Liờn h n bng tun hon 18 nhúm chớnh (nhúm mi) bng tun hon c phõn da theo s electron cỏc lp ngoi cựng: lp s: nhúm (s1 ) - (s2 ) lp p: nhúm 13 (p1 ) - 18 (p6 ) (Tr He, H) lp d: nhúm (d1 ) - 12 (d10 ) S chu k bng s lp n, vi ns l lp ngoi cựng 1.4 Cu hỡnh electron ca mt s nguyờn t Cu hỡnh electron ca cỏc nguyờn t thng c vit di dng kốm theo cu hỡnh electron ca cỏc khớ him cú s th t nh hn ng gn nú cng vi cỏc lp cũn li Vớ d, cu hỡnh electron ca magiờ (Z = 12): [Ne] 3s2 thỡ c hiu 1s2 2s2 2p6 3s2 1.4.1 Khớ him 1.4.2 Z t 11 n 17 1.4.3 Z t 21 n 31 1.4.4 Z t 39 n 49 1.5 Xem thờm Bng tun hon S lng t Kim loi chuyn tip 1.6 Tham kho Chng Chm lng t ma trn thy tinh v sau ú Louis E Brus quan sỏt thy chỳng dung dch dng keo vo nm 1985.[7] ut ng chm lng t" c t bi Mark Reed.[8] Cỏc nh nghiờn cu ó nghiờn cu cỏc ng dng cho cỏc chm lng t tranzito, cỏc t bo nng lng mt tri, ốn LED, v laser it H cng ó kho cu cỏc chm lng t vi vai trũ l tỏc nhõn cho k thut chp nh y hc v chỳng cú th tr thnh qubit in toỏn lng t Chm lng t c thng mi húa u tiờn mt sn phm s dng chỳng l dũng Sony XBR X900A ca TV mn hỡnh phng c tung vo nm 2013.[9] c tớnh in t ca mt chm lng t cú liờn quan cht ch vi kớch thc v hỡnh dng ca nú Vớ d, cỏc khe h nng lng (band gap) mt chm lng t m xỏc nh phm vi tn s ca ỏnh sỏng phỏt t l nghch vi rng ca nú Trong cỏc ng dng thuc nhum hunh quang tn s ca ỏnh sỏng phỏt tng kớch thc ca cỏc chm lng t gim Do ú, mu sc ca ỏnh sỏng phỏt thay i t mu sang mu xanh kớch thc ca cỏc chm lng t c lm nh hn.[10] iu ny cho phộp cỏc trng thỏi kớch thớch v phỏt x ca chm lng t c iu chnh cao Vỡ kớch thc ca mt chm lng t cú th c thit k ch to nú, tớnh cht dn in ca nú cú th c kim soỏt cn thn Chm lng t cú nhiu kớch c khỏc nhau, chng hn h mng nano gradien a lp (Gradient multilayer nanolm), cú th c to thc hin mt lot tớnh cht phỏt x mong mun Chm lng t dung dch keo c chiu x vi ỏnh sỏng UV Chm lng t cú kớch thc khỏc phỏt ỏnh sỏng mu khỏc hiu ng giam gi lng t 2.1 S giam gi lng t cht bỏn dn Chm lng t lý tng t lp InAs/GaAs Chm lng t l mt tinh th nano c lm t vt liu cht bỏn dn m kớch thc ca nú nh lm xut hin cỏc c tớnh c hc lng t C th, exciton ca nú c gii hn c ba chiu khụng gian Nhng tớnh cht in t ca cỏc vt liu th hin c tớnh trung gian gia nhng ln cht bỏn dn v cỏc phõn t ri rc.[1][2][3] Alexey Ekimov ln u tiờn phỏt hin chm lng t vo nm 1981[4][5] [6] mt Trong mt cht bỏn dn tinh th cú ng kớnh nh hn kớch thc ca nú exciton Bohr bỏn kớnh, cỏc exciton c ộp, dn n giam gi lng t Cỏc mc nng lng sau ú cú th c mụ hỡnh húa bng cỏch s dng ht hp mụ hỡnh ú nng lng ca cỏc quc gia khỏc ph thuc vo di ca hp Chm lng t c cho l ch giam CHNG CHM LNG T 3D gii hn hm súng electron mt chm lng t õy, cỏc chm lng t hỡnh ch nht v hỡnh tam giỏc c hin th Trng thỏi nng lng cỏc chm hỡnh ch nht cú nhiu s-type v p-type Tuy nhiờn, mt du chm tam giỏc chc nng thu súng c trn giam i xng (Click vo cho hỡnh nh ng) yu 'nu bỏn kớnh ca h l vo th t ca cỏc exciton Bohr bỏn kớnh; chm lng t c cho l ch giam mnh m 'nu h bỏn kớnh nh hn bỏn kớnh Bohr exciton Nu kớch thc ca cỏc chm lng t nh cỏc hiu ng lng t thng tr connement (thụng thng di 10 nm), cỏc tớnh cht in t v quang hc c ỏnh giỏ cao iu chnh c Band gap energy Cỏc khe h cú th tr nờn ln hn ch giam mnh m kớch thc ca chm lng t nh hn bỏn kớnh Bohr Exciton mt b * nh cỏc mc nng lng tỏch ( ) m ab = r ab ni mt l bỏn kớnh Bohr=0.053 nm,m l lng, l lng gim, v l hng s in mụi kớch thc ph thuc (Hng s in mụi) iu ny dn n s gia tng tng nng lng phỏt thi (tng ca cỏc mc nng lng khong cỏch vựng nh hn ch giam mnh l ln hn so vi mc nng lng cỏc khong trng ca ban nhc mc ban u ch giam yu) v cỏc khớ thi cỏc bc súng khỏc nhau; ú chớnh xỏc l nhng gỡ xy ỏnh mt tri, ni cỏc hiu ng lng t giam l hon ton chim u th v cỏc mc nng lng tỏch n mc m ph nng lng gn nh liờn tc, ú phỏt ỏnh sỏng trng Connement energy Cỏc thc th exciton cú th c mụ hỡnh húa bng cỏch s dng ht hp Cỏc electron v l cú th c xem nh l hydrogen Tỏch cỏc mc nng lng cho cỏc chm lng t nh hiu cỏc mụ hỡnh Bohr vi cỏc ht nhõn hydro ng giam gi lng t Trc ngang l bỏn kớnh, hoc kớch thay th bng cỏc l ca in tớch dng v thc, ca cỏc chm lng t v b * l bỏn kớnh Bohr Exciton lng electron tiờu cc Sau ú, cỏc mc nng lng ca cỏc exciton cú th c biu din nh l gii phỏp cho cỏc ht mt hp tng trt (n = 1) vi lng thay th bng trng lng gim Vỡ vy, bng cỏch thay i kớch thc ca Hunh quang xy mt electron b kớch thớch cỏc chm lng t, nng lng giam ca exciton th gión vi cỏc trng thỏi c bn v kt hp vi cỏc cú th c kim soỏt l Trong mt mụ hỡnh n gin, nng lng ca cỏc photon phỏt cú th c hiu l tng s nng lng Bound exciton energy Cú thu hỳt Coulomb gia cỏc electron mang in tớch õm v l mang in tớch khe h gia cỏc mc b chim úng v mc nng dng Nng lng tiờu cc liờn quan n vic thu lng cũn trng, cỏc ngun nng lng giam ca l v hỳt t l vi nng lng Rydberg v t l nghch vi cỏc electron b kớch thớch, v nng lng rng buc ca bỡnh phng ca hng s in mụi kớch thc ph exciton (cp electron-l trng): 2.2 SN XUT thuc vo[11] ca cht bỏn dn Khi kớch thc ca tinh th bỏn dn nh hn bỏn kớnh Exciton Bohr, s tng tỏc Coulomb phi c sa i phự hp vi tỡnh hỡnh Do ú, tng cỏc ngun nng lng cú th c biu din nh l: ( ) 1 = Econnement = + 2a2 me mh 2àa2 Eexciton = Ry = Ry r me E = Ebandgap + Econnement + Eexciton = Ebandgap + Ry 2àa2 ni l lng gim, mt l bỏn kớnh m l lng electron t do, m l lng l, v l hng s in mụi kớch thc ph thuc Mc dự cỏc phng trỡnh trờn c rỳt bng cỏch s dng cỏc gi nh n gin húa, cỏc tỏc ng l rừ rng; nng lng ca cỏc chm lng t ph thuc vo kớch thc ca chỳng nh hng connement lng t, ú chim u th di kớch thc quan trng dn n s thay i cỏc tớnh cht quang hc Hiu ng ny giam gi lng t trờn chm lng t ó c thc nghim kim chng[12] v l mt tớnh nng ch yu ca nhiu cu trỳc in t hin i.[13][14] Bờn cnh ú giam c ba chiu (tc l, mt chm lng t), cht bỏn dn lng t gii hn khỏc bao gm: Dõy lng t, ú gii hn in t hoc l hai chiu khụng gian v cho phộp tuyờn truyn phớ mt phn ba Ging lng t, ú gii hn in t hoc l mt chiu v cho phộp tuyờn truyn t khụng gian hai chiu 2.2 Sn xut Cú mt s cỏch gii hn exciton bỏn dn, dn n cỏc phng phỏp khỏc sn xut cỏc chm lng t Núi chung, dõy lng t, ging nc v chm c trng tiờn tin epitaxy k thut cỏc tinh th nano c sn xut bng phng phỏp húa hc hoc bng cỏch cy ion, hoc cỏc thit b nano c thc hin bi nh nc-of-the-ngh thut in thch bn k thut.[15] Dots Quantum vi tng bc y mnh phỏt thi t tớm n m ang c sn xut mt quy mụ kg ti PlasmaChem GmbH truyn thng cỏc quỏ trỡnh húa hc S tng hp ca cht keo chm lng t c thc hin bng cỏch s dng tin cht,[3] hu c hot ng b mt,[16] v dung mụi Vic lm núng dung dch nhit cao, cỏc tin cht b phõn hy to thnh monome m sau ú to ht nhõn v to cỏc tinh th nano Nhit quỏ trỡnh tng hp l mt yu t quan trng vic xỏc nh cỏc iu kin ti u cho s phỏt trin tinh th nano Nú phi cao cho phộp sp xp li v ca cỏc nguyờn t quỏ trỡnh tng hp thp thỳc y s tng trng tinh Nng ca monome l mt yu t quan trng l phi c kim soỏt nghiờm ngt quỏ trỡnh tng trng tinh th nano ỏ trỡnh phỏt trin ca cỏc tinh th nano cú th xy hai ch khỏc nhau, trung v phõn kỡ" nng monomer cao, kớch thc ti hn (kớch thc tinh th nano m khụng phỏt trin hay thu nh) l tng i nh, dn n s tng trng ca gn nh tt c cỏc ht Trong ch ny, cỏc ht nh hn tng trng nhanh hn so vi nhng ngi ln (t tinh th ln hn cn nhiu nguyờn t phỏt trin hn cỏc tinh th nh) kt qu l trung ca s phõn b kớch thc ht n nng sut gn monodisperse Kớch thc trung l ti u nng monomer c gi nh vy m kớch thc tinh th nano hin trung bỡnh luụn l hi ln hn so vi kớch thc ti hn eo thi gian, nng monomer gim, kớch thc quan trng tr nờn ln hn so vi kớch thc trung bỡnh hin ti, v phõn phi defocuses Cú nhiu phng phỏp keo sn xut nhiu cht bỏn dn khỏc Chm in hỡnh c lm bng hp cht nh phõn nh chỡ sunphua, selenua chỡ, cadmium selenide, cadmium sulde, indium arsenide, v indium phosphide Dots cng cú th c lm t hp cht bc ba nh cadmium sulde selenua Nhng chm lng t cú th cha khong 100 n 100.000 nguyờn t chm lng t, vi ng kớnh t 10 n 50 nguyờn t iu ny tng ng vi khong 2-10 nm, v lỳc 10 nm, ng kớnh gn triu chm lng t cú 2.2.1 Keo tng hp th c xp hng u n cui v phự hp vi chiu Keo bỏn dn tinh th nano c tng hp t cỏc hp rng ca mt ngún tay cỏi ca ngi cht tin thõn hũa tan cỏc gii phỏp, ging nh Lụ ln ca cỏc chm lng t cú th c tng hp 13.4 CH THCH ca cỏc electron nguyờn t C th hn, i vi mi electron nguyờn t, Slater mun xỏc nh hng s che lp (s) v s lng t hiu dng (n*) t nh n s (r) = r n ( ) (Z s)r exp n cung cp mt phng phỏp xỏc nh gn ỳng cho hm súng ca mt in t n l Slater nh ngha n* theo quy tc nu n = 1, 2, 3, 4, 5, thỡ ln lt n* = 1, 2, 3, 3.7, 4.0 v 4.2 ú l mt s tựy chnh nhm mc ớch lm mc nng lng nguyờn t cú c sau tớnh toỏn n khp vi cỏc kt qu thc nghim 13.4 Chỳ thớch [1] Slater, J C (1930) Atomic Shielding Constants (PDF) Phys Rev 36 (1): 5764 Bibcode:1930PhRv3657S doi:10.1103/PhysRev.36.57 [2] Housecro, Cathetine E.; Alan G Sharpe (2008) Inorganic Chemistry Prentice Hall tr 21 ISBN 978-013-175553-6 [3] Clementi, E.; Raimondi, D L (1963) Atomic Screening Constants from SCF Functions J Chem Phys 38 (11): 26862689 doi:10.1063/1.1733573 [4] Clementi, E.; Raimondi, D L.; Reinhardt, W P (1967) Atomic Screening Constants from SCF Functions II Atoms with 37 to 86 Electrons Journal of Chemical Physics 47: 13001307 doi:10.1063/1.1712084 [5] Miessler, Gary L.; Tarr, Donald A (2003) Inorganic Chemistry Prentice Hall tr 38 ISBN 9780130354716 33 Chng 14 Sai s chng cht v trớ b c s 14.1 Sai s chng cht v trớ b c s (BSSE) Vic xỏc nh th nng tng tỏc gia cỏc phõn t l cn thit vic hiu nhng thuc tớnh húa hc v vt lý ca vt cht Vỡ th, thp niờn va qua ó t c nhng thnh tu ỏng k vic hiu c bn tng tỏc gia cỏc phõn t cng nh xỏc nh gn ỳng tt nht th nng tng tỏc, c bit i vi nhng h tng tỏc yu Tớnh toỏn c hc lng t da vo thuyt obitan phõn t ab-initio úng vai trũ trung tõm vic phỏt trin hng nghiờn cu loi tng tỏc yu, iu ny cha tng c thc hin trc ú Cú nhiu yu t úng gúp n vic phỏt trin xa hn da trờn quan im ab-intio i vi th nng tng tỏc gia cỏc phõn t, nhng yu t ú bao gm s phỏt trin, ci thin k thut v phn mm tớnh toỏn cho phộp dựng nhng phng phỏp tng quan electron cao v b hm c s ln Tớnh toỏn ab-initio ca th nng tng tỏc cú th c thc hin da trờn hoc cỏch tip cn siờu phõn t hoc cỏch tip cn nhiu lon Tuy nhiờn, c hai cỏch tip cn u cú nhng gii hn ca nú, c th l gii hn v b hm c s Cỏch tip cn siờu phõn t cú th c ỏp dng n tng tỏc van der Waals v liờn kt cng húa tr Cỏch tip cn ny d hn v thng c s dng vi nng lng tng tỏc (EINT) gia hai phõn t A v B nh lng khỏc gia ime AB v hai phõn t thnh phn A v B: EINT=EAB(AB)-[(EA(A)+EB(B)] (1) Tuy nhiờn, nhiu th thỏch v tranh lun tip tc xy vi vic tớnh chớnh xỏc nhng tr s nng lng EAB, EA v EB nhn c tr s gn ỳng tt nht EINT Vic tớnh nng lng tng tỏc theo biu thc (1) khụng phự hp, bi vỡ tớnh nng lng ca EA ti b b c s A ta ch xột electron cú mt trờn nhng obitan vi b c s A cho mi ht nhõn trờn A Phộp tớnh ny tng t i vi nng lng EB ti b c s B ca B Tuy nhiờn, tớnh nng lng EAB ca ime AB thỡ nhng electron ca A hoc B ime khụng ch cú mt trờn nhng obitan ht nhõn ca riờng nú m cũn trờn nhng obitan ca ht nhõn ca phõn t lõn cn vi b c s AB = A + B Vỡ th, tr nng lng tớnh c õm hn giỏ tr thc cú ca ime iu ú cú ngha rng tớnh nng lng ca ime ta ó s dng b c s ln hn so vi b c s ca hai monome Sai s ny c gi l sai s chng cht v trớ b c s, gi l BSSE Cú hai cỏch loi b sai s: hoc dựng b c s y cho mi monome ban u hoc hiu chnh nng lng ca ime Tuy nhiờn, vic dựng b c s y rt khú thc hin vỡ gii hn v mt tớnh toỏn Gii phỏp thng c ỏp dng nht hiu chnh sai s ú l tớnh nng lng theo biu thc: EINT,CP = EAB(AB) [EA(AB) + EB(AB)] (2) Chỳ ý rng EA(AB) c tớnh vi mt b c s cha nhng obitan A trờn mi ht nhõn A v nhng obitan A khỏc (thờm) phự hp khụng gian tng ng vi v trớ cõn bng ca monome A ime Phộp tớnh cng tng t i vi EB(AB) Gii phỏp ny c gi l hiu chnh " lch thng bng (Counterpoise) ca Boys v Bernadi S khỏc gia phng trỡnh (2) v (1) chớnh l BSSE: CP = [EA(A) + EB(B)] [EA(AB) + EB(AB)] (3) Rừ rng vic thc hin hiu chnh nh trờn phự hp vi bn cht ca BSSE Nhng giỏ tr ca EINT,CP nhiu trng hp thng dng hn, EINT li õm hn giỏ tr tht ca nú Chớnh iu ny ó dn n mt s tỏc gi cho rng phng phỏp Counterpoise d oỏn BSSE quỏ ln vỡ nguyờn lý Pauli hn ch mt phõn t chim nhng hm c s ca mt phõn t khỏc tớnh toỏn nng lng EAB Sau ú, mt s phng phỏp Counterpoise khỏc c a thay th, nhiờn khụng cú mụ hỡnh no thnh cụng v c chp nhn nh hng ca BSSE khỏ ln i vi nng lng tng tỏc mc dự khú nh lng rừ rng Tuy nhiờn, cú mt vi trng hp ngoi l rng, nu chỳng ta s dng mt b c s khụng y , vic khụng hiu chnh BSSE cú th dn n EINT phự hp thc nghim hn so vi hiu chnh nú iu ny bi vỡ s thiu ht hm phõn cc cn thit úng gúp n nng lng phõn tỏn EINT mt b c s c bự p bi sai s s chng cht v trớ b c s ime Nh vy, s cú mt ca BSSE khụng nhng khụng hiu chnh c sai s m cũn lm gia tng s thiu ht ca b c s Tuy vy, hu ht trng hp BSSE dng nh bự p nhng sai s s thiu ht b c s v 34 14.2 THAM KHO mc lý thuyt s dng Túm li, sai s khụng b loi b nu khụng hiu chnh BSSE Hin nay, nhng ỏp dng ca phng phỏp Counterpoise rt rng rói v ó cung cp nhiu bng chng mnh m cho vic ng h giỏ tr ca phng phỏp ny 14.2 Tham kho 35 Chng 15 S lng t chớnh S lng t ớnh l mt s lng t, ch yu th hin mc nng lng ca electron nguyờn t Mụ hỡnh nguyờn t Bohr ch miờu t c trng thỏi nng lng thp nht, n = Nhng trờn thc t cú vụ s lp nng lng ri rc khỏc Do cú nhiu s lng cỏc lp, v khong cỏch gia chỳng cng ln thỡ cng gn nhau, nờn nng lng biu hin nh mt vựng liờn tip, mc du chỳng l cỏc g ri rc, hay cũn gi l c lng t húa eo thuyt lng t hin i, mt vi v trớ tn ti ca electron nguyờn t tng ng vi s khỏc hỡnh mu ca súng ng Nh xy mt dõy n guitar S khỏc bit chớnh l cỏc súng electron hot ng c ba chiu ca khụng gian, dõy n gita ch dao ng chiu Mi hỡnh mu súng c nh dng bi mt s nguyờn n, v c gi l s lng t chớnh Giỏ tr ca n ch rừ s lng nh ca biờn (antinode) tn ti mt mu hỡnh súng ng, s lng nh cng nhiu, trng thỏi nng lng cng cao nng ca electron c a bi cụng thc E = k2 e4 m 2h2 n2 ú k l hng s tnh in, e l in tớch ca electron, m l lng ca nú, h l hng s Planck v n s lng t chớnh Du (-) cho thy th nng ca nú luụn luụn õm Do nng lng cú t l nghch o bỡnh phng vi n, nờn nng lng tin n thỡ n tr nờn rt ln, nhng nú khụng bao gi t ti giỏ tr Cụng thc trờn c a mt phn gc ca mụ hỡnh nguyờn t Bohr v c s dng vi nguyờn t hirụ, nhng khụng ỏp dng c vi cỏc nguyờn t cú nhiu hn electron 15.1 Tham kho 36 Chng 16 Thuyt FMO uyt võn o biờn phõn t l mt lý thuyt ỏp dng ca thuyt võn o phõn t nhm mụ t tng tỏc HOMO - LUMO in ca phõn t cũn li Orbital liờn kt ca mt phõn t v Orbital khụng liờn kt ca phõn t cũn li (c bit l HOMO v LUMO) tng tỏc ln gõy lc hỳt 16.1 Lch s T nhng quan sỏt ny, thuyt võn o biờn phõn t Nm 1952, Ken'ichi Fukui cho mt mt trang vit (FMO) ó n gin húa hot thnh tng tỏc gia trờn t Journal of Chemical Physics (Bi bỏo v Húa lý) vi HOMO v LUMO ca hai phõn t khỏc Nú giỳp nhan A molecular theory of reactivity in aromatic gii thớch d oỏn ca y tc Woodward-Homan hydrocarbons (tm dch: uyt phn ng phõn t ca dnh cho phn ng nhit cn vũng, cú th túm tt bng cỏc hidrocacbon thm.[1] Dự b cụng lun thi by gi, phỏt biu sau: nhng sau ú cựng vi Roald Homann, ụng ó c trao tng gii Nobel Húa hc vi cụng trỡnh nghiờn cu ay i trng thỏi nn/cn bn ca vũng c ch phn ng Cụng trỡnh ca Homan trung l c phộp v tớnh i xng tng ca to chui cỏc phn ng cn vũng húa hu c nh (4q+2) v (4r) l s l" tớnh i xng võn o phõn t; ụng l ng tỏc gi e Conservation of Orbital Symmetry (tm dch: S (4q+2) l s ch h thng electron thm, ng bo ton tớnh i xng orbital (phõn t)") vi Robert Burns vựng khụng gian; tng t, (4r) l s ch h thng Woodward, ngi ó tng nhn c mt gii Nobel electron khụng thm, khỏc vựng khụng gian Cú th trc qua i nhn rng tng ca cỏc h trờn l thỡ phn ng Fukui c lp nghiờn cu cỏc tng tỏc thụng qua cỏc c phộp xy v mt nhit hc.[2] quan sỏt võn o biờn ca phõn t, v cỏc tỏc ng c th ca Võn o phõn t liờn kt cú mc nng lng cao nht (HOMO) v Võn o phõn t khụng/phn liờn kt 16.3 ng dng cú mc nng lng thp nht (LUMO) lờn c ch phn ng, t ú dn ti tờn gi sau ny ca hc thuyt l uyt Võn o biờn phõn t (gi tt: uyt FMO) Sau 16.3.1 Cng vũng ú, ụng dựng nhng tng tỏc ó nghiờn cu lm rừ y tc Woodward-Homann 16.2 Hc thuyt Fukui nhn thy xp x hiu qu cho hot phn ng, cn phi quan sỏt cỏc võn o (HOMO/LUMO) ngoi cựng (võn o biờn) Vic ú thụng qua ba bc quan sỏt thuyt võn o phõn t (orbital) hai phõn t tng tỏc: Orbital liờn kt ca nhng phõn t khỏc thỡ y Phn dng in ca mt phõn t hỳt phn õm Phn ng cng vũng l phn ng ng thi to ớt nht hai liờn kt mi, v ú chuyn binh hai hay nhiu phõn t mch h thnh vũng.[3] Trng thỏi chuyn ca nhng phn ng ny liờn quan c th n cỏc electron ca phõn t chuyn ng trờn vũng (gi kớn) cho phn ng cn vũng Nhng phi ng ny cú th c d oỏn nh vo quy tc WoodwardHomann v ú c xp x bng thuyt FMO Phn ng Diels-Alder gia hai phõn t anhydrid maleic v cyclopentadiene c phộp xy theo quy tc Woodward-Homann bi cú sỏu electron dch chuyn cựng mt vựng khụng gian v khụng cú electron no chuyn vựng Dn ti, tng ca mt (4q+2) v 37 38 CHNG 16 THUYT FMO khụng (4r) l l, cú ngha phn ng c phộp v mt nhit hc Ngoi ra, thuyt FMO cũn i xa hn d oỏn chn lc lp th, mt khớa cnh khụng c Woodward & Homann núi ti Vỡ cú mt h [4+2], n gin ta xột phi ng ca butadien v eten HOMO ca butadien v LUMO ca ờtilen u phn i xng (i xng quay), nờn phn ng c phộp.* * Lu ý: Khi LUMO v HOMO ca eten v butadien u i xng, thỡ phn ng c phộp Nhng khỏi nim ny liờn quan n s o ln nhu cu electron DielsV mt chn lc lp th ca phn ng gia anhidrid Alder. maleic v cyclopentadien, sn phm endo c u tiờn, cho ta li gii thớch ti u dựng thuyt FMO Anhidrid maleic cú mang nhiu nhúm hỳt electron, lm cho nú thiu in t v tỡm kim phn ng vi nhng 16.3.2 Phn ng chuyn v sigma phõn t di electron, tuõn theo phn ng DielsAlder mu Do ú, phn ng ca HOMO v A sigmatropic rearrangement is a reaction in which LUMO c phộp din tin Bt lun, sn a sigma bond moves across a conjugated pi system phm exo bn hn v mt nhit ng lc hc, nhng with a concomitant shi in the pi bonds e shi in vi cỏc tng tỏc orbital (khụng liờn kt) th cp, nng the sigma bond may be antarafacial or suprafacial In lng trng thỏi chuyn endo c gim xung v giỳp the example of a [1,5] shi in pentadiene, if there is y nhanh tc hỡnh thnh nờn endo c u tiờn v a suprafacial shi, there is e- moving suprafacially mt ng hc phõn t Vỡ cú liờn kt s cp nờn sn and none moving antarafacially, implying this reaction phm exo c hỡnh thnh, nhng chm hn s is allowed by the Woodward-Homann rules For an hỡnh thnh ca sn phm chớnh, endo.[2] antarafacial shi, the reaction is not allowed ese results can be predicted with FMO theory by observing the interaction between the HOMO and LUMO of the species To use FMO theory, the reaction should be considered as two separate ideas: (1) whether or not the reaction is allowed, and (2) which mechanism the reaction proceeds though In the case of a [1,5] shi on pentadiene, the HOMO of the sigma bond (i.e a constructive bond) and the LUMO of butadiene on the remaining carbons is observed Assuming the reaction happens suprafacially, the shi results with the HOMO of butadiene on the carbons that are not involved in the sigma bond of the product Since the pi system changed from the LUMO to the HOMO, this reaction is allowed (though it would not be allowed if the pi system went from LUMO to LUMO) 16.4 CH THCH To explain why the reaction happens suprafacially, rst notice that the terminal orbitals are in the same phase For there to be a constructive sigma bond formed aer the shi, the reaction would have to be suprafacial If the species shied antarafacially then it would form an antibonding orbital and there would not be a constructive sigma shi It is worth noting that in propene the shi would have to be antarafacial, but since the molecule is very small that twist is not possible and the reaction is not allowed 16.3.3 Phn ng nhit An electrocyclic reaction is a percyclic reaction involving the net loss of a pi bond and creation of a sigma bond with formation of a ring is reaction proceeds through either a conrotatory or disrotatory mechanism In the conrotatory ring opening of cyclobutene, there are electrons moving suprafacially (on the pi bond) and moving antarafacially (on the sigma bond) is means there is one 4q+2 suprafacial system and no 4r antarafacial system; thus the conrotatory process is thermally allowed by the Woodward-Homann rules e HOMO of the sigma bond (i.e a constructive bond) and the LUMO of the pi bond are important in the FMO theory consideration If the ring opening uses a conrotatory process then the reaction results with the HOMO of butadiene As in the previous examples the pi system moves from a LUMO species to a HOMO species, meaning this reaction is allowed.[2] 16.4 Chỳ thớch [1] J Chem Phys 20, 722 (1952); doi:10.1063/1.1700523 39 [2] Fleming, Ian (1978), Frontier Orbitals and Organic Chemical Reactions, London: Wiley, tr 29109, ISBN 0471018198 [3] Miller, Bernard (2004), Advanced Organic Chemistry: Reactions and Mechanisms, Upper Saddle River, NJ: Pearsons, tr 5354, ISBN 0130655880 Chng 17 Toỏn t Hamilton Trong c hc lng t, toỏn t Hamilton hay Hamiltonian l mt toỏn t tng ng vi nng lng ton phn ca h gõy nờn s bin i theo thi gian, i (r, t) = H(r, t) t c ký hiu l H, hoc Nh ta ó bit thỡ nng lng ton phn ca h bng tng th nng v ng l toỏn t Hamilton Trong ú H nng ca h; Gi s (r, t) cú th vit di dng tớch hm theo thi gian vi hm ta ; = T + V H (r, t) = (r) f (t) o hm theo t.Ta cú: t (r, ú t) = (r) df (t)/ dt V o hm bc theo r.Ta cú: V = V = V (r, t) V l toỏn t t liờn hp trờn khụng gian Hilbert vi i lng quan sỏt l th nng T = ^ pã^ p 2m = p2 2m = 2m 2 p l toỏn t t liờn hp trờn khụng gian Hilbert vi i lng quan sỏt l ng lng ^ p = i T l toỏn t t liờn hp trờn khụng gian Hilbert vi i lng quan sỏt l ng nng t (r, t) /r2 = f (t)d2 (r)/dr2 ay vo phng trỡnh Schrửdinger Ta cú (r) f (t) i (r) df (t)/ dt = H Chia v cho (r) Ta c phng trinh vi phõn f (t) i df (t)/ dt = H Gii phng trỡnh vi phõn ny ta c f (t) = eiHt/ Vy hm súng c vit di dng (r, t) = (r) eiHt/ ay vo phng trỡnh Schrửdinger ban u, ta c phng trỡnh Schrửdinger khụng ph thuc vo thi gian 2m + V (r) (r) = E (r) Kt hp toỏn t trờn, ta cú toỏn t Hamilton c s Khi gii phng trỡnh ny, ta tỡm c hm riờng v dng phng trỡnh Schrửdinger giỏ tr riờng ca toỏn t Hamilton.Khi tỡm c giỏ tr riờng, ta cú th xỏc nh cỏc mc nng lng v xem nú co b giỏn on hay khụng Khi tỡm c hm riờng, = T + V H ta cú th tớnh xỏc sut nhng ni tỡm thy ht ^ pã^ p = + V (r, t) 2m 2 17.0.2 Xem thờm + V (r, t) = 2m phng trỡnh Schrửdinger 17.0.1 Phng trỡnh Schrửdinger v toỏn C hc lng t t Hamilton Xem bi vit chớnh phng trỡnh Schrửdinger 17.1 Tham kho Cho hm súng (r, t) Ta cú phng trỡnh Schrửdinger ph thuc vo thi gian ca hm súng ú l 40 Chng 18 Tng tỏc trao i theo nguyờn tc: t nguyờn t khong cỏch vụ cựng (hai nguyờn t c lp khụng tng tỏc, cú ngha l ta cú gn ỳng bc khụng Lỳc ny, phng trỡnh Schrodinger c vit bi: [1 + 2m (E0 e2 ra1 )]a (q1 ) =0 vi E0 l mc nng lng thp nht Nghim tng quỏt cú th c vit bi: (q1 , q2 ) = a (q1 )b (q2 ) + b (q1 )a (q2 ) Mụ hỡnh bi toỏn xỏc nh tng tỏc trao i , l cỏc h s tuyn tớnh Tng tỏc trao i l mt hiu ng lng t xy a hai nguyờn t li khong cỏch gn nhau, v hm súng ca hai hay nhiu in t ph nhau, cú tỏc ta cú gn ỳng bc nht Lỳc ú, s tng tỏc dng lm tng hay gim nng lng t ca h, lm gia cỏc in t v iụn, nng lng ca h c cho cỏc spin song song hoc i song song vi V thay bi: mt bn cht, tng tỏc trao i l tng tỏc tnh in c bit gia cỏc spin Hiu ng ny c phỏt hin mt E = 2E0 + E cỏch c lp bi Werner Heisenberg[1] v Paul Dirac[2] Lỳc ú, nghim tng quỏt ca bi toỏn cú th thay i: vo nm 1926 (E 2 e2 R e2 r + e2 ra1 + e2 rb1 )a (q1 )b (q2 ) + (E er + rea2 + reb2 )b (q1 )a (q2 ) = (dựng iu kin trc giao a (q)b (q)dq = ) e2 e2 = ( r reb1 Mụ hỡnh tng tỏc trao i c Heisenberg v Dirac Nu ta t: C R + xut, London l ngi phỏt trin v a mụ hỡnh re )|a (q1 )|2 |b (q2 )|2 dq1 dq2 a2 tớnh toỏn da trờn mu n gin v nguyờn t hydro e2 e2 = (r vi hai nguyờn t t cnh (hỡnh v) v lỳc ú A ra1 e phng trỡnh Schrodinger c vit bi: rb2 )a (q1 )b (q1 )b (q2 )a (q2 )dq1 dq2 e R 18.1 Mụ hỡnh tng tỏc trao i [1 + + 2m [E V (R, ra1 , ra2 , rb1 , rb2 , r)] = vi , ln lt l cỏc toỏn t ng nng ca in t, E l nng lng ca h, V l hm th nng = = V = x21 x22 e2 R + + y12 + y22 e2 r + + e2 ra1 z12 v A (E C) = E = C A hay E = 2E0 + C A z22 e2 ra2 (E C) A = v cú th rỳt nng lng: Bi toỏn cú th vit n gin thnh: e2 rb1 e2 rb2 = (q1 , q2 ) = (x1 , y1 , z1 , x2 , y2 , z2 ) Bi toỏn c gii bng phng phỏp gn ỳng liờn tc H s A c gi l tớch phõn trao i ca h, c vit tng quỏt nh sau: Aij = a (q)j (q)i (q )j (q )[Vij (|qq |)+gi (q)+ gj (q)]dqdq 41 42 18.2 Tng tỏc trao i v tiờu chun st t Khi ỏp dng mụ hỡnh tng tỏc trao i mu st t, nng lng ca h cỏc spin (nng lng tng tỏc trao i) c vit bi: Wex = i,j Aij (j j ) vi Aij l tớch phõn trao i gia spin th i v j, i , j l spin th i v th j Nh vy, cc tiu húa nng lng thỡ spin cnh phi hon ton song song vi Vi giỏ tr Aij > , ta cú h trng thỏi st t (tng tỏc trao i dng), nu Aij < , ta cú h trng thỏi phn st t 18.3 Tng tỏc trao i giỏn tip Trong mt s vt liu c bit (in hỡnh l cỏc perovskite) thỡ t tớnh c to khụng trc tip t cỏc spin liờn kt trc tip vi m xy mt cỏch giỏn tip, cú ngha l, tng tỏc trao i cng c to mt cỏch giỏn tip gia cỏc iụn thụng qua iụn O2+ Cỏc in t trờn mc eg cú th nhy bc qua iụn O2+ m gi nguyờn hng spin cho phự hp vi quy tc Hund õy l c ch liờn kt giỏn tip gia hai iụn thụng qua O2+ Nu iụn cựng húa tr (vớ d Mn4+ vi Mn4+ ), tng tỏc trao i s l õm, ta cú tng tỏc siờu trao i to tớnh phn st t Trong trng hp iụn khỏc húa tr (vớ d Mn4+ vi Mn3+ ) ta s cú tng tỏc trao i kộp to tớnh st t Cng tng tỏc trao i giỏn tip ph thuc vo yu t: di liờn kt: Mn-O Gúc liờn kt Mn-O-Mn 18.4 Xem thờm St t ụmen t 18.5 Tham kho [1] Mehrkửrperproblem und Resonanz in der antenmechanik, W Heisenberg, Zeitschri ỹr Physik 38, 67 (June 1926), pp 411426 [2] P A M Dirac, Proceedings of the Royal Society of London, Series A 112, 762 CHNG 18 TNG TC TRAO I Chng 19 Vt lý bỏn c in Vt lý bỏn c in, hoc gi tt l bỏn c in cp n mt lý thuyt ú cú mt phn ca mt h thng c mụ t theo kiu c hc lng t cỏc phn khỏc c mụ t theo kiu c in Vớ d, cỏc trng vt lý bờn ngoi s l khụng i, hoc thay i s c mụ t theo kiu c in Núi chung, vt lý bỏn c in l mt s phỏt trin theo ly tha ca hng s Plank, kt qu l vt lý c in vi ly tha 0, v xp x ln u tiờn khụng tm thng ca ly tha (1) Trong trng hp ny, cú mt liờn kt rừ rng gia nhng h thng c hc lng t v cỏc xp x bỏn c in v c in cú liờn quan, vỡ nú cú b ngoi tng t i vi s chuyn i t quang vt lý sang quang hỡnh hc 19.1 Sỏch tham kho R Resnick; R Eisberg (1985) antum Physics of Atoms, Molecules, Solids, Nuclei and Particles (n bn 2) John Wiley & Sons ISBN 978-0-471-873730 P.A.M Dirac (1981) Principles of antum Mechanics (n bn 4) Clarendon Press ISBN 978-0-19-852011-5 W Pauli (1980) General Principles of antum Mechanics Springer ISBN 3-540-09842-9 R.P Feynman; R.B Leighton; M Sands (1965) Feynman Lectures on Physics Addison-Wesley ISBN 0-201-02118-8 C.B Parker (1994) McGraw-Hill Encyclopaedia of Physics (n bn 2) McGraw-Hill ISBN 0-07051400-3 19.2 Tham kho 43 44 CHNG 19 VT Lí BN C IN 19.3 Ngun, ngi úng gúp, v giy phộp cho bn v hỡnh nh 19.3.1 Vn bn Cu hỡnh electron Ngun: https://vi.wikipedia.org/wiki/C%E1%BA%A5u_h%C3%ACnh_electron?oldid=31403058 Ngi úng gúp: Mekong Bluesman, Nguyn anh ang, Newone, DHN-bot, Escarbot, JAnDbot, ijs!bot, Kimiroo, VolkovBot, TXiKiBoT, SieBot, Loveless, DragonBot, Maianhvk, Idioma-bot, Qbot, Alexbot, MelancholieBot, Luckas-bot, Amirobot, Xqbot, SassoBot, Ledinhthang, Tnt1984, TuHan-Bot, EmausBot, Cheers!, Ripchip Bot, Cheers!-bot, MerlIwBot, enhitran, AlphamaBot, Addbot, Mốo mp, Gaconnhanhnhen, Tuanminh01, AlphamaBot4, TuanminhBot, P.T., Phammanhhung21 v 44 ngi vụ danh Chm lng t Ngun: https://vi.wikipedia.org/wiki/Ch%E1%BA%A5m_l%C6%B0%E1%BB%A3ng_t%E1%BB%AD?oldid=24218759 Ngi úng gúp: Earthandmoon, Taitamtinh, Cheers!-bot, AlphamaBot, Damian Vo, TuanminhBot v Mt ngi vụ danh in li Ngun: https://vi.wikipedia.org/wiki/%C4%90i%E1%BB%87n_li?oldid=30732213 Ngi úng gúp: DHN, Mekong Bluesman, Squall282, Vpphan, anhdstl, Minbk, Magicknight94, Luckas-bot, Xqbot, Prenn, KamikazeBot, ick and snowshow, TjBot, Cobe tinhnghich1603, Tnt1984, EmausBot, RedBot, Phuong Dolly, Cheers!, Cheers!-bot, enhitran, Alphama, AlphamaBot, Matnaden.kiet, Addbot, Bsnguyenthanhtu, Tuanminh01, TuanminhBot, Hunh Nhõn-thp, Hancaoto, Saitohsuzuko001 v 23 ngi vụ danh in Mt Tri Ngun: https://vi.wikipedia.org/wiki/%C4%90i%E1%BB%87n_M%E1%BA%B7t_Tr%E1%BB%9Di?oldid=22654141 Ngi úng gúp: Mekong Bluesman, Apple, JAnDbot, VolkovBot, Duyt-ph, SieBot, Qbot, JAn Dudớk, Luckas-bot, Eternal Dragon, Batin, PNG, TuHan-Bot, EmausBot, WikitanvirBot, Cheers!-bot, MerlIwBot, AlphamaBot, Addbot, OctraBot, itxongkhoiAWB, GHAWDAS, Tuanminh01, TuanminhBot, ẫn bc AWB, Bachsanab1 v ngi vụ danh Hiu ng lỏ n Ngun: https://vi.wikipedia.org/wiki/Hi%E1%BB%87u_%E1%BB%A9ng_l%C3%A1_ch%E1%BA%AFn?oldid=26340033 Ngi úng gúp: Sholokhov, TuHan-Bot, ZộroBot, JackieBot, Cheers!-bot, DarafshBot, AlphamaBot, angquecui, AlphamaBot2, Addbot v TuanminhBot Húa hc lng t Ngun: https://vi.wikipedia.org/wiki/H%C3%B3a_h%E1%BB%8Dc_l%C6%B0%E1%BB%A3ng_t%E1%BB%AD?oldid= 23672570 Ngi úng gúp: Mxn, DHN, Mekong Bluesman, Zatrach, YurikBot, Lu Ly, Newone, DHN-bot, ijs!bot, Kimiroo, Medimare, VolkovBot, TXiKiBoT, SieBot, Loveless, Alexbot, Ktrungthuy, Muro Bot, Luckas-bot, SilvonenBot, Rubinbot, TuHan-Bot, EmausBot, Cheers!-bot, MerlIwBot, AlphamaBot, Addbot, Tuanminh01, TuanminhBot v ngi vụ danh Lai húa (húa hc) Ngun: https://vi.wikipedia.org/wiki/Lai_h%C3%B3a_(h%C3%B3a_h%E1%BB%8Dc)?oldid=25822357 Ngi úng gúp: Apple, JAnDbot, VolkovBot, SieBot, Qbot, Alexbot, Y Kpia Mlo, Luckas-bot, Eternal Dragon, Xqbot, Jbtvmd, ButkoBot, Tranminh360, Namnguyenvn, TuHan-Bot, EmausBot, ZộroBot, Cheers!, ChuispastonBot, Cheers!-bot, AlphamaBot, Hugopako, Addbot, Gaconnhanhnhen, Mail.love.angel, ẫn bc v 11 ngi vụ danh Liờn kt húa hc Ngun: https://vi.wikipedia.org/wiki/Li%C3%AAn_k%E1%BA%BFt_h%C3%B3a_h%E1%BB%8Dc?oldid=23672603 Ngi úng gúp: DHN, Robbot, Mekong Bluesman, Vng Ngõn H, Sz-iwbot, ỏi Nhi, YurikBot, Lu Ly, Newone, DHN-bot, JAnDbot, ijs!bot, VolkovBot, TXiKiBoT, YonaBot, SieBot, Qbot, OKBot, Ktrungthuy, Luckas-bot, SilvonenBot, Toilatuan0315, ArthurBot, Darkicebot, Xqbot, TobeBot, TuHan-Bot, EmausBot, WikitanvirBot, Cheers!-bot, MerlIwBot, JYBot, AlphamaBot, Buiquankcd, Addbot, OctraBot, Tuanminh01, ẫn bc v ngi vụ danh Lý thuyt VSEPR Ngun: https://vi.wikipedia.org/wiki/L%C3%BD_thuy%E1%BA%BFt_VSEPR?oldid=30721525 Ngi úng gúp: Trung, Tnt1984, TuHan-Bot, EmausBot, ZộroBot, JackieBot, Colaido, Makecat-bot, AlphamaBot, AlphamaBot2, Addbot, Mốo mp, TuanminhBot v ngi vụ danh Nng lng ion húa Ngun: https://vi.wikipedia.org/wiki/N%C4%83ng_l%C6%B0%E1%BB%A3ng_ion_h%C3%B3a?oldid=26738587 Ngi úng gúp: Mxn, Apple, JAnDbot, ijs!bot, VolkovBot, TXiKiBoT, BotMultichill, AlleborgoBot, SieBot, DragonBot, BodhisavaBot, Nallimbot, Luckas-bot, SilvonenBot, ArthurBot, Xqbot, TobeBot, TuHan-Bot, Cheers!-bot, AlphamaBot, Addbot, Tuanminh01, TuanminhBot, P.T. v ngi vụ danh Orbital nguyờn t Ngun: https://vi.wikipedia.org/wiki/Orbital_nguy%C3%AAn_t%E1%BB%AD?oldid=26818717 Ngi úng gúp: JAnDbot, VolkovBot, Qbot, AlleinStein, Luckas-bot, Dangquang kdc, Future ahead, Rubinbot, Xqbot, Mightyzero, Ledinhthang, Volga, Trn Nam H 2001, Banhtrung1, Tnt1984, TuHan-Bot, EmausBot, Cheers!, WikitanvirBot, Mjbmrbot, Cheers!-bot, AvicBot, achanh96, Trong1996, AlphamaBot, Earthshaker, Addbot, Tuanminh01, TuanminhBot, angchungyeulinhtam, P.T. v 10 ngi vụ danh y tc Hund th nht Ngun: https://vi.wikipedia.org/wiki/Quy_t%E1%BA%AFc_Hund_th%E1%BB%A9_nh%E1%BA%A5t?oldid= 30745550 Ngi úng gúp: Mekong Bluesman, Bunhia, Trung, YurikBot, JAnDbot, SieBot, Sholokhov, Muro Bot, ArthurBot, Xqbot, TuHan-Bot, Cheers!-bot, MerlIwBot, AlphamaBot, Addbot, TuanminhBot v ngi vụ danh y tc Slater Ngun: https://vi.wikipedia.org/wiki/Quy_t%E1%BA%AFc_Slater?oldid=24214868 Ngi úng gúp: Sholokhov, AlleinStein, Luckas-bot, Pq, Con Trõu Mng To, TuHan-Bot, ChuispastonBot, Cheers!-bot, AlphamaBot, Addbot, Tuanminh01, Togira Ikonoka 123 v ngi vụ danh Sai s ng t v trớ b c s Ngun: https://vi.wikipedia.org/wiki/Sai_s%E1%BB%91_do_ch%E1%BB%93ng_ch%E1%BA%A5t_ v%E1%BB%8B_tr%C3%AD_b%E1%BB%99_c%C6%A1_s%E1%BB%9F?oldid=20992126 Ngi úng gúp: DHN, Qbot, TuHan-Bot, Cheers!bot, AlphamaBot, AlphamaBot2, Addbot v Mt ngi vụ danh S lng t ớnh Ngun: 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Tp_tin:Flag_of_Israel.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/d/d4/Flag_of_Israel.svg Giy phộp: Public domain Ngi úng gúp: http://mfa.gov.il/MFA/AboutIsrael/IsraelAt50/Pages/The%20Flag%20and%20the%20Emblem.aspx Ngh s u tiờn: e Provisional Council of State Proclamation of the Flag of the State of Israel of 25 Tishrei 5709 (28 October 1948) provides the ocial specication for the design of the Israeli ag Tp_tin:Flag_of_Italy.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/0/03/Flag_of_Italy.svg Giy phộp: Public domain Ngi úng gúp: ere has been a long discussion on the colors of this ag Please read the talk page before editing or reverting this image Pantone to RGB performed by http://www.pantone.com/pages/pantone/colorfinder.aspx Ngh s u tiờn: see below Tp_tin:Flag_of_Japan.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/9/9e/Flag_of_Japan.svg Giy phộp: Public domain Ngi úng gúp: Law Concerning the National Flag and Anthem (1999) (Japanese) (English) Ngh s u tiờn: Various Tp_tin:Flag_of_Mexico.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/f/fc/Flag_of_Mexico.svg Giy phộp: Public domain Ngi úng gúp: is vector image was created with Inkscape Ngh s u tiờn: Alex Covarrubias, April 2006 Tp_tin:Flag_of_Norway.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/d/d9/Flag_of_Norway.svg Giy phộp: Public domain Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to Ngh s u tiờn: Dbenbenn Tp_tin:Flag_of_Portugal.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/5/5c/Flag_of_Portugal.svg Giy phộp: Public domain Ngi úng gúp: http://jorgesampaio.arquivo.presidencia.pt/pt/republica/simbolos/bandeiras/index.html#imgs Ngh s u tiờn: Columbano Bordalo Pinheiro (1910; generic design); Vớtor Luớs Rodrigues; Antúnio Martins-Tuvỏlkin (2004; this specic vector set: see sources) Tp_tin:Flag_of_South_Korea.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/0/09/Flag_of_South_Korea.svg Giy phộp: Public domain Ngi úng gúp: Ordinance Act of the Law concerning the National Flag of the Republic of Korea, Construction and color guidelines (Russian/English) Ngh s u tiờn: Various Tp_tin:Flag_of_Spain.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/9/9a/Flag_of_Spain.svg Giy phộp: CC0 Ngi úng gúp: ["Sodipodi.com Clipart Gallery Original link no longer available ] Ngh s u tiờn: Pedro A Gracia Fajardo, escudo de Manual de Imagen Institucional de la Administraciún General del Estado Tp_tin:Flag_of_Sweden.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/4/4c/Flag_of_Sweden.svg Giy phộp: Public domain Ngi úng gúp: is ag is regulated by Swedish Law, Act 1970:498, which states that in commercial activities, the coats of arms, the ag or other ocial insignia of Sweden may not be used in a trademark or other insignia for products or services without proper authorization is includes any mark or text referring to the Swedish government which thus can give the commercial mark a sign of ocial endorsement is includes municipal coats of arms which are registered. Ngh s u tiờn: Jon Harald Sứby and others Tp_tin:Flag_of_Switzerland.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/f/f3/Flag_of_Switzerland.svg Giy phộp: Public domain Ngi úng gúp: PDF Colors Construction sheet Ngh s u tiờn: User:Marc Mongenet Credits: Tp_tin:Flag_of_the_Netherlands.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/2/20/Flag_of_the_Netherlands.svg Giy phộp: Public domain Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to Ngh s u tiờn: Zscout370 Tp_tin:Flag_of_the_United_Kingdom.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/a/ae/Flag_of_the_ United_Kingdom.svg Giy phộp: Public domain Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to per data at http://flagspot.net/flags/gb.html Ngh s u tiờn: Original ag by Acts of Union 1800 Tp_tin:Flag_of_the_United_States.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/a/a4/Flag_of_the_United_States svg Giy phộp: Public domain Ngi úng gúp: SVG implementation of U S Code: Title 4, Chapter 1, Section [1] (the United States Federal Flag Law) Ngh s u tiờn: Dbenbenn, Zscout370, Jacobolus, Indolences, Technion Tp_tin:Folder_Hexagonal_Icon.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/4/48/Folder_Hexagonal_Icon.svg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: Own work based on: Folder.gif Ngh s u tiờn: Original: John Cross Vectorization: Shazz Tp_tin:Gleisdorf.Solarbaum.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/c/ce/Gleisdorf.Solarbaum.jpg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to Ngh s u tiờn: Anna Regelsberger Tp_tin:HydrogenOrbitalsN6L0M0.png Ngun: https://upload.wikimedia.org/wikipedia/commons/a/a4/HydrogenOrbitalsN6L0M0 png Giy phộp: GPL Ngi úng gúp: http://ultrastudio.org/en/Atomic_orbitals (source code http://ultrastudio.org/en/Special:Review? review=3e6218d9-c881-348a-a5c5-bef719a323dd&pkg=0&cls=2) Ngh s u tiờn: Carlo Barraco Tp_tin:Mafate_Marla_solar_panel_dsc00633.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/3/33/Mafate_Marla_ solar_panel_dsc00633.jpg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to Ngh s u tiờn: David Monniaux Tp_tin:Nellis_AFB_Solar_panels.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/d/de/Nellis_AFB_Solar_panels.jpg Giy phộp: Public domain Ngi úng gúp: 070731-F-8831R-001 from http://www.nellis.af.mil/photos/media_search.asp?q=solar&btnG x=0&btnG.y=0 Ngh s u tiờn: USAF Tp_tin:Newworldmap.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/d/d3/Newworldmap.svg Giy phộp: Public domain Ngi úng gúp: Chuyn t en.wikipedia sang Commons Ngh s u tiờn: Zscout370 ti Wikipedia Ting Anh Tp_tin:Pentadiene.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/4/4a/Pentadiene.jpg Giy phộp: Public domain Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to Ngh s u tiờn: Mmurali13 19.3 NGUN, NGI ểNG GểP, V GIY PHẫP CHO VN BN V HèNH NH 47 Tp_tin:Phase_change_-_en.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/0/0b/Phase_change_-_en.svg Giy phộp: Public domain Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to Ngh s u tiờn: F l a n k e r, penubag Tp_tin:Portal-puzzle.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/f/fd/Portal-puzzle.svg Giy phộp: Public domain Ngi úng gúp: User:Eubulides Created with Inkscape 0.47pre4 r22446 (Oct 14 2009) is image was created from scratch and is not a derivative of any other work in the copyright sense, as it shares only nonprotectible ideas with other works Its idea came from File:Portal icon.svg by User:Michiel1972, which in turn was inspired by File:Portal.svg by User:Pepetps and User:Ed g2s, which in turn was inspired by File:Portal.gif by User:Ausir, User:Kyle the hacker and User:HereToHelp, which was reportedly from he:File:Portal.gif (since superseded or replaced?) by User:Naama m It is not known where User:Naama m got the idea from Ngh s u tiờn: User: Eubulides Tp_tin:QD-pyramide.JPG Ngun: https://upload.wikimedia.org/wikipedia/commons/f/f8/QD-pyramide.JPG Giy phộp: CC-BY-SA3.0 Ngi úng gúp: de.wikipedia Ngh s u tiờn: Alexander Kleinsorge Tp_tin:QD_S.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/9/99/QD_S.jpg Giy phộp: CC BY-SA 3.0 Ngi úng gúp: No machine-readable source provided Own work assumed (based on copyright claims) Ngh s u tiờn: No machine-readable author provided Grumerr434 assumed (based on copyright claims) Tp_tin:Quantum_Dots_with_emission_maxima_in_a_10-nm_step_are_being_produced_at_PlasmaChem_in_a_kg_scale.jpg https://upload.wikimedia.org/wikipedia/commons/8/88/Quantum_Dots_with_emission_maxima_in_a_10-nm_step_are_ Ngun: being_produced_at_PlasmaChem_in_a_kg_scale.jpg Giy phộp: CC BY-SA 3.0 Ngi úng gúp: Photo taken on 28.11.2012, edited in Photoshop last time on 29.06.2013 Previously published: http://www.plasmachem.com/shop/en/226-zncdses-alloyed-quantum-dots Ngh s u tiờn: Antipo Tp_tin:Quantum_confinement_effect.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/8/87/Quantum_confinement_ effect.jpg Giy phộp: CC BY-SA 3.0 Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to Ngh s u tiờn: Jpailee Tp_tin:Quantum_dot.png Ngun: https://upload.wikimedia.org/wikipedia/commons/6/68/Quantum_dot.png Giy phộp: CC BY-SA 3.0 Ngi úng gúp: http://commons.wikimedia.org/wiki/File:QuantumDot_wf.gif Ngh s u tiờn: Saumitra R Mehrotra & Gerhard Klimeck Tp_tin:Question_book-new.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/9/99/Question_book-new.svg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: Chuyn t en.wikipedia sang Commons Created from scratch in Adobe Illustrator Based on Image: Question book.png created by User:Equazcion Ngh s u tiờn: Tkgd2007 Tp_tin:Science.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/5/54/Science.jpg Giy phộp: Public domain Ngi úng gúp: ? 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Tp_tin:Solar_land_area.png Ngun: https://upload.wikimedia.org/wikipedia/commons/d/db/Solar_land_area.png Giy phộp: CC BY 2.5 Ngi úng gúp: http://www.ez2c.de/ml/solar_land_area/ Ngh s u tiờn: Mlino76 Tp_tin:Solar_panels_on_house_roof.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/8/8e/Solar_panels_on_house_ roof.jpg Giy phộp: CC BY-SA 3.0 Ngi úng gúp: http://256.com/solar/ Ngh s u tiờn: Gray Watson User:E090 Tp_tin:Sp2-Orbital.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/1/11/Sp2-Orbital.svg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: is vector image was created with Inkscape Ngh s u tiờn: is le was made by User:Sven Tp_tin:Sp3-Orbital.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/9/9f/Sp3-Orbital.svg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: is vector image was created with Inkscape Ngh s u tiờn: is le was made by User:Sven Tp_tin:Sustainable_development.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/7/70/Sustainable_development.svg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: Inspired from Developpement durable.jpg Ngh s u tiờn: original: Johann Drộo (o lun ã úng gúp) Tp_tin:Symbol_book_class2.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/8/89/Symbol_book_class2.svg Giy phộp: CC BY-SA 2.5 Ngi úng gúp: Mad by Lokal_Prol by combining: Ngh s u tiờn: Lokal_Prol Tp_tin:Symbol_list_class.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/d/db/Symbol_list_class.svg Giy phộp: Public domain Ngi úng gúp: Self-made in Inkscape, similar to Image:Symbol support vote.svg Ngh s u tiờn: Mysid Tp_tin:TicketParkingMeter.jpg Ngun: https://upload.wikimedia.org/wikipedia/commons/6/6a/TicketParkingMeter.jpg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: Chuyn t en.wikipedia sang Commons Ngh s u tiờn: e original uploader was Pilatus ti Wikipedia Ting Anh Tp_tin:Translation_to_english_arrow.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/8/8a/Translation_to_english_ arrow.svg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: Own work, based on :Image:Translation_arrow.svg Created in Adobe Illustrator CS3 Ngh s u tiờn: tkgd2007 Tp_tin:Wiki_letter_w_cropped.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/1/1c/Wiki_letter_w_cropped.svg Giy phộp: CC-BY-SA-3.0 Ngi úng gúp: L nh phỏi sinh t Wiki leer w.svg: Ngh s u tiờn: Derivative work by umperward Tp_tin:Wikiquote-logo.svg Ngun: https://upload.wikimedia.org/wikipedia/commons/f/fa/Wikiquote-logo.svg Giy phộp: Public domain Ngi úng gúp: Tỏc phm chớnh ngi ti lờn to Ngh s u tiờn: Rei-artur 19.3.3 Giy phộp ni dung Creative Commons Aribution-Share Alike 3.0 ... 17 4.4.2 Trong nh 18 4.4.3 Trong giao thụng 18 4.4.4 Trong cỏc thit b ri ... hng nm cn c ny s dng[28] 4.4.2 Trong nh Solar parking meter [7] Solar Generation V - 2008 Photovoltaic solar panels on a house roof 4.4.3 4.4.4 Trong giao thụng Trong cỏc thit b ri 4.5 Xem thờm... kin Cú hai chng trỡnh mc tiờu c bn: mc tiờu hot ng v mc tiờu th ng Trong trng hp cỏc mc tiờu hot ng, chm lng t c chc húa vi cỏc trang web liờn kt u c th chn lc liờn kt vi cỏc t bo u Nhm mc tiờu