Nam thu nhat MPSI va PTSI GD HACHETTE NHA XUAT BAN GIAO DUC SupérieurAMBASSADE DE FRANCE AU VIETHAM INGENIEURS D'EXCELLENCE AU VIETNAM Hoa hoc (Tai bain ldn thit nhat) ‘ANDRE DURUPTHY 2 5 Gido su céc lép dy bi Nam thi? nhat ‘Trung Trung hoc Paul - Cézanne 6 Aix-en-Provence MPS! va PTSI ANDRE CASALOT Gido su Trutng Dai hoc Téng hgp Provence (Aix-Marseille 1) ALAIN JAUBERT Gigo su céc l6p dy bj ‘Truong Trung hoc Thiers & Marseille CLAUDE MESNIL Gido surcéc lp dy bj ‘Trutng Trung hoc Hoche 6 Versailles Ngudi dich : BAO QUY CHIEU NHA XUAT BAN GIAO DUCéi ndi dau Sach nay duge soan thao theo chuung trinh mi, ban hanh thang 7 mim 1995, cua nim thir nhét Ban MPSI- va Ban PTSI, Nhang phiin rieng cho churmg trinh MPSI se duve chi r0 trong sach. Cae chummy cing theo MOLbS cue 2 Bai gidng: trinh bay mot cAch ro rang cée noi dung ciia chuong trinh, CO nhiéu vi dy va ap dung, gitip cho each tip can due cu thé va hap din. Cudi méi chug 66 mye Diu edn ghi nhé. @ Bai tap: nhidu va da dang, gitp danh gid kien thie va nang lye theo timg bute va sdu ky, thuing dye tri lirede dé thi tuyén, Bai fap duye phan loai theo hai dé mye nhim trie nghigm sy hiéu bai va tinh vang chéc eta kidn the thu diye, Céie bai tap déu c6 10i gidi dé 6 cud sich. @ Phy luc: B6 sung nhimg digu cin thidt dé thye hign, ngay tir du nam hoc, nhung bai thi nghi¢m ding ti phep do phd quang, phép do do dan dién, phép do dign thé va phép do pH. @ Sach két thic bing bang danh phap hoa hoe v6 co, bang nhimg hang sé héa ly va mue lye tra ciu. Sach due ¢ he héa ho ja tanh 11 chuong, Hn tut nh bay vé Cau tao chat, Nhigt dong hoc va Dong hoc cia nhimg ‘© Theo dung chun hoc lung ti doi voi nguyen te dang hidro va 4p dung nhomg ket qua d6, vi do inh, bai gidng chi trinh bay nhumg ket qua chinh, ma kho in dang thong thang cho nhting nguyen tie khide. Tiép theo la Phan lout tudn hoan cdc nguyén 16 va Kién tric phan te. Thuyet Lewis va mo hinh VSEPR, khai ni¢m vé lien ket phan cuc va lien két cOng hod ui chuyén ché (khong dinb vi) va kha nigm vé mesome dunye trinh bay qua nhong vi dy don gin iu tao va td chite vat chat é trang thai ngumg ty duge trinh bay trong hai chuong. Chung dau fa vé nhung khai migm corbin eda edu trac tink thé (mang, © mang, nut, mt.) va. ve nhumg lién ket khde nhau bao dim su 6 ket ciia tinh thé, Chuomg sau 1a vé cae kigu tap hop nguyén ti hode ion thang gap nhdt, trong moi quan he voi ban kinh cae hat hop thanh, Gidi han & nhamg dp dung Nguvén I thie nhdi cia nhiét dong hoc, bai giing ve Nhigt héa hye tinh bay nhung khai nigm co ban cn thigt cho khio sat phan tmg héa hoc. Vé dung dich nue chi yeu [a khito sat nhing hign tuyng oxi-héa khir, He thie Guldberg-Wagge, chi dua ra ma khong chtmg minh, cho phep xtc dinh mign uu the va mién t6n tai ca ede loai phiin ti trong phn img axit-bazo, phiin img ket ta va phan img tao phic Dua tren nhung kidh thie da hoe 6 16p cudi cp Trung hye phé thong, bai ging ve Dong hoa hoe dua ra dinh nghia chat che vé van 16e phan ing va winh bay dink lugng vé nhumg yeu W dong hoc. ‘Trinh bay ve nhang Co ché phan ring ta nhim minh boa nhong phuomg phap da duve ap dung tong Dong sage va cho phep lam ro sy khde nhau gita phuung trinh phan img ng cong va nhung gia doan corbin eda phan img; su khie nhau nay da duye dé cap 6 lép cusi cap phd thong. Khi bien soan, ching ti nie mong thye hign due MOL cudin sich c6 tinh tong sing va hap din, va hi vong rang no sé gitip nhiéu sinh vien thay yeu thich mon Héa hoe va chudn bi tit cho ede ky thi tuyén, Chung t0i se rat sung suwmg néu dat duye nhong mye teu ni Chung 104 xin cd ta nhomg 16 phe binh théa ding da dye lai ban thao cha chung ti. it Odile DURUPTHY va Magali GIACINO, ahang nga Chung 101 cang xin cm om inne nhamg got y, nhan xét va phe binh cia céc dong nghigp va sinh vien, CAC TAC GIALoi néi dau 3 Muc luc ... 4 7 Mo hinh lwong tir cia nguyen tir dang hidro ... 5 2 Nguyen tir nhiéu electron 34 3 Phan loai tufin hoan céc nguyen tO......... 56 | Kin tric phan tir S Kién tric tinh thé 6 Cau tric tinh thé 156 ) Ap dung Nguyen ly thit nhat vio Héa hoc 186 2 Phan tg héa hoc trong dung dich nude ..... 232 4 Can bang oxi héa - khit.... 264 10 Van t6c phan img .... 299 11 Coché phan mg trong Dong hoc déng thé 336 Loi gidi cde bi HOP en 376 Phu luc I: Phép do phé quang 399 Phu luc 2: Phép do dé dén dién .... = 401 Phu luc 3: Phép do din thé 404 Phu luc 4: Phép do pH .... 405 Phu luc 5: Danh phdp Héa hoc V6 co 407 Phu luc 6: Hang s6 axit - Hang s6 tao phitc - Thé oxi héa - khit chudn. Tich s6 tan 409 Phu luc 7: Hang s6 héa ly 413 Phu luc 8: Tinh chinh xéc ctia két qud - Nhing chit s6'c6 nghia 44MO HINH LUONG TU CUA NGUYEN TU DANG HIDRO Me dau O cudi thé ky XIX, Vat Is hoc ~ voi nhiéu thanh neu cia minh = thé hign nhue la m6t ly thuyét da hoan chinh. Vat ly hoc phan bigt hai linh vec la: 1 Vat chat, 140 boi nhimg hat vat chat tuan theo nhing dinh luat Co hoc. Nhing dinh lu@t nay dyea trén nhing tien dé ciia Isaac Newton va nhiing thanh tua cia Gidi tich todn hoc. Sw dp dung ching cho Thien van hoc thé hign mi man &rnhang tien dodn duage thc nghiom xdc nhdn (se quay tro lai ctia sao chdi Halley, se t6n tai cia hanh tinh Hai vuong thudc Thai duong he) 1 Bue xa, thé hign tinh chat song va tudn theo nhing dinh ludt dign tie ctia James Maxwell. Quang Jy vat quang hinh thude vao link vuc nay. Tuy nhién, c6 nhiéu hign tugng vé trong tac anh sding = vat chdt da khong thé duge gidi thich dinh lugng. Myc 1} ™ Bit nhomg két qua gidi phuong trinh Schrodinger cho nguyen tit hidro: xée sudt Eu 6 mat electron; nhimg s& lung tir n, I, ‘m,; nhtmg orbital nguyen tirs, p, d. ®@ Hidu cach gidi thich phd phat xa cda nguyen tir hidro. Dieu c&n Biét tRusc (Chuong trinh Trung hoc) ™ Chuyén dong tron déu trong tudng CouLoms, = Nhong ién s6ng dien tir. Photon va sy truyén nang Iugng gita anh sng va vat chat. 1 Phé vach va cfu tao cdc mete nang hung ‘cia nguyen ti,1 Su hinh thanh vat ly lugng tu —__ 1.1, Nhac lai vé tuong tac anh sang - vat chat @ Nhomg tung tic nay thé hign nhiéu céch: higu tmg quang di¢n (do H.HERTZ tim ra nim 1887) (H.1), baw xa cla nhang vat bi d6t néng, phd vach cia nguyen ti (H.2) CA thuyét hat va thuyét sng déu khong thé gidi thich din lnyng nhong hign tuyng nay, nim 6 bien gidi chung cia hai thuyét. 1 Su luyng tirhoa ning luyng diye M.PLANCK dua ra nim 1900 d6 gidi thich phé cia vat bj dot néng: Ong neu ra tien dé 1a sy trao déi nang lugng gitta vit chit va bie xa duye thye hign bing cach hap thy hoge phat ra nhong ning lang n. € trong dé n 12 mot sO nguyen va & 1 mot lung nang lung co bin goi 1a luyng tir nang luyng, Da nhain duye sy phd hyp dinh ung véi thye nghi¢m khi chp nhgn Ping: d6i véi bike xa don sie c6 tdn sO v (tie 1A mach sO @) thi lugng tr nang luyng duye cho béi hé thie e=hv=ho ay trong dé h 1a mot hing ph6 quat, duge goi 1a hdng Planck, gid tri duge chp nan hign nay 1a : I= 6,6260755.10- J.s = 6,683.10 4.5 h duge goi 1A hang Planck rat gon : n= x105.10 ys dn a) b) 700 ho 00 00 A(am) Nam 1905, A.EINSTEIN ngogi suy quan diém ciia Planck va cho ring: bite xa don sic c6 tin s6 vduge edu Go béi nhimg hat nding luyng goi [2 photon va co nhamg tinh chat sau * Photon [a hat khong kh6i lung, chuyén dong trong chan khong véi van t6c nh sang c. © Mot photon tin sO v c6 nang lung 1d ¢ = Av va dong luyng 1a h : ‘i p =~ diwrong d6 1a vecto don vj cia hudng lan truyén. ¢ Nho mo hinh nay, A.Einstein da gidi thich duge nhamg dinh twat vé higu img quang dien, > Dé luyén tap : BT 1 E: thdu kinb thach anh S: dn thiy ngan E:dign nghigm F: kim bode 1 di dng Ps i em HLL. Thi nghigm lam ro higu ting quang dign. Khi tim kem bi chiéu sang nb phat ra electron, dign nghiém, ban ddu tich dign dm, dan dan phéng dign, 4.2. Phd phat xa cia nhang nguyén te khdc nhau Phd phat xa (hode hdp thu) cua mot nguyen 1 luon ludn gdm cing nhang vach phd: dé la datc tinh cita nguyen 16 nay: a) heli b) thity ngdn,1.2. Phé cla nguyén tu hidro 1.2.1. Sy thu duge phd Khi hidro 6 ap suit thap (khong 1,5 mbar) duye chifa trong Ong thiy tinh dudag kinh nhd, hai du 66 hai dign cue kim loai Moi higu dign the ing din duge dit vao hai cyc: khi dat t6i khodng vai trim von thi thay c6 dong dign chay qua Ong va Sng phat ra anh sang. Khi 46 co mot dOng g6m electron va ion duong ; hang hat nay va cham dan hdi voi nhong phan tir hidro va lam phan ly mot so phan th. Nhu vay 1a co mot hén hep g6m electron, ion, phin tir va nguyen tr hidro. Nhang hat nay duye kich thich khi va cham va phat ra nhang bite xa dign tir khi ching bi mat kich thich. Sy phan tich anh sang do Ong phat ra tao thanh phé phat xa cha nguyen tir hidro (H.3). 1. 8 8888 8 8 3 om oz 001 HONG NGOAI (IR) xi KIEN TU NGOAI (UV) & Ee 7 & & yon uyad i a ce .2, Dang vé cla pho Phé phat xa gb ® Day Balmer Day nay, duye tim thdy ditu tien vao nim 1885, gdm bén vach & mién khd kign (H.4). mnhang day vach mang ten nhong ngudi tim ra Balmer nhan thay ring bude song cita bon vach nay thda man he thae sau, v6i 40 chinh xac lén hon 1/1000: cC const, n neN* (1.2) Day nay cor gidim thi cdc vach cang xit lai g: g6m nhigu vach 6 mign tirngoai (UV) ong cang in hau va curmg do cang giim. Bat diu ta mot bute sng goi IA bude song gidi han 2y( td nén lin tye va me nhgt rat nhanh. H.3. Pho nguyén ut hidro o gdn mién kha kién. Ddi voi mdi day, vach gidi han duoc biéu thi boi cdc dau cham cham. ” |e [a | | Ms 2 (am) [656.3 | 486,1 | 434,0/410,2 mau | dé as chim | tim H.4, Phd phat xa nguyen tit hidro bao gdm bén vach trong mién kha k@ Nhung day khic Ten day] ] Mito [Ay om) Nam 1906, Lyman tim duge mot day d min ti ngoai xa, Nam 1908, Fymae Pap) on Paschen tim duge mot day mién hong ngoai (UV) gin, Sau d6 mhemg tates Poe | day khae duye tim thay trong mign héng ngoai. Tat ci cde day may 6 UY. cing cau tic ohu day Balmer (d0 xit lai nhau cia cdc vach, cudng do vach, buve séng giéi han). RYDBERG va RITZ chi ra ring bunic s viet dunsi dang = Paschen| 3 | LR gin | 8200 Bracken | 4 ik 1460 ng cia tat c& cde vach 6 thé due Zz | 14 . HS. Dac tinh cia nhtng vach 2a) nvapeN*, pon (13) chink cia nguyen tie hidro. wp’ Dai lung Ry duve goi la hdng Rydberg: xc bing cach do buse song gii han ciia mot day. Ann ; Hign nay da biéi moi day vach W5 06 thé dhnge xée dinh chinh cho iin =27 Ry = 10979708, 014+ 0,013n071 So yen n 1a dai luwng dc trmg cia méi day (H.5) > Dé luyén tap: BT 4 1.3. NhGing mé hinh nguyén tu 1.3.1. Lich str Nam 1901, J.PERRIN dé xust mo hinh hanh tinh : “MOi nguyen tir gm hai phan: mot phdn 1 mOt hay nhigu khdi tich dign duomg rat manb, kigu nhu mat tri duong ma dign tich rat lin, cdn phan kia Lk nhomg hat nho, kigu nhu nhang hanh tinh Am; nhong khdi nay chuyén dong do tae dung cia nhang lye dign va dign tich am tng cng bing ding dign tich duong do d6 nguyen tra trung hoa di¢n” Nam 1903, 1.-1-THOMSON dé xudt m6 hinh ri¢u ed: nguyen tir mo qua el hd c6 dien tich diame, nhong electron chuyén dong ben trong qua clu nay. Nam 1911, E.RUTHERFORD lam thi nghigm tan x@ hat cc bd Id vang mong (H.6). Ket qua quan sat cho thay mo hinh Thomson la khong ding. hp bay sing {wo eh at hat a ctu do ech D ich chi nhimg nbap ny sing Tao ban ng. ter hong bi Igch HG. Tan xa hat c do ld vang. ngudn radium Hiiu hét cdc hat a@ di qua ma phat a hate chim bat a san jh ung khong bi lech tuy Id vang gdm hang ngan lop nguyen titDo 46 Rutherford da sim 46i mo hinh hin tinh thanh nhu sau : mot hat nhan trung tim duy nhat tich dign dung, céc electron quay quanh hat nan theo nhang quy dyo tron (H.7). ‘Ta tinh bay mo hinh nay qua vi du la nguyen ti hidro. Nguyen tir hidro g6m mot proton va mot electron. Kh6i lung proton gn biing 2000 Kin khoi luyng electron nen c6 thé coi proton nhu e6 dinh; he ©. quy chiéu c6 g6c 14 nhan c6 thé coi Ia he Galilée. Nhing lye tée dong len electron P e6 khoi lung me, 1a Iyc hip din Fer Vile tinh dign f_; do hat nhan tic dong VN SY <) 1.7. Mo hinh hanh tinh nguyen tie Nguyén tie duege bi€w thi 1a iti. Dat OP=ru, . Nhang lye nay tuan theo nhang ti¢n dé NEWTON va COULOMB Ter =—Gamig.m py *E r = _ Celdte) fa =O 4ney or Modun cia lye hap din rat nhé so véi modun cia lye tinh dign : lal 2 4 lig] 420 Gem, _ 460.1078? 1 4.3,14.8,85.10" '6,67.107"19,11.107911,67.10°7 © 2.27.10! Nhu vay c6 thé bd qua tuong tac hap din so voi tuong téc tinh dign, Ap dung cho electron trong hé ma géc 1a nhan nguyén tit, nguyen ly co ban cia dong luc hoc duye biéu dién boi a=——— “© (4 Ia gia tc cita electron) neg 7? me Cac kiéu quy djo suy tir phuong tinh nay se duye trinh bay trong gido tinh Co hoc ; 6 day chi xét nhimg quy dao tron ma tim 1a hat nhan, C6 thé lap due (xem phdn dong khung, trang sau) he thie gita bin kinh cia quy dao tron va ning luyng toan phin £ cia nguyen ti : oil 8xe9 7 Nhung m6 hinh ¢6 dién nay khong abdt quan. Khi chuyén dong tren nhamg quy dao tron, cdc electron c6 gia tc phap tuy€n khac khong. Ma theo vat ly c6 dién thi hat tich dign c6 gia te s¢ phat ning luyng lién tye; do d6 ning lug cita nguyen tir sé gidm lien tuc va electron sé din din roi vao nhan : nhu vay nguyen tir sé 1 mot co edu khong bén vang!Biéu thie ciia co ning eta nguyén tirhidro Dang eich bigu dim theo he quy chiéu Frenet (dip. fy «iy ) H.8) Khi ds, veoto gia te e6 than phiin 1a: Ban kinh cong R cla vong won bing ‘an kinh r eda n6. Voi quy dao tron tam. & ge th: i, = iin, He thie 6 tren €6 dang. Gia te tgp twyé bing khong nen ehuyén dong tron ny phai 1 déu Chui cia vecto van te v phu thude theo he thie : © Vazegm, Vr Nang lung toin phn Ee bing tng dong nang K eta thé nang tome tac inh digo (Nhu sé thay trong gio trinh Vat If. the nang img véi lye Unh dign cho bdi he thie : ‘Theo quy use, chon hing bing khong ghfa 1a coi thé nang bing khong khi proton vi electron vo cing xa nhau, Khi as HB. He quy chigu Frenet. lip la vecto dom vi cua tigp tuyén voi dudng cong. iy la vectr don vi phdp tuyén (vdi dudng tron, n6 tring voi ban kinh) hudmg vé tm duong tron, ig vudng géc voi malt phding cua duong cong. Tam dién (tir .iiy stig) 1a thuan. 1.3.2. M6 hinh Bohr (1913) m DE khac phuc nh khong nhat quin cia m6 hinh Rutherford, Niels BoHR da van dung thuyét lugng tir h6a cia Planck va chap nhan ring muda cho quy dao tron fa bén vag thi bin kin r eda quy dao va van We v cia electron phai théa man he thee: mevr=nh , vine N* Chuin cia vecto van te v lien he véi bin kinh r theo he thie: Anegm, Vr A din én he there Didu kign lung tirhoa me. dae? _ Dai lung mee? Me truyén thong, n6 duge goi la ban kinh Bohr va ki higu Bap. we mee? my Ancosh® 6 a= (4) nhang quy dao bén ving cia electron fa nhamg vong tron e6 bin kkinh r sao cho: =n ayC6 thé suy ra nhimg gid tr Weng mg cia nang lung toan phin E iia nguyen tk. Vir bi luong tir hod bdi n nen E cung bi lung tirhoa nhu vay: (Ls) Mo binh Bohr la mot thanh tyu rat Ién, ‘Tir nhong mie nang lung cia md hinh may va tir gia thuyet Hinstein vé nang ling cha proton vor tan sv, 6 thé suy ra dang vé eta phd nguyen ti hidro. 1.3.3. Vé su can thiét cla mét mon Vat ly mdi ‘Tuy da duye hoan chinh them nhigu, mo hinh Bohr khong thé gidi thich duve pho ctia nhimg nguyen tirkhie nguyen tirhidro electron - bra die pit thigt Ba tuedo va dimg yer. Ae oe photon X ten bia 6 bure song A photon X tan xa 6 be song A runic va cham sau va cham electron bi bat ra Nhidu su kien thue nghi¢m khdc, vi du hieu tmg Compton (H.9), da thic dy nhomg nha vat ly mé rong lug tinh séng-hat ra cho tat ed cae hat, nur da lam vi photon, Nam 1923, Lde BROGLIE sing lp ra mon eo hoe song. Cong tinh cia de Broglie duye b6 sung bang nhong cong trinh ct E.SCUR "INGER, W.HEISENBERG, W.PAULL va P.A.M.DIRAC va thud: duye got phé bin la Vat ly luomg ti, Nhe Vat ly lung tir ma da c6 nhong tign bo quyét dinh trong vige tim higu nhang hien tuyng rit khde nhaw nhir chat ban din, Val ly thign van, laser va di nhien la 66 e& mon H6a hoc! ‘Ta hay x61 nhumg y tung lim cia thuyet may. 1.4, Nhang khai niém co ban cua Vat ly luong tu 1.4.1. Vat ly cé dién va Vat ly luong tir reo the ‘Tuy ring Vat ly lun P dung due cho myi hg, Vat ly e6 dién van con Ja mOU ind hinh chap nhan duge déi v6i nhiéu truimg hop. Ot tidu chi cho bist khi mao eo thé 4p dung duye Vat ly ly lug tir? Lagu co t6n tain 68 dién va khi nde ein den Vieu chi nay dua trén hing Planck /, mot dai luyng c6 thé goi La hing dic tng cho nhamg hign tuyng luyng tir. Truxse hét, nh Tai ring: h~6,63.104 Js 1 4.119. Higu ng Compton (1922). Mot chum tia X ban vao bia graphit , nhimg tia X bt tan xa (theo huomg 0) boi nhang electron cia graphit, ¢6 butoc sing 2° lon hum bude song ca nhtong, tia X 16 Higu (2° — 2) pu thude vao g6e tan xa 0. Higu ing nay khong thé gidi thich bang vat C6 dién.‘fh dng nhat ver mot “tae dung” nghia 1A tich cia mang lugmg % thor gian ode do dai = dong lung hoge 1 mot momen dong (H.10) : h 1a “ung rtac dung” cng nhu ¢ 1 luyng tH di¢n tich. Neu hg ma bien "tae dung” c6 cang 60 16m vin / thi bat bude phir dang dén Co hoe luyng tt, Nguye Iai, neu “tic dung” rat kon so voi Mi thi cdc dinh tuat eda Vat ly e6 dign vin ap dung duve. Vi du ¢ Nang luyng ion hoa nguyen tir hidro xe dinh bing thye aghigm 1a = 13.6 eV (*), gia tri nay khong phy thude vao md hink nguyen tt. * Mat khie, trong pho cita n6 c6 vach ma bunte song gin vi 0.6 4am. Trong chan khong, butte song 2 lien he vii tin sO bi he thee cedv Vi 1/v déng nat voi thoi gian nen n6 bigu thi thei lung dac trung cia ‘mot trang thai nang lugng cha nguyen tir hidro, Van dung n6 dé to thinh mot “tic dung” a dae trrmg cho he nay’ 13, 6.10-".0,6.10" ~ 2 2 4,3.10™. 3.10! Js 6h Tac dung nay ©6 cing ©6F lin véi fr: chi o6 thé khdo sat nguyen ti hidro trong khudn khé cia Vat ly Iurmg ti! 1 . Niding ham séng 1.4.2.1. Binh nghia MOi hat chuyén dong duve gan voi mot song md bien do phu thude cdc toa do khong gian va thoi gian cia hat nghia la ¥ Gy y, 2.0. Y duve goi Ia ham song cha hat. ¥ khong c6 ¥ nghia vat ly nhumg chira dumg tat cd cae thong tin lien quan ti hat. ¥ ¢6 thé 1 mot ham phac, 1.4.2.2. Ham song va xac suat ®@ Xét diém Mo (Xp.¥ 9.29) & thoi diém t. Xac suat tim thy hat 6 ia can My ( nghia 1a 6 trong lap phuong co canh dx, dy, dz ma tim 1a M,,) lagi? (HI) ‘Theo dinh nghia, x4e suat dP nay la: (1.6) ¥ * thu duye bing cach d6i i thanh P= ¥* (X95 90.20.04 (X95 Yo sto Oudedy.de © ¥ la ham phitc lién hop cia ¥ > -itrong ¥ (7? = =1) © dvdy.dz 1 nguyen t6 thé tich trong toa dd Descartes; mot cach téng quat hon thi do [a nguyen 6 thé tich ma tim kb Mg , ky higu la d*r(Mo ) © Dai lung ¥ *. %, duye goi la binh phuong cia chudn. NO déng nhit voi xae suit theo don vi thé tich va biéu thi mat dO xae sudt c6 mat hat & digm Mg va thoi diém t, ky higu la DUMy.) Chivthich: Néu Ya ham voi nhang gid tr] thee thi ¥.¥ chink la > 12 1.10. Momen dong hoc Néu hat P c6 kh6i lugng m va van 160 ¥ thi vec momen dong hoc L cia no d0i voi diém 2 duge dinh nghia boi [= 2P amv Chi ¥ rang mews, diege lung te hoa boi Bohr, biéu thi chudn ca momen dong hoc cia electron d6i voi nhan. (*) electron — von (eV) la ndng lugng ma mot electron 6 duge khi n6, ban déu dimg | ven, duge gia 16c boi hiéu sé) dién thé mot von JeV = 1,602.107'°F H.11, Nguyén (6 thé tich trong toa do DescartXac suit P(e) tim tify hat wong thé tich ¢ (H.12) duge tinh bing tich phan theo binh phuong cia chudn; vi vay ¥duye noi 1a binh phuong cong diepe. P= fff patna ea) = [fy annvanna ea 1.4.2.3. Chuan hoa Y nghia xc sudt cha Y ddi hoi ¥ phai thda man mOt sO diéu kign: néu Ady thé tich 18 toan bd va ty thi chic chan 1a tim thdy hat 6 bat ky thoi diém nao nghia 1a xéc suat tim thay hat trong toan bd va try fa bling mot, Vi vay ¥ phai théa man diéu kign sau, goi la diéu kign chudin héa : Wrsnrsonesin YY 2T=L GD 4.4.2.4, Trang thai én Dinh nghta : He 6 trang thdi n dink néu céc dic trung cia n6 khong phy thude thoi gian. C6 thé chimg minh ring khi 46 ham song ¥ (x, ¥, z, 1) 06 thé viét dudi dang tich (E 1a nang lung ca trang thai mo ta boi Y) + Y (x,y, 260) = (x, ¥, 2).exP LED), Khi d6 dai lung lign hop ¥*(x,9,2,0 duge viet bY *(x,9,2).expEiED). Mat do xdc sudt. c6 mat hat 6 digm M 1a: D(M,1) = * (M,1).4(M,1) = * (M).exp(-LE.2).Y (M).exp(i.E.2) Ma: exp-i.E.t).exp(+i.E.) =1 Cho nen : D(M,1) =¥ *(M).4(M) ‘Theo ding v6i dinh nghfa cba he Gn dink, m4t do x4c sust c6 mat chi phy thude diém duye xét. Tir day vé sau, ta chi xét nhimg he Gn dinh va chi quan tam téi phiin khong gian ¥(0) cia ham song. inh (con goi l& trang thai ding) 1.4.3. Phuong trinh vdi cua nang lugng cua hé 6n dinh 1.4.3.1, Phuong trinh Schrédinger C6 thé n6i phuong trinh Schrodinger la phuong trinh co ban ca Vat ly lugng tt. Néu £ 1a nang luong toan phan cia he (t6ng dng nang K va thé nang E,, ) thi phuong tinh Schrodinger viet dusi dang tung trumg 1a : HY=E.¥ ‘Trong phuong trinh nay : ‘© H bigu thi mot toan tir (xem phdn dong khung, trang sau), goi 1a todn tie Hamilton, Khi H duge ap vao ham ¥ thi s¢ bién ddi ¥ thanh mot ham khdc. Bigu the cia H phy thude he khdo sit nghia 14 phy thude nhing tuong Lic ca hat phai chju tac dong. ° E..¥ biéu thi tich cia ham séng ¥ voi gid tri nang lugng E gan voi ham ¥. H.A2. Xdc dinh P(), xdc sudt tim thdly hat 6 trong thé tich t. Mat dong E gii han thé uch Chiat thanh vO sO hinh lap phuong nhé co thé tich dr va dy 10ng xdc sudt co mat trong méi hinh lap phuong ; nhue vay tinh dugc tich phan b6i ba vi co ba bién.Gidi phumg trinh Schrodinger 1a xde dinh nhong hi Ue dung ciia Hse bing tich cia ¥ voi mot dai lung nm / ma sau ki chiu vo hung E> nung ham nay duye gor A nhung ham riéng cua toan tir Hamilton; hong gid tri cia luymg cla he. E ket hop veri nhimg ham nay goi lt nhing tri riéng ct a nang Whang ham rieng cua todn 1 0 la mhitng heim tha mn sing dng thie sau : OF = af ; trong 46 a 1a moe vo hong. Két qua cia vige dp 0 va0 mot trong nhiang ham riéng f la dng f nhan voi mot s6 got la tri rieng ket hop v6 J. mot trong nhomg him riéng may 18 bing s6 thye a oan tit va ham rieng. 1 Tosin tir 0 18.mot ddi tuymg toan hoe maki dave Ap vio | Vide + sham .x —>flx) s@ bién d6i ham nay thank mpt ham Rid: Nim hm ring eatin tr ao sy ha tn Vidu a Tod se “tri tuyet dé N" bign dd fx) thank Ya) ing thie 5 a. Ho, Ge. Toan tit “dao ham theo x, = bién di fix) thanh “_ dk af(x) DE ding kiém chime ring nnbimg ham x—> Aexp (ax): trong d6 A va a la thie) ahaa hm ring oan tt, ve ing kha v6 1.4.3.2. Luang tur héa nang luong Nehi¢m cia phuong trinh Sehrddinger 1a nhimg ham ¥ phu thude tham, so £, Nhtmg ham nay chi c6 thé dong v: sO tinh chat nat dinh nay chi c6 duye doi voi nhaw hoa. ma dic lnvng, > Luyén tap : BT 21. i du, chung phai théa man digu ki tro ham song neu chung co mot n chudin hoa gid tri nhat dinh cia F : nang 1.4.4. Bat dang thtrc Heisenberg Bie nhimg riéng gan von tr gigi vi mo kh Diéu may cong dui chung tung tng voi mot a dong lung, iia hat cho phép xac dinh duye gid tri c6 thé €6 nhat ci fai lunyng (¢6 thé) quan sat due” eda hat may : BS 1 nung 17} thai may. ‘Tuy ohien, moi dai tuyng vat ly eta the déng thoi quan sat dinye doi vot eae da die dung” vi du nur nang henge Nhomg dai lung nay duye noi La “khong tung bi nhang bai dding thie Heisenberg. ong thé gi 1 fa tich cba thn lung hién hop” ngh hug 1.4.4.1, Nang lugng va thai lugng (durée) Neu mot hé co thi luyng song co St thi nang tu tan trong mot khoang 66 dd ror Nang ugg ctia mot trang thai chi duye xae dinh mot cach chi thor Img song trang that e E cia no se bi phan FE sao cho Este (18) 2a ih xae néu rat dai nghia 1a néu trang thai nay rat ben. He qua cia sy gid han nay la tit cd ede vach phd du c6 mot do rong hat dinh. 141.4.4.2. Vi tri va dong long Nou mot hat dr caeh ge Br va eo dd phan tin 1a dF thi ehudn Iumng ciia no bi phan tan trong khodng op sao cho h dpdr> Pern he chi xée dinh chinh xée néu 6 trang thai nay he 66 do gian rat lon, Eq la nang ligmg cha mot trang thdi kich thich; — d¥4_44° ral nhé so VG cée tn sO bite xa trong Exla nang heme omic co ban; mign kha kién va cd mién héng ngoai Toi home sng srung bin eta trang thd’ kieh Vg. 4 AQum.y =e A= 410" He thich la or = 1078s, dv/v co 5.1077! DO mér rong dv cia vach phé se c6 co ton nh — Chi thich: Co nhiéu nguyen niin Kheic (eam mor thé nao? rong vach phé ma noi chung dnh hiing cia Dikign: 2 =10ym ching quan trong hon nhieu so véi nhang bat E,, bi phan tan trong mot khodng 66 dd rong dinh Heisenberg, fh 22.0 trang th i 4 Neu vy-y1 ld tan sO eta bike xa img voi sy dich Keb thieh ae OE, 4 Nang lung a 1" chuyén gita E, va Ey thi AE 49) = Eq ~ Ey = hy 91 Vi E, bi phan tan trong SE, nen AE, ,, ca fin tan hur vay: do dé ¥, e trang that Di phan tan hur vay: do d6 vy sbi phan tan "meth By ae trong khodng 8 (H.13) sao cho 1 .1,6.107 Hz . - - 2. H.13, Mot nguyen nhin lam md rong vach pho OV pot = M6 hinh luong tu cua nguyén tu hidro ——___ 2.1. Ham s6ng va nang luong cua nguyén tu hidro 2.1.1. Lap phuong trinh He g6m mot electron va mot proton duye khio sat trong khudn khé gan dung Born-Oppenheimer nghia 14 cho rang nhan fa hoan toan dinh vi; digu nay [a chinh dang vi khdi luong ciia nhan rat In so voi electron (1840 Lin doi voi nguyen ti 4), Nguyen Ur tiidro ung voi nhang trang thai lien két cia be: trong kiéu tang thai nay, proton va electron 6 gin nhau. 15Hon nda, nhu da thiy tromig m6 hinh Bohr, ¢6 thé bé qua tuong tic hip din so von tuxmg tic tinh dign, Khong gtan duge quy chi¢u vé tam di¢n Oxyz ma g6c tring voi vi tri cha han, DO: VoL MMM Nguyen tir hidro cé [dp (day 1a he ta x6 thi khong gian 1 ding huomg nen vi tt cla cae true 1a tay y. The nang cia he c6 nguén g0e tinh dign va chi cin dé y W6i khodng céch nhan-electron cho nen ding toadd cdu ge O rat R tiga (H.14) Vige grat phuong tinh Schrodinger cho he nay din (di nhong ham séng ¥ phy thude cae bien 7, Ava g. 2.1.2. Ham song Dat tién nghiém rang ¥r,A y) la tich ciia ba ham, méi ham chi phy thude mot bién ; Ar, 8g) =Rir). HO). My) © R¢r) goi la phdn xuyen tdm ciia ¥ vi chi phy thude vao 7. © Tich 6/0). 249) thug duve ky higu 1a ¥(A, ¢g) goi la phdn gdc chia ¥Vi no chi phu thude vao cae toa dO g6e Ova g. 2.1.2.1. Binh nghia cdc sé lugng te Y nghia xée suat ca ¥ va nhomg digu kign toan hoe kéo theo (binh phurng tng duye, tinh ¢6 dao ham, tinh xéc dinh duy nhat & m6i diém cia khong gian) da Sp dat nhumg digu rng bude cho cic ham R, Ova thé hign & nhang thong s6 goi [a s6 lung ti, = XQ) phy thude MOL hong SO mi + my 1 MOL SO nguyen tuMg doi va duye gor 1a sd’ lrymg 1 1, do d6 FY) C6 Ki HigU P,(9) © (8) phy thude hai thong sO: Im, 1 va f: (1 s0 nguyen duong hoe hing sd khong va duye goi la 56 lugng tie phuomg vj (hoje phu), do 46 OW) CO ky hieU Ay, (A) © R(r) phy thude hai thong sO: ¢ van; ni sO nguyen dug va duye goi 1a x0 hieong tir chinh, do a6 R(r) 66 ky higu. Ry, ¢(r). Ham song nghi¢m cia phuong trinh Schrodinger phy thude ba sO lung tt, n, © va mys biét nhong gia tri nay thi ham rigng duge hodn tan xe dinh : Pact, 119.9) = Ry, AP) « O, tm lO) « Py, () 2.1.2.2. Hé thre gitra nhUng sé Iuong tir Phép tinh chimg t6 ring ba sO lug tirmay khong doc lip doi véi nhau : #2, sO luyng tir chinh, la sO nguyén duwng : ne (12,3) #1, 80 luwng tir phuung vi (hodc s6 yng tit phy), la so nguyén duvng, hoac bing khong, c6 gid tri nhé hon a : Fe O,1,..(n=1)) my , 86 ung tir tir, La mot s6 nguyén tuwng déi 6 trong khodng —¢ va tl: (f-DO 16 He la dng hong hi ca tinh | chdt ctta nd la nw nhaw dé voi moi huong khong gian HL14. Bigu dién 19a d6 cdu. © Trong toa do Descartes, diém M dure xdc dink boi b6 ba (x. V, 2. Nhumg cang co thé ding b6 ba (r, 4 @) trong do 8 va g la nhimg s6 do goc con r la khodng cach r=0M = (Oz; OM); 9 = (Ox; OM;) © DE bao gdm duye toan bd khdng gian, phai cho r bién thién ie 0 dén +2, ObiGn thien tieO den ava pin thién tie0 dén 2x He thie gitta toa dé Descartes va toa dé cau la = cos = sin@. cos sin. sin p2.1.2.3. Ky higu ham séng Ham song cita nguyén tie hidro va orbital nguyén te (vist tt 1 AO)!" ta hai ten déng nghia. BO ba (n, €, my) dunye ding dé chi cic AO Yy,¢4q, nhumg trong thyc tf hay ding cée cha s, p, d, f..(c6 ngudn gdc tir tigng Anh sharp, principal, digfuse, fundamental, img voi nhimg gid tri khéc nhau ciia £ (H.15). Ung voi méi gid tri cla £ c6 (26 + 1) gid ti cia m; trong khoing (646). H16. ghi ten nhumg ham rieng cia nguyen tir hidro tng véi nhang gid tri du cian. 2.1.3.Vai trd cla sé long tu chin n 2.1.3.1. Tri riéng clia nang lugng Gidi phuong tinh Schrodinger khong nhang cho biét nhang ham riéng micu ti nhong trang thai én dinh cda nguyen tt hidro ma cdn cho biét nhong tri rigng cia ning lung E, Phép tinh chimg 16 ring nang lung rigng ciia hg mo t bdi ham song Vy fy, BA: 4 -me 1 E, ee 8eo.h7 n* Nang luyng cia nguyén tir hidro duyc luyng tir héa béi sé luyng tir chinh n. Chit thich: Biéu thite ciia E, cho boi Co hoc hegng tit cang chinh la biéu thite do mo hinh Bohr. Thay ban kinh Bohr ag vao hé thite trén se duge : ™ 8r.80.y Thay cdc hang co ban trong E,, bang gid tri x6 cua chung + Bigu dé mac nang lung cia nguyen tirhidro thé hign & H.17. Cha g ring c6 vO sO mOc nang lung mg voi nhong trang thd4i lien két ca he g6m_ nhan va electron. 2.1.3.2. Su suy bién mirc nang Iugng cia nguyén ter hidro Trong Co hoc luyng ti, mot mic nang luyng duye n6i khi c6 nhigu ham s6ng mg véi gid tri nay cua ming luyng. bj suy bién Doi v6i nguyen tir hidro, tir khi'n khéc 1 thi ¢6 nhiéu ham rieng 6 cing sO Iuymg tirchinh n nghia a c6 cing nang Iuyng. Digu nay suy true tigp tir nhong he thuc git cae sO lugng tk # img voi moi gid tr chan C6 n gid tri cha £ trong (0; (n-1)), # tng voi mbi tri cha ¢ c6 (2¢ +1) gid tri ca mj trong (-6; + 6). [*] tigng Phap viét 1 O.A. ; day 1a viet theo tigng Anh, da quen dang & Viet Nam [ND] 2 HoshocdTH e yojlij2]3 KihicuAO| s |p [da | sf Hinh 15. Ki higu cdc orbital nguyén te 420 4s H.16. Danh phap (cach goi tn) nhang ham riéng ciia nguyén tie hidro, ° camey CoS osueey 08906 a 1sitev Bs ost an f{#—— -s,01ev 3,606 HIT. Nhang mite nding tong ing voi nhing trang thai lien ket cla nguyén tie hidro. Trang thai lién két la trang thai co E dm ; trang thdi co E = 0 img voi nguyén tit bi ion h6a. Khi dé nhdn va electron tao thanh he & trang thai khuéch tan,10973731,534+0,013 m! — (.10) TE QMQ.CN Red eh Rezane aghucrn 7 Sai sO tung doi — the ngheem) = 6.107 chimg 16 sy pha Ry cvwenghi hop Ba tuygt vo Chit hich: # Sv phic hop gia f9 thuyét va thu nghiém con c6 1hé diage cdi thien, MOt trong nhimg nguyen nian sai lech Ia gid shit rng nbn ding yen. Thue 1, ie (nhin + electron ) la: mot Bai toan hai vat, chi c6 tm Kid luge la ding yen. Cor hoe c6 dién ching minh ring kéi qua van ding néu thay m, bang khdi lame rit gon pect h? (electron + nha) sao cho: = eM (a4 ta kid long nin) m+ M Thay 11 va0 cong tee trén th gid tr} Ry thuyét hoan toan phi hop voi id tri thuc nghigm. © Gi tr tink duge 0 tren thudmg diaye ky higu la Ry, Vind ting voi Khi coi nhdn la.v0 cing nang so v6i electron # Ry d6i voi deuterium va tritium khong cing gid tri Adi voi proton; nhue vay phé cita chiing c6 khidc chit it > Dé luyén tap : BT 6,7 va9. oe “| m7 “azn us i “ase 10 s aad Face [athlon nen Poche ‘th hai Tale is Lyman H.19. Phd phat xa cia nguyén vir hidro. Biéu dé nang huwmg cho phép gidi thich nhamg day vach khac nhau ciia pho. Di voi méi day, sw chuyén dich, twang ting VOI Aig. duuge bi hj béing dueeng mai ten.2.3. Khao sat nhGng ham séng cua nguyén ti hidro 2.3.1 Biéu thiic orbital cla nguyén tu hidro ‘Nhong biéu thi nay déu chifa ban kinh Bohr do ; ¢6 thé coi ag la chudn (étalon) 49 dai dic trung cia nguyén tit H.21 1a biéu thie cla phin xuyén tam va phin géc cia AO hidro. Di nhién 1a céc ham s6ng nay duye chudn h6a nghia 1a théa man he thie $f evan pian ¥>(M).d°r(M) Trong toa 40 cu, nguyen 10 thé tich d>7(M) ma tim Ia diém M(r, @ 9) 66 bidu thie I d3z(M)=r?.dr.sin0.d0.dg(H.20), do 46 ditu kig¢n chudn héa 1: an pe (ae 2, 2 im a 7 7 R'().¥° (6,9)? dr.sin6.d0.dp =1 Nhong hing ¢ trong R(r) va ¥(8, g) duye chon sao cho R(r) va 4 g) thod man riéng re diéu ki¢n chudn héa, vay: FPorasia fF LP @orsinaaodg=1 Chi thich : Hai ham song kiéu p, %y.11 va Y,1-1, la ham phite. Tinh chat uyEn tinh cia phuomg trinh Schrédinger cho phép thu duge nhang him thuc Vi Ynaave Yai1 tng voi cing mpt nding tung nén ham (A. Pn + BY q3-1) clang la nghiém cita phuong trinh va ting voi cling nang luagng do (A va B la hai heing, thye hodtc phitc). Nhuevay thu duage hai ham thyec, thong ky higu la np, va npy, nhung khong con c6 thé gan cho chting mot gid if rnd dp H.20. Nguyén 16 thé tich trong toa do caw Cang nhut trong toa dé Descartes nguyén 1 thé tich dr duoc iu thi boi tich cua ba dich chuyén truc giao ma o day la {tri cia SO lugng tie tie my .H.22 cho biéu thitc cia nhtng AO 2p nay. r-(1.d6).(r.sin.dg). ae m ¥(0,9) orbital 1] o 0 z= 1s 2 0 0 2s 241 ° 3 | 0 ° 3s off lS ses i H.21. Phdn xuyén tam va phdn géc ciia mOt sO ham song nguyen tit hidro,"“,* H.22. Biéu thite cua nhang AO 2p thc. Bai todn nay cong dt ra cho cdc ham kiéu d: ngodi ham ¥%,.9, ee AO nd Va phic; vi vay cng ding phuong phap trén dé duge nhong ham thye (H.23). 3/2 2 1 1 4 Yoo0=8d22)=[4 we ‘2.22 = Bd,2_ 2 (2) WIR od H.23. Bigu thie cua nhang AO 3p thyc. Oi chung, ¥fr, @ g) la nhang ham ba bién va mat d9 xdc sudt D = ¥? cong nh vay: Vi vay khdng thé biéu dién mot cach khong cén than sy bign thien cia nhong ham nay. Trong nhang phan sau, ta st n6i ro nhong quy ude biéu din thutmg ding. 2.3.2. Khao sét ¥va Ytheo r CO dinh bién Ova — 6 gid tr DAL KY Op va Yo nhumg khOng lam trigt teu ¥(@, g). Khi r thay déi thi diém M toa d0 (r, 9, Qo) chay tren nia dudng thing 4p xuit phat tir O va xc dinh béi Oy va go (H.24). Nhu vay, nhang dung cong Mr, 9, @o) vaD (r, Op, Po) cho bist 1a cae ham ¥/va D se bign thien thé ndo khi M rdi xa hat nhan theo Ay. Vi da 66 dinh 6 va g nen céc bign thien cba Yr) va Dir) 1a ti Ie thuan v6i bign thien cba R(r) va binh phuong cia n6 (#.25). Vi R(r), va do 46 ¥, trigt tieu va d6i du & mot sO gid tri cia r nen ham sng trigt ti¢u & moi diém cia hinh céu tuong img goi I hinh cdu nat. > Dé luyén tap: BT 11. H.24, Nita dudmg thding Ap dugc xc dink bdi gid tri cia O,va 9» Oxde dinh mot hinh non tron xoay c6 dink Ia O va nita g6c dinh 1d Oo. po xdc dinh mot ita mat phdng; Ag ld giao cha hhai mat nay.4 or 4s 6 8g ahem asgei-ho 4, e oa 1 °: -024 z -O1 a - + ° rT" 2 3g 468 011% oP.B ay one \e3?- Ras cosas? sis ay » an a 0 0,02: ° 3 ° z we | & H.25. Bign thién cua aj'?.R(r) : chit ¥ sy thay d6i thang do cdc duimg cong. 2.3.3. Khao sat va ¥/* theo (0, 9) Co dinh bién r & gid tri bat, ky ry nhumg khong lam trigt tidu Riv). Khi 8 va r thay déi thi diém M( ry, @ g) chay ten hinh cu ban kinh ry, tam O. Nhu vay, nhung dung cong Yr, & g) va D(ry, @ g) cho biét la cdc ham ¥va D se bién thién thé nao khi nia dutmg thang OM d6i huéng. ‘Ta nhac lai cach biéu dién c6 dién theo toa do clu Cue O 1a vi ti cia nan, truc cue 12 O;, g6e quay quanh true cue 1d g. ‘Tren nia dung thing xac dinh béi céc gid i cia Ova gy, ly mot doan p We thudn voi gid tri ca YH ry, 8 9) (hode gid tr tuyet doi cia Y¥ndu nd Am) hoae cia (Y(r9, 8 @))7. Tap hep nhang diém nhw vay lam thanh nhang mat thé hign tinh bat ding hung ciia ham song. (H.26) Vi c6 dinh r nen nhomg bign thién cia Yfr) va D(r) wong tng Ui Ie thud v6i bign thien cia Y(8, g) va ¥7(8 9). 2.3.3.1. Khao sat orbital s Nhong orbital s, dic trumg boi sO Iuong tir / = 0 c6 thanh phin g6c Y khong di: nhong mat chi thi cia ¥ va D I nhong hinh edu vi vay ede orbital § c6 doi ximg céu (hoge ching la déing huedmg). 2.3.3.2. Khao sat orbital p Ta se khao st nbung orbital 2p thuc, nhung cdc ket qua due cho cée AO np vi ¥(A. y) khong phy thude vao n. 66 thé mar rong Sy tdn tai truc tron xoay Biéu thav gidi ich cia céc orbital 2p (H.22) Lum néi bat tinh tong duong (thay ¢ bing x hoge y s¢ chuyén mot AO 2p. thanh 2p, hose 2py) va tinh doi xtmg tron xoay quanh mOL trong cde tryc toa dd : Adi B a irs 2 10 é 11.26, Mat 5 thé lion nhimg bign thién cita ¥ theo Bva @ con r cb dinh & ry. D6 dai p, doc theo ita duimg thing A xde dinh boi Ova 9, t1 18 voi | (7 ,8,9)|vi AO2p., vide cO dinh r va z s@ x4e dinh mot vong trOn 12 giao cla hinh cu, tam O ban kinh r, voi mat phing c6 d9 cao z : 6 vong tn nay thi 2p, khOng d6i (H.27). M6i mot orbital 2p nhan mot trong céc tryc toa do lam true tron xoay. @ Sy tén tai mat phing nit Mat phiing nat 1a mat phang 6 d6 ham trigt tieu : 46 1 mat phang z = 0 A6i VOi 2p, ; ¥ = 0 AOI Vi 2p, ;.. Mat phing nay 1 mat phdng phan d6i xtmg cia ham song : néu My va My 1d hai diém d6i ximg qua mat phdng nay thi ¥ (M)) =~ % (M2) Neuye lai, n6 14 mat phing d6i xtmg 463 v6i binh phuong ham s6ng te 1 mat d9 xie suit e6 mat: DOM) = DM). 1 Mit chi thi cia ¥va D CO dinh r thi (2p,) va (2p,)? ham cia va gs rp.) =A. 6080 5 Wap.) = A*.c0s 0 Vi (2p) khong chia g nen sy quay g6c @ quanh tryc z khong lam thay d6i gid ti cha (2p,) va binh phuong cia n6. Nhong mit thu duye béi céch bigu dign toa dO cue I tron xoay quanh true z nén chi cin kho sit nhang kinh wyén cia ching nghia 14 hong dung cong la giao cia mat nay voi mat phing chifa tc ton xoay, 6 day la Oz (H.28). Nhtmg dudng cong nay chi ring mat d0 xac suat c6 mat electron Ia cue dai doc theo true Oz sit phing nit.xOy 11.28. Nhang kinh tuyén ciaa nhang mett chi thi ca ¥va D déi voi AO 2p, : a) p= IA, cosdl b) p= A?.cos” 0 Cach biéu dién nay lam ro tinh bat déng hudng cia AOp. 2.3.3.3. Khao sat orbital d Ta se khio s4t nhng orbital 3d thyc, nhumg céc két qua c6 thé mé rong cho cic AOnd vi ¥(8, p) khOng phy thude n. Bigu thie gidi tich ca cée orbital 3d (H.23) cho thdy tinh tuong duong ca céc AO Bdyy, dx Va dye (vi du thay x bing z sé chuyén AO 3d, thanh AO 3dyz)). Orbital d.2_\2 duge suy tir orbital dy bang céch quay quanh truc Oz mot g6c #4, Ta khdo st nhang tinh chit cba AO 3d yy 16i suy ra cho nhimg AO 3dzx, 3dyz va 3d,2_,2- Neuve Iai, orbital d,> se khdo sat rieng. 9 ca0 76 (2 hinh cfu bin kinb 7 , tam 0. H.27. Giao cia nhang mdt (3) va (a) 1a duomg cong Ts T la mot hinh tron tam o trén Oz. O moi diém cia T : 2=2q va r=19. Do db 2p, c6 cing gid tr) moi diém cia T.& Yéu t6 d6i ximg © Bidu thie gidi tich cha orbital 3d chi ring g6e O 1a tam di ximg cho mdi orbital my : neu My va My 1 hai diém doi ximg qua O thi (My) = (M2). © AO Bd yy tHE thudn vor tich x.y nen trigt tid khi x hoge y tigt teu ; vay 3d4y 6 hai mat phdng nut la nhong mat phdng co phuong trinh 1a sx = 0 nghia 1a Oyz va Oxz, Hon ntta, néu Mj, vi M2 1a hai diém doi xing qua Oyz thi x1 =—x2 vay = y2, do dé Y(M)) = -¥(My). Nu M, va My 12 hai diém di xtmg qua mt phdng c6 vet 1a nhimg dudmg phan gide cia Ox va Oy thi x =y) va x2 =y1 do dé ¥(M,)=¥/(M3). Nong mat phang nay 1a nhong mat phing doi ximg cba AOXy © Mat phing Oxy ld mat phing d6i xtng cla AO 3d. ways ‘Mat chi thi cia Ya D Nheng mat chi thi nhang bit bat nhomg yeu 16 doi xtimg ni CY Me. V2 Goi BCom 2COk thien cia nhang AO3d theo vag Lam néi en (H.29), rte dey Fetal de i > GTO ud 4 amt dey Cho ring OAnd c6 tinh bit ding hudng rit manh ; mat dO electron cha céic OAdyy, dey Va dye la cye dai dc theo céc phin gidée cia céc tc ; cdn mat d0 electron ciia cic OA d_2_,2 Va da Ra oye dai doc theo cc true. > Dé luyén tap : BT 18 va 19. 2.3.4, Mat dang mat do Tap hop nhung diém eda khOng gian ma 6 46 D(M) c6 gid tri khong d6i duye goi 18 mat déing mat do xde sudt. Khi cho D(M) nhong gid tri khic nhau, ¢6 thé ve trén cing mot dé thi nhong mat ding m§t 49 khéc nhau. DOi vGi mi mat nay, c6 thé chi ra gid tr] tuong tmg cia D = ¥* nhung thudng ding Sy w? ar nghia 1a mat dd tim thy electron 6 bén trong thé tich + gigi han boi mat duye xét. H.30 trinh bay hai ech danh chi s6 cc mat, qua vi dy cia AQ, 4.1.29. hang mat chi thi cia Y? theo @ va y cua cde AOd Nhang mat nay néu ro tinh bat dang hung cia cdc orbital nay.4.11.30, Miang ma ») ding mat dé cia orbital 1s, la nhang mat cdu ddng tam, due biéu dién o day being kinh tuyén lag Tao) ctia ching. a) Gid tri ght chi sor hinh cdu ban kinh r la bang (18)? a3, nhan voi 1000. b) Gid tr} ghi chi s hinh cau ban kinh la bang xc sudt ¢6 mat electron trong qué cau nay. Hinh 31 1a kinh tuy€n cia nhamg mat ding mat do xéc sudt sao cho xde suit tim thdy electron & ben trong thé tich r gidi han béi nhong mat c6 xée suit 14 50% va 99%. Céch biéu dién nay cho thdy r0 ring do dudi khong gian cia AO, tmg v6i sO luyng tirn, Ling khi n ting. 50% 50%. ee H.31, Kinh tuyén cia nhang met dding mat do cua mot vai orbital. Gid tr} ghi chi s6' matt la xdc sudlt c6 matt electron trong thé tich & bén trong métt nay. Chi ¥ rang d6i voi nhang AO ki€u p va d, thé tich tong ting voi mot xdc sudt cho trudc c6 thé gdm boi nhieu thé tich tach biet.2.3.5 Mat 46 xdc suat xuyén tam Digu thi vi 1A xét sy bien thien xéc sust tim thay hat é céch hat nhan 1a r, gita hai qui clu déng tam c6 bin kinh vO cing gin nhau lar var + dr. Xie suit thay hat d diém M(r, @ g) nghia la 6 ben wong nguyen 16 thé tich d3r =r? dr.sind.d0.dola @P = DXM) dr =¥?(M).aPr DE duye MO xée suit chi phy thude r, ta Hy tich phan theo nhamg bién @ va 9 (H.32). LE poe veg oy 2 a= fi 7 R(0.¥*(6,9).7dr.sin8.db.dg Mu6n vay, dua nhang s6 hang chi phu thudc rra ngoai du tich phan P(r) = Rr). dr.” Py? “ aP(r) = R2(r).r° arf, ¥(0,9).sin0.d0.dp Ma ¥(@ g) duge chudn hoa voi moi AO nghia la: Fey _ i: fy 1°(0.p).sin8.d8.dp =1 Vay dai lung dP(r)/dr img voi mat do xc suat theo don vi dai va duyc goi M4 mat dO xuyén tdm, ky higu Id D,(r). ap a =D) = Rn? aay) 7 4 Khao sit mat d9 xuyén tam cia orbital 1s c6 bigu thie la 312 (2 erie A 4 var 1Y Ta c6 D,() = (2) 4e-2t/40 1? 0 Yi0.0 = Lay dao ham cia D,(r) 48 khio sit sy bign thien AD) _[ LV gt g-2rlay {yt dr (ag) © ao a9 Dao him tigt tieu khi r = 0, 7 = agva khi ro nen n6 duung khi r < ao va am khi r > ag (H.33). Su-c6 cye dai cho phép thdy lai ¥ tuing vé lop electron, nhung ¥ turing nay chi 1a bé ngoai: Xde sudt c6 mat electron 6 trong mién 0,9dp va 1,1 ag chi la 10,8%(xem BT 20). Tuy nhien, theo quy ude, vin goi gid ti cia r lam cho D,(r) eye dai !& ban kinh orbital 1s : ban kinh orbital 1s bing ban kinh Bohr ap. “Thi nghigm thé tich a) d’r=17sind.dr.d0.dg H.32. Thay d6i thé tich nguyen 1. Thay thé thé téch aiém @r=r) dr.sind.dddp bing vo hinh cdu c6 nguyén 16 thé tich la de =4z7} dr. 0,318. H.33. So sdnh bign thién cua mat dd D(r) va mat dp xuyén tam D,(r) iia orbital 1s.Hink 34 bigu din nhong bin thien cba D,(r) d6i voi nhong AO diu tien: ban kinh coa AO it phy thude s6 Iuyng tir phy / nhung ting r6 ret theo s6 lugng tir chinh 1, > Dé luyén tap : BT 17 va 20 2.3.6. Két luan va cach biéu dién theo quy udc Nhang yéu t6 cia he duye neu r0 tren cc orbital c6 sO Iuyng tir chnh 7 1a 1 va 2. Cang c6 nhu vay véi céc orbital ma n lén hon. Dac bigt, di voi n bat ky : * Cac AOs e6 A0i xing cu. * Cac AOp c6 déi xing tru quanh mii tryc toa d6 va c6 mat phing phan d6i xg di qua tam va truc giao véi truc tron xoay. Mat do xe suat 1A cue dai dge theo true tron xoay tuung ting. * Cac AOd €6 0 la tam A6i xing; cic AO dyy, dzx, d,zc6 mat dO xc suat cue dai doc theo cic phan gic chinh cia cdc mat phing tung ling; d6i voi orbital d,2_,2 thi cuc dai nay é doc theo nhimg true Ox va Oy. Déi véi orbital d_2 thi cy dai nay doc theo truc z. Trong thyc 1, nhing tinh chat d6i ximg cla céc AO duye biéu dién don gin hoa nhu sau : vé dang cia mat chi thi nhong bién thien cia ¥°(0,9) va ghi déu cia ¥/@, g) trong méi mi¢n (H.35). Thudng ding quy ude ve du nhur sau : mién t6i img véi ham séng duong, mién sing tng voi ham s6ng am. Cich bigu din nay cho biét déng thoi cdc tinh chit d6i xing va bat ding huxing cia him song. N6 chia dymg phiin 16n cdc thong tin cn thiét khi Kho sat lien két héa hoe. © ©. SS @0 : © ; A dgip : : : Cdes . ames ; { H.35, Duong cong biéu dign tho sw bién thién cia Y? theo Ova g. hing duomg cong nay thé hign ro tinh bdt ding huomg va tinh diing hong cha nhtng ham tong ting va nhang yeu 16 d6i xing cia ching. Mién ma ham song la duong diege gach dam. 449.D,(r) 05. i ° 1. 2 3 Mao a.D40 oat A aot Di, ons o 2 6 10 rlag 0244 » f.0.0 » aoe 0,04. O23 10 lag 012-440-Delr) oF oas aos a3 10 lag H.34. Bign shién cita dai luong dy.D,(r) cia mot orbital nguyén tit hidro. Swe t6n tai nhang hinh cdu niit thé hign boi su trigt titu D,(r) a6i voi r khdc khong. Chi ¥ rding m6t AO ns co (n = 1) hinh cdu nut, cOn mot AO np chi c6(n - 2).2.4. lon dang hidro 2.4.1. Hé dang hidro Nhang hg nay gdm mot nhan dign tich +Ze va mot electron duy nbdt : ching luda luda a nhong ion vidy He* (Z=2), Li?* (Z= 3) va Be** (Z=4). DE khio sit nhong ion may, ta coi nhan Ri ho’n toan dinh vj va bo qua tung tic hip din so véi tuong tc tinh dign, Khi do nhimg trang thai lign két cia nhimg he nay durye mo t& béi cfc ham song 1 nghi¢m ca phung trinh Schrédinger dong dang véi cia nguyen tirhidro, chi sai khéc mt thira s6 Z. 2.4.2. Orbital va nang lung * Cang nhunguyén tirhidro, Yr, @ g) fa tich ca ba ham mot bign : Hr, 8 9) = Rng). 8, 1mj8)- On, (P) © Nhong s6 lugmg tir, va my cong théa man nhomg he thée nhu v6i yen tir hidro, Biu thie gidi tich cia céc AO cia ion dang hidro duyc suy tir biéu thée ca orbital nguyén tirhidro bing céch thay aq bing ag /Z ‘* Nhang gid tri ri¢ng ca ning lugng phai nhan vi Z? (1.12) Voi mdi gid tri cia n, electron cia ion dang hidro lién két voi nhan manh hon so voi nguyén tir hidro, hang gia tr cia r img v6i cye dai cita mt do xéc sudt xuyen tim duye suy tir nhing gi tri tung tmg cha nguyen tr hidro bling cach chia cho Z : 60 duéi khOng gian cia ion dang hidro yéu hon so véi nguyen tirhidro, > Dé luyén tap : BT 8 va 16. DIEU CAN GHI NHC ™ HAM SONG VA XAC SUAT CO MAT Méi hat duye gin mot ham song Y{x, y, z, £) ma bién do phy thudc cdc toa do khong gian va thoi gian, Y duye goi la ham song cia hat. Xdc sudt d°P(M) tim thay hat trong nguyen t6 thé tich d°7(M), c6 tam Ia M, la: OP =? (x,y, 2,0). dM) ¥? bigu thi mat d9 xac sudt D(M, 1) c6 mat hat & lin can M 6 thei diém t. ¥ phai théa man “diéu kién chudin hoa” : Wham? D6i voi hé On dink, mat A xiic suit c6 mit hat khong phy thuge vao thai gian. ay™ NHUNG HAM SONG CUA NGUYEN TU HIDRO Ham séng ¥, nghi¢m cia phuung trinh Schrodinger, duye goi la ham riéng. Nhong ham riéng, m6 ta electron cia nguyén tir hidro, con duye goi la nhimg orbital nguyén ti, viet tt la AO. Y phu thude vao sO luyng tira, , my 2 Yaa, (85 9) = Ry, (0.8, 9) n, sé luyng ti chink, 1 mot s6 nguyén duwng :n € (1, 2, © (, 80 luyng tir phuong vi (s6 luyng tir phu), 1a cé gid trinhé hona: f € (0, (n-W)) ny : ofif2}s] ki sipidadlys) ™ NHUNG NANG LUONG RIENG CUA NGUYEN TU HIDRO * m, sO luyng tir tu, la mOt s6 nguyén tung d6i, nim trong khoding -I va +1. M6i AO duye chi béi mot chr Ning luyng rigng £,, cia nguyén tir hidro & trang thai img voi ham ring Vp, |, 60, =(eV) 1" Nang luyng ctia nguyén ti hidro duye luyng tir héa béi s6 luyng ti chinh n. C ning Img tuvng tg véi nig trang thai lien két cia hé tao béi nhan va electron, Vo sO mic D6i voi nguyen ti hidro, mdi ‘n tung img voi n? ham orbital khéc nhau nhung cing nang luyng £,, : trong nguyén tirhidro, nhung trang thai ndng hnyng E, bi suy bién n? lan. ™ PHO NGUYEN TU HIDRO Khi nguyen tir hidro chuyén tir trang thai nding luyng E,, toi trang th voi 0 << q, thi phat ra photon 6 tan s6 V4 840 Cho MV 54 = Eg 5+ Do dé buvie sing 4, (gon Cita photon théa man he thie : &( 7 + Ry lahang Rydberg vg 1 xe dinh day vach ; khi n e6 dinh thi g xsie dink nhtng vach khéic nhau cia cung mot day. @ NHUNG TINH CHAT BOI XUNG CUA CAC AO * Cac AO s 06 doi ximg. * Cac AO p cé déi ximg tru quanh mdi truc toa dé va cé mat phiing phan déi xung di qua tam. va truc giao voi truc tron xoay. Mat d6 xdc suit 1a cuv dai doc theo true tron xoay tung ting. * Cae OAd CAO dyy, day, dy, 66 mat dO xéic suait cue dai doc theo cae phan gic chinh cia cae mit phiing tung ting ; d6i voi orbital d_>_,> thi cur dai na doc theo nhung truc Ox va Oy. D6i voi orbital a. 2 thi cuv dai nay doc theo truc 7, ™ NHUNG HE DANG HIDRO Nhung hé dang hidro gém mot nhan dign tich +Z.e va mot electron duy nit. Nhung ham riéng cia ching Yr, 8, 9) duve suy tr orbital cia nguyen tirhidro biing cach thay ay bing O ta tam doi ximg ; ¢: ay! Z nang luyng phai nhan vei Z?. Voi gid tri cia ny electron cia ion dang hidro lién két voi nhan manh hon so véi nguyén ti hidro. Do du khong gian cia ion dang hidro yéu hon so véi nguyen tr hidro. nhang gia tri riéng c 29B AI TAP Nhimg de ligu sau diege ding trong nhimg bai todn voi dp dung s6 hang Planck : h = 6,63.107 3.5 3,00.108 m. N 4 =6,02.1079 mot! Ban kin Bohr ag + aq =52,92pm van 16 anh sang hing Avogadro khdi liemg electron ; me =9.11.10*' ke dign tich electron ~e : e = 1,60.10"'°C. AP DUNG TRUC TIEP BAI GIANG “| Song dién tu va nang lugng photon Tinh nang lung cla nhong photon tmg véi cde séng dign tirsau song radio (7. = 1500nm) ; TR (100 wm) : baw xa khit kien (SOOnm) : UV (100 nm); tia X (0,15nm) 2 Chuyén doi Chimg minh ring buve song % va bign thién nang lung (ung img AE lien he voi nhau theo he thie 4 = I241/AE neu A do bing nm va AE bing eV 3 Phan ung héa hoc va phan ting hat nhan 1) Trong phan img h6a hoe, céc nguyen ti 66 thé & trang thai kich thich, Khi d6 chung c6 thé phat ra cde photon do bi mat kich thich. Mot mol photon ma bunve song trong chin khong ki 2 = 400nm e6 ning 2g bao nhieu? Nhomg bare xa tung img cia im é mign ph nao ? 2) Trong phan img hat nhan, cae nhan nguyen tt khi mat kich thich phat ra cdc tia y ma bude séng trot chan khong [a co pm, Xae dinh cd 16n cia do chénh nang amg git hai mie nang lgmg cia hat nha, 3) So sinh hig (s6) nang lung gita hai ham cia nguyen tir va har mie nang luyng cia nhan. Tir day ¢6 thé rat ra ket luan quan trong gi? 4 Day Lyman in sO tinh bing Hz cia cde vach day Lyman eta suyen tirhidro cho bii cong thie sau : 288.10! - Un?) ‘Tinh nhong burte song img voi n = 2, 3 vad va bute song gigi han Ajj). Nhong vach nay nam tong mién no ca phé dign tir? 5 Nguyén ly té hop Phé phat xa cia nguyen tir hidro gdm nhung bie xa 6 bune séng la > /875nm ; 656,3nm ; 486,Inm ; 121,6nm ; 102,6nm. 1) Nhang bie xa nay thude mién nao (UV, kha kien, IR, ...) ctia phd dign tir? 2) Ritz da thay ring mot sO Un sé tug mg duge suy tir ede tin s6 khde bing «6 hop tuyén tinh. Kigm cchtimg he thire nay. © Nhiing mirc nang lugng cla nguyén tu hidro 1) Nang lug ion hoa nguyen ti hidro tir trang thai co ban 1 13,6 eV. Bure xa c6 bude séng ngdn nhat ma nguyen trhidro c6 thé phat ra 2) Viet bigu thay, theo so luyng ti chinh n, cla nang luyng dic trmg nhng trang thai én dinh khae nhau cia nguyen tt hidro, Tinh nang lung cia mie die trmg béi n = 4. Khi nguyen tir bi khir kich thich thi bude song cia bie xa 6 thé phat ra tir mie nay 1 bao nhieu? 7 Trang thai kich thich 3d Xét nguyen tirhidro drtrgng that kich thich 34 1) Nhong chuyén dich phat xa c6 thé c6 1a gi? Bicu hén tren mot se do, 2) 3) Tinh nang lung ion héa ca nguyen we hidro & trang thai kich thich nay (theo eV va theo kJ. mol!) Deetigu inh buve song eta nhing photon tung tmg Nhimg nang lug riéng cia nguyen tie hidro la Ey =~ 13.6/n7 (eV), (n nguyen > 0) 8 ton dang hidro 1) Nhdc lai din nghia ion dang hidro 2) Nhimg nang luyng ri¢ng cia he nay thoa thie E,, =-E,/n® trong dé n 1a si nguyen dime E; biéu thi gi? we 303) Nhung ion Be* va Li?* 6 phai 1a nhomg he dang hidro khong ? 4) Nang luyng ion héa cia He* va Li2* wong img 1h 54,4 eV va 122 eV. Co thé tim duye he thie don giin gita sO dign tich va ning Iuyng ion héa cha nguyen tir hidro ? 5) Tinh ning luyng rieng cia bon mie dau tien cia nhang nguyen ti nay, So sinh véi nguyen ti hidro. Vi sao c6 thé n6i ring Z cang ting thi electron bj liga ket cang manh ? 9 Khir kich thich 1) Nhang nguyen tir hidro 6 trang thai co bain bi kich thich béi tia UV 06 bude song 97,35 nm. So lugng tit chinh cia trang thai nay 1a bao nhieu ? 2) Khi nhang nguyen tir nay bi khir kich thich thi chting c6 thé phat nhang bite xa 06 bude séng bao nhieu? 10 bing hay sai ? Nhan dang nhong ménh dé sai va chinh lai : 1) Nang lugng cia electron trong nguyén tir hidro chi phu thudc sO lugng tir chinh n. 2) Cac AO s c6 adi xtmg chu. 3) Mat nuit 1a mat ma 6 d6 ham s6ng 1 cye tiéu. 4) Céc AO 2p,, 2py va 2p, 1d tron xoay quanh cdc truc toa d0. 5) Cic AO 2px, 2py va 2p, C6 cing phiin g6c. 6) He** 12 ion dang hidro. 7) Trong Li?* , ning lugng céc AO chi phy thude so lung téchinh n, 8) Nguyen ti bj kich thich Ia nguyen ti da mat mot electron, 9) Ban kinh cae AO gidm khi sO Iuyng tir chinh ting 10) Cac AO 3p, va 2py €6 cing phin go. 11) AO ¥449 06 di xing cdu. 12) Céc AO 3dyy, 3dyz Va 3dzy [A trdn xoay quanh cae tryc toa do. 13) AO ¥%433 1 AO kiéuf. 14) Khi phét ra mot photon thi nguyen ti tré vé trang thai co bin. 15) Nang luyng ion héa He* I6n hon bén lan so voi nguyen tirhidro. 11 Nnang mat nat 1) Nhdc lai dinh nghia mat nat. 2) X4c dinh nhtng mat nut cia AO 3s. Darligu: 312 a= (2) gp ote }e a») WE 9a VAN DUNG VON KIEN THOC * a - s. ‘ 12* thong Iveng photon cia may phat v6 tuyén ‘Mot my phat digu tin phat séng dng hudng 6 tin so 103,5 MHz. va cOng sugt 15kW. Cho ring bic xa dune lan truyén khong bi hap thy. Mot anten thu song tren bé mat 0.4m? thing géc voi hung lan truyén ; anten 6 cdch xa may phat ld SOkm. 1) Tinh théng lugng photon phit ra, tte 14 sé photon phat ra trong mOt gidy. 2) Thong lugmg photon anten thu duye 1a bao nhieu ? 13 Lugng tir 1a gi ? Tinh "tic dung" dic trung cia hai hé sau, so sénh voi Ava két luan : © MOt anten vo tuy€n phat s6ng 100 MHz voi cong sudt SkW. ‘© Mot nguyen tir natri c6 nang lung ion hda la 5,1 eV; phé phat xa cia né gém 3 vach trong mién ving ( = 590 nm), 14+ Kich thich nguyén tu hidro bang nhiét Xét mOt tap hop g6m N nguyen tir hidro 6 nhiet 40 7. Ching duye phan b6 trong nhtmg trang thai ning lugng khéc nhau va cho ring sy phan bo nay tuan theo thong ke Boltzmann :Ng I Np Sexn(Bp = Eg RT) wong dd: By va By Whai mde ndng hayng, Np va Ng WT nguyen td hai mae nang lung tuMg tng, TAA nbagt dd tayet doi va. MOL ing phd quit got Wrdng Bolzmann, 1) Tinh, § 300K. ti sd Ny / Ny ting vii hai mic ning ugg dtu tiga, 2) Ti sd nly ts 3) GO abit dQ ndo thi ti sé may W107 2 4) Lagu oo thé thu duye nhang nguyen ti hidro kieh thich Khi tng nhigt dd? Daz ligu > hdng Boltzmann k sé uré thdnh bao nhieu khi 138.1073 .KE 15+ Kich thich bang va cham hang moe ning laamg hung tir hoa cho bdi he thie E, =-126/n? (eV); nls nguyen 1) Nang lugng ion hoa mot nguyen ti hidro 1 bao nhieu ? 2) Musin kich thich mot nguyen ti hidro tir mike co” ban (mn = J) den mu kich thich thi nhat ( 2) bing va cham thi electron phii co dong ming 10i thigy 1 bao nhieu ? Néu ban diu electron & trang thai nghi thi muti ting tc n6 cin dign dp ti thiéu 1 bao nhieu ? 3) Nguyen ti hidro, da duye kéch thich hu & tren, hi wd vé trang thai co bin (n = /) phat ra mot photon. Buse song eta photon nay 1a bao nhieu ? 16+ Phé cia heli ion héa Phé cia He* cé nhidu day vach. Day Pickering ing voi sy chuyén vé mac |. Xe dinh buve song cia nbimg bur xa thude mign kha kign, 117° Ban kinh AO 1) Khio sit mat dQ xéc suat xuyen tam img voi AO 2s va 2p. 18> nnang yéu té adi xing cla AO Mss 1) Xae dinh cae yeu 10 doi ximg ola AOI 22 5 nhong mat phing doi xtmg va phin d6i ximg cila chiing 14 nhamg mat phing nao ? 2) Xe nhang mit ae 2 6 ph trinh tuong img y y. y2 tong 16 phin khong Xae dinh du cla AO Ms gian mA n6 xéc dinh 3) Mat do xée suat 1 cue dai & nhamg hung nao ? Datki¢n: My 19: Nnang yéu t6 déi xing cua AO 3d AO 3d 06 biéu thie sau : (y" oe a) “93098 1) Nhang mat phdng doi ximg va phin d6i ximg 1a nhong mit phing nao ? 2) Xét nhong mat phinig c6 phuong winh : x = y=0,2=05: Xe dinh du cia AO 3d tong 16 min khong gian ‘ma no x4c dinh. 3) Mat do xde suit A cue dai & nhung huxing ndo ? 20 ~ xéc suat c6 mat 1) Nhic Iai dinh nghia mat dQ xéc sudt xuyen tam D,(). 2) C6 duvmg cong biéu di’n D,(r). Chimg 16 ring xi sudt P(Ry , Rp) tim thy electron & trong khoing om °hai hinh edu ban kin Ryva Rp, cing 66 tam La hain, €0 ¥ nghta d6 th) don gia 2 Dang bigu thie D,(7) cia AO Ly (da neu ong io tinh) biGu dign PCR, , Ry ) bing mot tich phan, 4) Dang may tinh, tinh gid tf PCR, ,Ry) trong hai trang hop sau a) Ry =09a9 + Ry = b) Ry =0Saq : Ry = 1,Saq. slag « Dae tigu : Tich phan kiéw [exp(-n.7.d1 dace tinh bang cach tich phan hai tan. 2 1 Phuong trinh Schradinger mét chiéu Xét MOL hat P Khoi Lung m chuyén dong doc theo tre x. The nang E,(x) eta n6 bing khong trong khoang + BL vO cing & ngodi khoding nay. Phuong trinh Schréx nger cia he nay By 827m" dx? 1) Giai phuong trinh vi phan nay , ding nhong diéu kign gic han ~ EV W- al2) = WEF a2) = 0 Dé ¥ ring vi E,(x) 1 chin nen mat do xée sual c6 mat cia hat P cong phai 1a chin do d6 ¥fx) phi Lt ham chin hoae Ie cla x 33 S-Hosngcn 2) Chudin ha céc ham tim duye 3) Chimg 16 ring nang lung toan phin £ cia hat P bi lug tirhda, Lap bigu dé nang luong tung img, 4) Tinh nang Iuong eda P trong hai trummg hop sau = # P 1a mot electron (m= 9,1, 10 kg) ; a = 500 pm; © Pla mot phan ti No (M(N) = 14 g.mol! hm. 22+ phé tien tuc MOt 86 ngoi sao C6 phé phat xa lien tye nhur d6i voi nguyen tir hidro, Hien turmg may 1 do cée ion H®* bat duge nhang electron ty do c6 mat wong moi tnaimg. Cée electron chuyén dong voi nhimg van We khde nhau, ké tir v = 0 : v vin nhé so voi van te anh sang trong chan khong c. Nang lung ban dau cia hé (ion electron) la bing E,, + K trong d6 K la dong nang cia electron true khi bi bit va E,, =0 landing Jugng cia nguyen tir hidro da bi ion hoa. Su bat electron tao ra mot nguyén tir hidro tugog lung tha E,, va kem theo la phd ra photon i sv Viet bigu thie cia tn sO v theo van te cia electron khi electron bi bat & mae ning lung dc tumg béi n= 2, Tin sO may c6 bi lung tir hoa khong ? Nhung gid tri gidi han ca ching Ia gi?Muc tTiéu 1 Biet phuong phap gan ding mot clectron va higu img chan. ™ Bit sp two n ca electron, nhung so lugng tir img vi nguyen ly Pauli 1 Higu cach xac dinh cu hinh electron cit nguyen tiré trang thai co ban bing cach ap dung nguyén ly Pauli, quy tie Klechkowski va quy tie Hund Higu cach xe din nang fame va bin kinh orbital Slater tirnhamg hing sé chan. Di€u cAn BiET TRUGC © Nhung nghigm eda phuong tinh Schrodinger cho nguyen dang hidro : dink nghia nhimg sO Iuong tin, mys nbomg AO s, p vad (xem ch.1). § Bicu dién nguyen tt theo phurmg phip Lewis (xem lip cudi cdip phd thong). NGUYEN TU NHIEU ELECTRON Me dau Mor nguyen tit co N electron lam thanh “bai toan co (N + 1) vat" : mot nhan va N electron, Tron 66 dién ciing nhue trong co hoc heen cor hon ik, gua ta chi biét gidi bai todn voi N= I nghia la voi nguyen nie dang hidro. DE nghién ciw nguyen tie nhiéu electron (N >2) edn phai ding dén nhing gid thiét lam dom gidn he nhung van phai tudn thi nhimg dac tinh co ban cia he khao sat. Hiéu luc cia phuong phap mé ta gdn ding do sé phai kiém ching bang cach so sanh voi thye nghiém. 34| ; Nhing phuong phap nghién cuu nguyén tu nhiéu electron 1.1. Dat van dé Vidu: Nguy@n tirnhidu electron don gin nhdt fd nguyen trheli (Z = 2), 6m hai electron. Trong khudn khé gin diing Born - Oppenheimer, nhan duye coi 1a hodn toan dinh vi. Ham sng ¥ mo ta he may phy Uude toa do cia hai electron ; vj tri cla electron i duye dinh vj béi bd ba (7), 4), gj) hoe (44.91%). Do do 712 ham cia sau bien (7, 8. Mr. Pr Or, 92) ThE ning Ep cia he gdm 3 96 hang (Hinh 1): electron (1) v6i nhan dign tich +2 ; © thé nang tuong tae tinh dign ‘thé nang tuong Lic tinh dign ca electron (2) véi nhan # thé nang tuong tac tinh dign ca electron (1) voi electron (2). 1.2. Phuong phap gan dung mét electron L bigu thi sy day gitta cic Arey nr electron ; sO hang may khong cho phép gidi chinh x4c phuong trinh Schrédinger. m Trong nguyen tt heli, sO hang Néu bd qua tung téc dy nay, nghia fa nu coi vi ui cia hai electron khong 6 quan hg gi v6i nhau, thi xc suit tim thy electron (1) 6 gin diém My hodn todn dd lap véi xdc suit tim thay electron (2) 6 gin diém Mp. Ly thuyet xc suit cho biét ring xde sudt thyt hign hai su kign déc lap biing tich xae suat cia mGi su ay ham s6ng mo ti hanh vi cia hai electron khOng tuung quan nay c6 thé coi nh tich hai ham s6ng ; mot ham mo ti hanh vi eta electron (1), ‘ham kia mo ta hanh vi ca electron (2) Yrs Bs Pry M2» Oa, Pr) = KAP). Xr fi him song m0 G hanh vi cia chi mot electron : 46 1a ham mot electron, cing goi Ia orbital . Ta khai quat hoa céch tiép can nay. +2) inh nghia Phuung phaip coi ham s6ng cia mOt hé nhiéu electron nhw 1a tich nhang ham song chi mo ti méi electron riéng biét duye goi la gén duing mOt electron ho¥e gan dting orbital. Méi ham séng mot electron duye goi la mot orbital. Glectron (1) dign tich-e lectron (2) ign tich -¢ ‘han A dientich +20 HLL. Dinh vi nhang khodng cach trong nguyen tit heli. ThE nang tinh dign co lién quan ti bakhoang cach ry, ry var) =e (1 1 é plea | eens 4neg nh 2) Areoni21.3. Higu ung chan Hoan toan bd qua tug tic dy gida cde electron a mot gin duing rat tho, Dé hoan thign them, ngu ta edi bien biéu thue thé ning mot electron tren co sd sau: mdi electron, ngodi vide chiu tac dyng cia trang hip din ca hat nhan, edn chju tac dung cia trudng diy cba cae electron khae ; x¢t trung binh, trae diy nay co doi xtmg edu. Theo phép gin ding thir nhat nay thi c6 thé coi méi electron nhw la chju tic dung cia hat nhan ma dign tich khong edn ta Z nda ma la (Z. = 3) 3c 1a mot hing s6 goi la hiing sO chiin, né biéu thi higu ting trung binh gay ra béi cic electron khic, Dai lugng (Z.- o) goi la sO dign tich higu dung (con goi la dign tich higu dung) va ki higu la Z* (6 va Z* phy thuge vio electron dang xét), Co thé tinh hang s6 chin theo nhang quy téc bén kinh nghi¢m Slater (xem. §5). 2 Nhiing két qua cua phép gan dung mét electron 2.1. Ham song mét electron "dang hidro" ‘Trong khudn khd gdn dung mdt electron v6 higu tmg chén, phurmg trinh Schrddinger ¥/ tich thinh mot sO phuong trinh bing s6 electron cla nguyen tk Mdi phuong tinh mot electron nay gidng het phuong trinh, Schrédinger cho nguyén ti hidro, nhang ham ri¢ng wag tmg % cong cing kiéu voi nhong orbital ca nguyen tir hidro : m6i ham bing tich cia phan xuyén tim va phdn g6c «phan goc ¥/@ g) gidng het truyng hop nguyen tirhidro va chi phy thude vao hai sO lugng wr ¢ va my ; # phn xuyen tim R,,¢(r) duye cai bi€n so voi nguyen tirhidro dé c6 thé xét dén dign tich hat nhan va hi¢u ting chdn. R,,e(r) phy thude hai so lug tirn va é Nhu vay m6i orbital 7 duge dic trung bai ba sO lung tien, &, mp) md nhong quy tc bién thien gidng het nhu doi voi ham ri¢ng cia he dang hidro. # nf sO nguyen duong ne (1,2,3..) + 61 sOnguyen dung hose bing khong 6€ 0,1. (2-1) * m; !& sO nguyen nim tong kho’ing -6 va +6 0,..(0 = 1), 2) me € (0, (-6 +1). ¢ TLE wynieeno ls [|p fa ls H.2. Danh phap orbital. Cang nine voi nguyén tie hidro, gid tri ita 86 hegmg tte phu quyét dink ky hiéu AO@ Phin g6c 1/8 y) xde dinh tinh chat doi xtmg ciia mbi orbital ; nhomg orbital 7 €6 cing tinh doi xtmg nhu cde AO cua nguyen tir hidro, Danh phap s, p, d. f vain duye ding (Hinh 2), 2.2, Biéu d6 nang lugng ‘Trong nhomg he dang hidro, nang luyng cia eae AO ehi phy thude vao so lung tirchinh n (15) Mire nding lugng dic trung béi n bi suy bién n? Min; mat khdc, E, ting khi n ting. ‘Trong hé nhiéu electron, su dua higu tg chin vao e6 hé qua IA ning luyng cia ham séng mot electron phu thudc vaon va (. ¥y bic cua nhng trang thai nang tuong cia cing gid trim va ( moi bj suy bign (vi Didu nay lam gidm bot su nguyen tir: chi nhung AO c du, 3 AO np hoac 5 AO nd) Chua 66 cong thie don gitin mio vé quan he gita ning lung cia cic AO va nhang sO lung tir, ¢. C6 hai quy tie kinh nghi¢m cho phép sp xép nang luyng cia céc AO so v6i nhaw * Trong mot Iép, ng! thi nang lugng ting : Ex.(1=0) < Exp (l= 1) 5 Egy = 0) < Egy (I= 1) < Egg (l= 2) 1a voi mot cho trunic ciia n,khi f ting © Voi mot gid tri cho true cia ¢, Khia ting thi ning lugng ting. Ej,(n =1) < Ep,(n = 2) < Ex(n =3) 5 Eqy(n=2) < Exp (= 3) < Egy (n=4) ‘Tuy nhién hai quy téc nay khong cho phép xép cc orbital theo thir ty ning, luyng tang dn, Vi dy, ching khong cho phép sip xép AO 2p va AO 38. Nhung thye nghiém cang chime t6 ring, doi voi moi nguyen wt, nam orbital v6i nang lugng thip nhat dye x€p theo thirty sau : Ey = z > ° HLS. Biéu dién AO bang 6 luong tit, Méi hinh vudng biéu thi mot orbital ; céc hinh vudng ké nhaw Khi cdc AO la suy bién nghita la cé cuing nding lugng.3 Spin cua electron 3.1. Spin cua mét hat Mot so sy kign thye nghigm va ly thuyét (phd vach eda kim loat kim (4.6), tht nghiem TERN va GERLACH (H.7), cOng tinh cba DIRAC trong Cor hoc lung tir tuong di tinh) da chumg 16 ring sirmo Ui trang thai ‘cia hat co bin bang mot ham sng chi lien quan dén wa dd khong gian khong cho phép gidi thich duye nhang hign tuyng d6. Vi vay phi chip nan ring nhang hat nay cdn c6 mot moment dong hoe nOi tai, duye gor 1 momen spin (hode chi goi dom gién 1a spin) SF, het nhur 1A n6 €6 Khoi Jugng hoge dign tich, chim nguyen tirbac cue ita nam cham dien tim thiy tinh Spin khong 6 dai lugng tuong duong trong Vat ly c6 dién nhumg ngudi ta chap nhan ring vecto S$ cang tuan theo cdc quy tic cla momen dong hoc orbital £ (xem ch.1 §2.1.4) : chi biét duye chudn va mot thanh phan cia nhang vecto nay va méi dai luyng déu bj Luyng trhéa. \j-vic+Da L. nhay mt don vi trong khoding -/ va +. US =ys+D.A S, =myh vi my thay d6i theo buse ms.h aay véi mg thay d6i theo buvc nhay mot don vi trong khodng -s va 4s. #5 duve goi la sO lugng tt spin ; n6 duye quyét dinh boi bin chat hat : 5 c6 thé a nguyén hoje bin nguyen, duung hoic bing khong (H.8). 5 0 12 1 aR electron, photon ; 1 gt | nhan 4He | proton, notron ; han 7H; ee 3 han °° han 3He han 4 4 fermion, HG. Phd phat xa ctut hot nari 6 hai vach vang cuimg do manh, fing vin hai bite xq 06 bude song ‘gd nha : 589.0 nan va $89.6 nm, Sue tén tai hai vach nay chi c6 the gidi thich la electron c6 momen dong hoc noi tai. H.7. Thé nghigm Stern va Gerlach (1922) Nguyen tir bac cO momen dong hoc orbital L bding khong va do 6 co momen tie bang khong ; le ra n6 phai khong chiu tac dung ita tie truaimg. Khi cho ching qua nam cham, nhang nguyen tte bac bi lech di ching 16 ching cO momen tit Hon niu, sau nhieu gio thé nghigm thay hai lop bac c6 kh6i luong bang nhau : diéu nay ching 10 nguyen tie bac cé mot monien tit bj lugng te hoa ma thanh phan trén truc z chi c6 thé 6 hai gid tri H.8, SO lugng tie spin s ca mot vai hat. Ninting hat c6 spin ban nguyén la nhimg hat c6 spin nguyén la boson. Tinh cach fermion cita electron c6 vai tro co ban trong cdu tric doan electron cia nguyén tt,ems due goi la 86 lwong té te spin ; ms quyét dinh hudng cla vecto § so voi trye = Chui thich_: Cang nh quan hé gitta momen orbital L va moment tit, nhtmg hat cé momen spin S khac khéng cing cé momen tit. Su kién nay la co 8 ctta hai phuomg phap phd nghiém la cong hutmg thuan tr electron (EPR) va cong hudng tir hat nhan (NMR). 3.2. Spin cua electron va ham séng Vi electron c6 spin bing 1/2 nén sO lugng tir spin m, chi c6 thé c6 hai gia tr +172 va -172. V phu thude ms (H.9). 4 nhu nhau di v6i moi electron nén vecto § chi Ham song mo ti tang thdi cia mdt electron qua toa dO khong gian va spin cita nd duye goi la spin-orbital : d6 la tich cia mot AO mot electron 7 Voi mOt ham spin. Vi chi c6 hai trang thai spin nén chi c6 hai ham rieng spin, thurg ki higu 1a va # tung tng voi m,= +1/2 va m,= -1/2. zduye xéc dinh béi ba sO luyng tir (n, é, my); ham spin duye xéc dinh chi béi mot sO luung tik m, + MOt spin-orbital duye hoan toan xe dinh khi biét ba sO luyng tir (7, £, my) vas6 luyng tir tirspin m,. 3.3 Nguyén ly loai trir Pauli Nhung hat c6 spin nguyen goi I boson. Nhamg hat ¢6 spin ban nguyen goi IA fermion. Hai loai hat nay c6 hanh vi tap thé khdc nhau vé co ban. Gia sir e6 he gdm N hat gidng het nhau. Hai trong s6 cdc hat nay, vi dy hat i va j, c6 thé cing 6 mOt trang théi duye khong ? Ly thuyét chimg 18 ring c6 thé c6 tinh thé nay d6i v6i céc boson. Nguge lai, cde fermion thi khong thé c6 Khong thé t6n tai mot hg fermion ¢6 hai hat 6 cong mot trang thai Electron (s = 1/2) a fermion ; vi vay trong cing mot he (nguyen tt, phan ti, tinh thé...) khOng thé cé hai electron & cing mot trang thai. ‘Trong khuOn khé gin ding mot electron trang thai cia m9t electron duye hoan toan xéc dinh khi biét spin—orbital cia no, Nhu vay sy ngan cdm trén c6 thé duye phat biéu nhu sau : Hai electron ciia cing mot hé (nguyén tty, phan ti, tinh thé, ...) khong, thé duye mo ta béi cing mot spin-orbital. Hai trang hop e6 thé xy ra : # NGu hai electron c6 cing him spin (nghia 1a c6 cing gid ti ms) thi ching phdi duye mo ti béi hai orbital khdc nhau, H.9. Ddc tinh cia momen spin S cua electron. Theo bat diing thite Heisenberg, chi cé WSU va Sz la c6 thé biét duoc déng thoi. hai gid tri £h/2. ‘hi c6 thé c6