Trn Minh Hng

Bi ging Ha i cng

Chng III. LIN KT HA HC V CU TO PHN T

I. NHNG KHI NIM C BN V LIN KT HA HC L thuyt v lin kt ha hc l mt trong nhng vn trung tm ca ha hc hin i v c bit c bn cht tng tc gia cc tiu phn, ngha l bit c lin kt ha hc to thnh gia cc tiu phn trong tng tc th mi hiu c nhng vn c bn ca ha hc nh: tnh a dng ca vt cht, c ch to thnh, thnh phn, cu to v kh nng phn ng ca chng. 1. Bn cht lin kt: lin kt ha hc c bn cht in v c s to thnh lin kt l lc ht gia cc ht mang in (e, ht nhn)

- Trong cc tng tc ha hc ch c cc e ca nhng phn lp ngoi cng: ns, np, (n - 1)d v (n - 2)f thc hin lin kt: l cc e ha tr - Theo c hc lng t, nghin cu lin kt l nghin cu s phn b mt e trong trng ht nhn ca cc nguyn t to nn nguyn t. 2. Cc loi lin kt Lin kt ni phn t - Lin kt ion: xut hin gia kim loi in hnh (kim loi kim, kim th) v phi kim in hnh (F, O, Cl, Br, I). > 1,7 - Lin kt cng ha tr: xut hin gia cc phi kim vi nhau hoc gia kim loi v phi kim, < 1,7 - Lin kt kim loi: xut hin gia cc kim loi vi nhau (hp kim) Lin kt lin phn t - Lin kt hydro - Lin kt Van Der Waals 3. Mt s c trng ca lin kt a. di lin kt (d, ): l khong cch gia hai ht nhn ca cc nguyn t tng tc di lin kt thay i ph thuc vo: kiu lin kt trng thi ha tr ca cc nguyn t tng tc bn hp cht b. Gc ha tr: l gc to bi hai on thng tng tng ni ht nhn nguyn t trung tm vi hai ht nhn nguyn t lin kt Gc ha tr ph thuc vo: bn cht nguyn t tng tc kiu hp cht

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Trn Minh Hng

Bi ging Ha i cng

dng hnh hc phn t (cu hnh khng gian ca phn t) c. Bc lin kt: l s lin kt to thnh gia hai nguyn t tng tc d. Nng lng lin kt, c trng cho bn lin kt: l nng lng cn tiu tn ph hy lin kt Nng lng lin kt ph thuc vo: di bi bn lin kt II. LIN KT CNG HA TR THEO C HC LNG T V vic gii chnh xc phng trnh sng Schrdinger i vi h phn t khng thc hin c nn kho st lin kt cng ha tr ngi ta a ra nhiu phng php gii gn ng khc nhau, trong c hai phng php c ph bin rng ri l phng php lin kt ha tr (VB) ca Heitler London v phng php orbital phn t (MO) ca Mullinken Hund. 1. Phng php orbital phn t (Molcular Orbital) a. Quan nim ca phng php MO Thuyt MO quan nim phn t ging nh mt nguyn t phc tp a nhn. Cc e chuyn ng quanh cc nht nhn. Phng php MO tm cch m t s chuyn ng ca tng e ring bit + b. Xt ion phn t H 2 - mt thi im bt k cc ht nhn v e c v tr tng i nh vy:
V tr tng i ca electron v hai ht nhn trong ion phn t hydro H+ 2

ra a
-

rb Rab b

Phng trnh sng Schrodinger:

2 2 2 8 2 m + + + ( E V ) = 0 x 2 y 2 z 2 h2

e2 e2 e2 1 V= R ab ra rb 4 0 xc nh hm sng H + , Mulliken v Hund tm cch m t s

Th nng V:

chuyn ng ca tng electron trong phn t: Khi electron nm gn ht nhn a hn, coi nh electron ch b a ht. Lc s chuyn ng ca e c m t bng hm sng ca nguyn t Ha: a = chuyn ng ca e c m t bng hm sng ca nguyn t Hb: b =
+ 2

1 ra e 1 rb e

Khi electron nm gn ht nhn b hn, coi nh electron ch b b ht. Lc s

H = C1 a + C 2 b Mt cch gn ng: hm sng ca ion phn t H + 2 : Th H vo phng trnh sng Schrdinger. Gii phng trnh c 2 p s: c1 = c2 = CS c1 = - c2 = CA
2

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Trn Minh Hng

H :
+ 2

Bi ging Ha i cng

C 2 hm sng c trng cho s chuyn ng ca cc e trong ion phn t

S = C S ( a1 b 2 + a 2 b1 ) A = C A ( a1 b 2 a 2 b1 )

- hm i xng - hm bt i xng

V phng din vt l: S tng ng vi trng hp mt electron tng ln trong vng khng gian gia hai ht nhn v phn ln m my electron tp trung gia hai ht nhn lc ht xut hin lin kt hnh thnh A tng ng vi trng hp xc sut c mt electron trn mt phng i xng bng khng, ngha l m y electron khng tp trung gia hai ht nhn lc y xut hin lin kt khng hnh thnh. c. Ni dung ca phng php MO Theo thuyt MO th phn t phi c xem l mt ht thng nht bao gm cc ht nhn v cc e ca cc nguyn t tng tc. Trong mi electron s chuyn ng trong in trng do cc ht nhn v cc electron cn li gy ra. Tng t nh trong nguyn t, trng thi ca electron trong phn t c xc nh bng cc OM. Mi mt MO cng c xc nh bng t hp cc s lng t n, l, ml l 0 1 2 3 AO trong nguyn t s p d f MO trong phn t Cc MO khc nhau bi s phn b mt electron tng i so vi trc lin nhn: - dc theo trc ni ht nhn - nm v hai pha trc ni ht nhn Cc MO c hnh thnh do s t hp tuyn tnh (cng hay tr) cc AO (tc l s xen ph) S t hp cng (t hp cng du) cc AO s to thnh cc MO lin kt, c biu din bng hm sng S (, ) c nng lng nh hn nng lng ca cc AO tham gia t hp S t hp tr ( t hp khc du) cc AO s to thnh cc MO phn lin kt, c biu din bng hm sng A (* ,* ) c nng lng ln hn nng lng ca cc AO tham gia t hp MO khng lin kt (0, 0 ) do cc AO chuyn nguyn vn m thnh. Cc MO ny khng nh hng ti lin kt. Nng lng ca cc MO khng lin kt bng nng lng ca cc AO to thnh n.

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Trn Minh Hng

Bi ging Ha i cng

S MO to thnh bng tng s AO tham gia t hp S to thnh cc MO t cc AO c th biu din bng gin nng lng

iu kin t hp: cc AO tham gia t hp phi: gn nhau v nng lng c mt electron ng k c tnh i xng i vi trc ni ht nhn ging nhau S phn b e trn cc MO cng tng t nh trong nguyn t, tun theo cc nguyn l ngoi tr, vng bn ca Paouli v quy tc Hund Cc c trng lin kt: Lin kt c quyt nh bi cc e lin kt (e nm trn cc MO lin kt) m khng b trit tiu.
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Trn Minh Hng

Bi ging Ha i cng

C mt cp e lin kt b trit tiu bi mt cp e phn lin kt tng ng Mt bc lin kt ng vi mt cp e lin kt khng b trit tiu Cho lin kt 2 tm:
BLK =

lk

Bc lin kt tng th nng lng lin kt tng cn di lin kt gim Tn ca lin kt c gi bng tn ca cp e lin kt khng b trit tiu Tm li: vic m t cu trc phn t gm cc bc: Bc 1: Xt s to thnh MO t cc AO Bc 2: Sp xp cc MO to thnh theo th t nng lng tng dn Bc 3: Xp cc e vo cc MO Bc 4: Xt cc c trng lin kt d. p dng phng php MO cho cc phn t bc hai Cc phn t hai nguyn t ca nhng nguyn t chu k I

Cc phn t hai nguyn t ca nhng nguyn t chu k II

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Trn Minh Hng

Bi ging Ha i cng

* 2 pz
2 p x , 2 p y

2 p z

2 p x , 2 p y
2s

2S

Cc phn t hai nguyn t cng loi ca cc nguyn t u chu k II + Phn t, ion Li2 Be2 B2 C2 N2 N2 Tng s e ha tr 2 4 6 8 10 11 2 p
z

2px

, 2py

Bc lin kt 1 di lin kt () 2,67 Nng lng lk (kJ/mol) 105 T tnh nghch t

2s

Gin u chu k

2 p z
2 p x , 2 p y
2S

1 2 3 2,5 1,59 1,24 1,10 1,12 289 599 940 828 thun t nghch t nghch t thun t

Cc phn t hai nguyn t cng loi ca nhng nguyn t cui chu k II + O2 F2 Ne2 Phn t, ion O2 O2 F2
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Trn Minh Hng

Bi ging Ha i cng
2pz

Tng s e ha tr

2px
x

11

12

13

14

15

16 0

2 p , 2 p Gin 2 p cui chu k 2s 2S Bc lin kt 2,5 2 1,5 1 0,5 di lin kt () 1,12 1,21 1,26 1,41 Nng lng lk (kJ/mol) 629 494 328 154 T tnh thun t thun t thun t nghch t thun t
, 2p y
y

Cc phn t hai nguyn t khc loi ca nhng nguyn t chu k II Cc MO to thnh tng t trng hp phn t 2 nguyn t cng loi chu k II: - Khi c hai nguyn t l nguyn t cui chu k: to gin cui chu k - Trong cc trng hp cn li: to gin u chu k Do cc nguyn t tng tc khc nhau v m in nn: - AO ca nguyn t dng in hn s gp ch yu vo MO phn lin kt - AO ca nguyn t m in hn s gp ch yu vo MO lin kt

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Trn Minh Hng

Bi ging Ha i cng

Phn t, ion Tng s e ha tr

2pz

N2 10

CO 10

CN 10

NO+ 10 3 1,06 1051 nghch t

Gin u chu k

2 p x , 2 p y

2 p z
2 p x , 2 p y

2s

2S

Bc lin kt di lin kt () Nng lng lk (kJ/mol) T tnh

3 1,10 940 nghch t

3 1,13 1076 nghch t

3 1,14 1004 nghch t

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Trn Minh Hng

Bi ging Ha i cng

e. Nhn xt Khi thm e trn cc MO lin kt s lm bc lin kt tng lin kt s bn hn Khi thm e vo cc MO phn lin kt s lm bc lin kt gim lin kt s km bn hn Khi thm e vo MO khng lin kt, bc lin kt khng thay i u im ca phng php MO + Gii thch c s tn ti ca H 2 v s khng tn ti ca Be2, Ne2 Gii thch c tnh thun t ca O2 (Cc phn t cha e c thn th thun t, cc phn t khng c cha e c thn th nghch t) Gii thch c mu sc ca cc cht: l do s hp thu c chn lc ca cht vi cc tia vng quang ph nh sng thy c. Chnh s hp thu c chn lc khi b kch thch ny ca cc phn t lm cho cc cht c mu sc (l t hp ca cc tia sng cn li khng b hp th) khc nhau Nhc im ca phng php MO: kh 2. Phng php lin kt ha tr (VB Valence Bond) a. Quan nim v lin kt cng ha tr theo phng php VB V d: Phn t H2 - mt thi im bt k cc ht nhn v cc e c v tr tng i nh vy:
1

r12 ra2 rb1

ra1

rb2 Rab b

V tr tng i ca cc electron v ht nhn trong phn t hydro

a
-

Phng trnh sng Schrodinger:

2 2 2 8 2 m + + + ( E V ) = 0 x 2 y 2 z 2 h2

Th nng V:

e2 e2 e2 e2 e2 e2 1 V = + R ab r12 ra1 ra 2 rb1 rb 2 4 0

- xc nh hm sng , Heitler v London l lun: Khi hai nguyn t xa nhau v cng, thc t ch cn ch ti tng tc gia e v ht nhn ca tng nguyn t. Lc s chuyn ng ca e c m t bng hm sng ca nguyn t Ha1 : Ca nguyn t Hb2:
1 ra 1 e 1 rb 2 b 2 = e phn t H2: = a1 b2 a1 =

Mt cch gn ng: hm sng ca Khi hai nguyn t H tin li gn nhau: e1 gn ht nhn b, e2 gn ht nhn a hm sng c b sung thm i lng:
'= a2 b1

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Trn Minh Hng

2

Bi ging Ha i cng

Mt cch gn ng: H = c1 a1b 2 + c 2 a 2 b1 Th H vo phng trnh sng Schrodinger. Gii phng trnh c 2 p s: c1 = c2 = CS c1 = - c2 = CA C 2 hm sng c trng cho s chuyn ng ca cc e trong phn t H2: S = C S ( a1 b 2 + a 2 b1 ) - hm i xng ( ) A = C A a1 b 2 a 2 b1 - hm bt i xng V phng din vt l: S - ng vi trng hp 2e ca H2 c spin ngc du: mt e tng ln trong vng khng gian gia hai ht nhn lc ht xut hin lin kt hnh thnh A - ng vi trng hp 2e ca H2 c spin cng du: mt e gim xung = 0 trong vng khng gian gia hai ht nhn lc y xut hin lin kt khng hnh thnh Lin kt gia cc nguyn t H c to thnh nh trn gi l lin kt cng ha tr. b. Ni dung c bn ca phng php VB v lin kt cng ha tr: Lin kt cng ha tr c s trn cp e ghp i c spin ngc du v thuc v ng thi c hai nguyn t tng tc (lin kt 2e 2 tm) Lin kt cng ha tr c hnh thnh do s xen ph ln nhau gia cc AO ha tr ca cc nguyn t tng tc (s t hp tuyn tnh cc hm sng nguyn t) Mc v kt qu xen ph ph thuc vo du ca cc AO: Xen ph dng: nu trong vng xen ph cc hm sng c du ging nhau xut hin lc ht gia cc ht nhn v cc electron lin kt hnh thnh Xen ph m: nu trong vng xen ph cc hm sng c du ngc nhau xut hin lc dy gia cc ht nhn lin kt khng hnh thnh Xen ph khng: khng xut hin c lc ht cng nh lc y lin kt khng hnh thnh Lin kt cng ha tr cng bn khi mt xen ph ca cc AO cng ln. V xen ph ph thuc vo kch thc, hnh dng ca cc AO v hng xen ph ca chng tnh cht c trng ca lin kt cng ha tr l: bo ha, nh hng v phn cc. iu kin to lin kt cng ha tr: Nng lng ca cc AO tham gia xen ph phi xp x nhau Cc AO tham gia xen ph phi c mt e ln Cc AO tham gia xen ph phi cng tnh nh hng Biu dim lin kt cng ha tr: H : H hoc H H c. Cc loi lin kt cng ha tr v bc lin kt Cc loi lin kt cng ha tr: ty thuc vo cch xen ph ca cc AO, tnh i xng tng i so vi ng ni cc ht nhn m ngi ta chia ra cc kiu lin kt , ,
2

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Trn Minh Hng

Bi ging Ha i cng

Lin kt cng ha tr : c hnh thnh do s che ph ca cc AO

dc theo trc ni hai ht nhn z. C th xut hin gia tt c cc loi AO: s s, pz pz, s pz, s d z , pz d z
2 2

Lin kt cng ha tr : c hnh thnh do s che ph ca cc AO v hai bn ca trc ni hai ht nhn z. Trng hp ny tng ng vi s che ph px px, py py, dxz dxz, dyz dyz, px dxz, py - dyz Do mt che ph thng nh hn nn lin kt thng km bn hn .

Lin kt cng ha tr : hnh thnh do 2 AO d nm trong hai mt phng song song che ph ln nhau theo c 4 cnh hoa. Trng hp ny tng ng vi s che ph dxy - dxy

Bc lin kt: lin kt n: bc 1 lin kt i: bc 2 lin kt ba: bc 3 Bc lin kt c th l s l khi c mt lin kt di ng V d: Cl2 bc lin kt = 1,13 C6H6 bc lin kt = 1,5

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Trn Minh Hng

Bi ging Ha i cng

d. Cc tnh cht ca lin kt cng ha tr Kh nng to lin kt v tnh bo ha ca lin kt cng ha tr Da vo c ch to lin kt ta c th bit c kh nng to lin kt cng ha tr ca mt nguyn t. C 2 c ch to lin kt: C ch ghp i: lin kt cng ha tr c hnh thnh do s xen ph ca 2 AO ha tr cha e c thn ca 2 nguyn t tng tc. Kh nng to lin kt cng ha tr theo c ch ghp i c quyt nh bi s AO cha e c thn Ch : s AO cha e c thn c th tng ln do kch thch: V d: C 2s22p2 C* 2s12p3 C ch gp chung: lin kt cng ha tr c hnh thnh do mt nguyn t tng tc a ra cp e ha tr t do, cn nguyn t kia nhn ly. Kh nng to lin kt cng ha tr theo c ch cho - nhn c quyt nh bi s AO trng v s AO cha cp electron ghp i Kh nng to lin kt cng ha tr ni chung (theo c hai c ch gp chung v cho nhn) c quyt nh bi s AO ha tr ni chung (AO trng, AO cha electron c thn v AO cha cp electron ghp i) Tnh bo ha ca lin kt cng ha tr: V mi nguyn t ha hc ch c mt s gii hn AO ha tr nn ch c kh nng to s gii hn lin kt cng ha tr. l tnh bo ha ca lin kt cng ha tr. V d: Cc nguyn t chu k I c 1AO ha tr to ti a 1 lin kt cng ha tr. Cc nguyn t chu k II c 4AO ha tr to ti a 4 lin kt cng ha tr. Cc nguyn t chu k III c 9AO ha tr to ti a 9 lin kt cng ha tr. Tnh nh hng v s lai ha cc AO Tnh nh hng v cu hnh khng gian ca phn t - Lin kt c phn b theo phng ti s xen ph ca cc AO l ln nht - Lin kt s bn nht khi mt xen ph cc AO l ln nht Cc lin kt to thnh c hng nht nh phn t c cu hnh khng gian xc nh. - V d: H2Se Se: 4s24p4
y 1s

4px

1s

H Se 4pz 26

Gc lin kt = 900

Trn Minh Hng

Bi ging Ha i cng

Thuyt lai ha cc AO tng mt xen ph, khi to lin kt nguyn t dng cc AO lai ha thay th cho cc AO thun ty s, p, d, f. Cc AO lai ha to thnh do s xen ph ca cc AO trong ni b nguyn t. c im ca cc Aolai ha: S Aolai ha to thnh = s AO tham gia lai ha Nng lng bng nhau Phn b i xng trong khng gian phn t bn hn Hnh dng: ging nhau: mt e dn v mt pha mt xen ph tng lin kt bn hn

iu kin lai ha bn Nng lng ca cc AO tham gia lai ha xp x nhau Mt e ca cc AO tham gia lai ha ln Lin kt to thnh bn Trong mt chu k: Ens - np: kh nng lai ha Li Be B C N O F Ne E2s 2p (eV) 1.9 2.8 5.7 8.1 11.4 18.9 22.6 26.8 Trong mt phn nhm: kch thc nguyn t mt electron gim kh nng lai ha Cc kiu lai ha thng gp: Dng lai ha Nguyn t trung tm sp sp2 sp3

V d

C2H2 BH3 CH4

V d:

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Trn Minh Hng

Bi ging Ha i cng

V:

D on trng thi lai ha ca nguyn t trung tm A trong phn t ABn y = 2 A trng thi LH sp gc LH 1800 x y = +n y = 3 A trng thi LH sp2 gc LH 1200 2 y = 4 A trng thi LH sp3 gc LH 109028 y - S cp e trn lai ha = S AOLH = s AO t do + s AO lin kt x - s e ha tr t do = STT nhm - s OXH ca A n s AO lin kt = s phi t B Ch : + trong cng thc ny coi B lun nhn s OXH m; + trong cc hp cht hu c: C+4 S lin kt to thnh trong phn t ABn Nu A l nguyn t chu k II: dng quy tc bt t xt s to thnh lin kt Nu A l nguyn t chu k III: s lin kt = s OXH n
Bc phn ng:
B=

D on cu hnh khng gian ca phn t i vi cc phn t ABn khng c cha AOLH t do: Gc lk = gc LH
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Trn Minh Hng

Bi ging Ha i cng

i vi cc phn t ABn c AOLH t do: - Hiu ng y ca t do > ca LK > ca - Nu A < B: m my e nm lch v pha B gc d b thu hp hn - Nu A > B: m my e nm lch v pha A gc kh b thu hp hn Kiu lai ha ca Dng phn t Cu hnh khng Gc lin kt nguyn t trung tm gian ca phn t sp AB2 ng thng 1800 sp2 AB3 Tam gic phng 1200 AB2 Gc 1200 AB4 T din 109028 sp3 AB3 Thp tam gic 109028 AB2 Gc 109028 Tnh phn cc ca lin kt cng ha tr m my e lin kt phn b gia 2 ht nhn nguyn t: - Khi 2 nguyn t tng tc ging nhau: m my e phn b i xng gia 2 ht nhn lin kt khng phn cc (ng cc) - Khi 2 nguyn t tng tc khc nhau: m my e phn b bt i xng gia 2 ht nhn lin kt b phn cc (d cc): + m my e lch v pha nguyn t c m in ln hn nguyn t b phn cc m + Nguyn t kia s b phn cc dng C th ni: lin kt cng ha tr c cc c mt phn tnh ion. AB AB AB A = B A < B A << B Lk cht khng cc lk cht c cc lk ion e. Nhn xt v phng php VB Phng php VB gii quyt c mt s vn ca lin kt cng ha tr Kh nng to lin kt cng ha tr Cc c trng ca lin kt Gii thch c cu trc v tnh cht ca nhiu phn t D hnh dung Nhc im ca phng php VB: cha c tng qut, cn nhiu hin tng thc nghim khng th gii thch c bng phng php ny: Tnh thun t ca O2 + S tn ti kh bn ca ion phn t H 2 Mu sc, quang ph ca phn t 3. So snh thuyt VB v MO Khi gii gn ng phng trnh sng Schroedinger, 2 phng php xut pht t lun im c bn khc nhau: VB: m t s chuyn ng ng thi ca cp e MO: m t s chuyn ng ca tng e ring bit. Ging nhau lin kt 2 tm: C 2 thuyt u dn n s phn b e trong phn t ging nhau. to thnh lin kt cng ha tr phi c mt e gia 2 ht nhn nguyn t
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Trn Minh Hng

Bi ging Ha i cng

to thnh lin kt cc AO phi xen ph nhau. Cch phn bit lin kt v ging nhau u im ca VB so vi MO: m t phn t mt cch c th: Cho php dng khi nim ho tr quen thuc Biu din phn t bng cng thc cu to Thuyt VB tin li khi trnh by l thuyt Nhc im ca VB khng gii thch c mt s trng hp u im ca MO so vi VB: Tng qut hn: m t c lin kt ha hc trong mi phn t (k c lin kt kim loi) M t c trng thi kch thch ca phn t Gii thch c mu sc v quang ph ca phn t Nhc im ca MO: kh 4. Cc phn t cng ha tr v lng cc a. Phn t cng ha tr c cc v khng cc Phn t cng ha tr c cc l do s phn b mt e trong phn t gn vi nguyn t m in hn, lm cho nguyn t c m in ln hn s phn cc m v nguyn t kia phn cc dng. Phn t cng ha tr khng cc l phn t to thnh t cc nguyn t cng loi (N2, H2, O2) hoc phn t c tnh i xng trong khng gian (CO2, CH4, C6H6 ) b. Lng cc v moment lng cc Phn t c cc : xut hin lng cc in gm hai tm c in tch bng nhau nhng tri du (+, - ) , nm cch nhau mt khong gi l di lng cc Moment lng cc: l i lng vect c chiu quy c t cc dng n cc m = q = e . Thc t thng c o bng n v debye (D) Moment lng cc ca phn t l tng vect moment lng cc ca cc lin kt v cc cp electron ha tr t do Cc phn t c cu to i xng u c = 0

Phn t cng ha tr: = 0 4 D. cng ln phn t cng phn cc

mnh.

30