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e 8. - E E P P E EP Mapooeya ocoa cpyypa ea oo ae ooe oeco aoo aox py. x eooe ee, oopo pae opy ex ce oycoa ooe co ypoeypx ceee coo, o pae apooeye cacece coca. Oopeeo o e apooeye ey aoa cyecy xece c, e ae aoec oopx pa oe opeee eepcc xapaep ee oopao epecpoa. Ta opao, ooeca apooeya oaae coeopa coca, ocoe oopx e ecoe aoece cacecx eepccx (exaecx) ceee coo. B pocx xecx poeccax pacopax poy pea oec cece ax coyape oey peaeo. B oe o oo peya yopoa apooey oxecx poeccax ocaec pee ceo cece aoec ace eoo aoo apooeypoo oeca. B x pacopo poc eepayp ae yeee o ax eecx coyape oey, a apooeypx oecax o e aop oe o a x cpyypy opaa e ca a exa eoc ypoeypx aoec. ax cce, cpoo oop, epeo oe xecoo oeaa a ye c poecca, ace o cxooo ca peaeo. B cyae apooeypx oeco pea opeeec e x co a ao, a ypoeyp aoec ao x. o xopoo o a pepe epeaoo aaa.

Ocoa aaa oeypo o coco o, o, cxo xapaepa aoec aox py, opeex opa apooey, pacp ppoy ee ypoeypo a. Ha o ocoe epee paccope epox coc ecx po yopoa apooey (eo) oxecx poeccax.

. oepa e, e aoecy oo cocee e, copaaec yo, oaa o co oopa, epexo ey oop pocxo poecce popoyocoo e ace e. Tao yo e oaae opeeeo ypee cpyypo, o a ce pe "", pe aya "oxa" opa paepo ya. Baoe pacooee oex ace ya ooc oec cacec aooepoc. Oao ec ec oee aoec ey aoa, aeo oco py o pya o e, o o cyeceo ee c apy. B peax apooeyax oee aoec eeo e coa ypeee oe, o ece oopoo opayec oya c oo cepeo. B oe o ya oya ye oaae opeeeo pocpaceo cpyypo. Cepea oo oy pocpaceo oopoa c ocoo oepae ee, oe o cpae c "oyo" oy (pc. 8.1). Teepaype epexo ey coco ya oy oopeeo c epexoa ey pa aa copooac ee Pc. 8.1. Pacpeeee ooapeaoo coco apooey.

c ee oye acB oapooeyax aoee ooc o pacco o epa poo poecc ye eax.

oy R payc oy, eoe oy peepea epen co ee xo opo ecopo ooceo ao epae eepayp aoa o ooe aoe epexo 1 o poa. B cepeax cceoax a aopepax peapay ea oo ooc eo c ocoo copoc p o pecppyec copoc oe eepayp ea. Oca oo a eoeoc ea p pax eepaypax. Oaaec o p eoo eaypa ea epexoax a opo ecopo pocxo oopeeo aeoe eee eo eoeoc ( C = 0,2 0,6 b1bK1). ee e oy a oo epec oyee ypoeypx ceee coo, a ceecy o cpyypx epecpoax cao apooeye.

ea xapaep x epecpoe eoo oye oo o, a opey ppoy oex aoec ee.

epa cpyypa oepo e opeeec xec ae aoec. Oee aoec ocoo opee opy cpyypy apooey. O pepe caoc oeypo cpyyp ec ae ya a po U(r) acoc ep aoec o pacco ey aoePc. 8.2. epo ep cy ac. Ha pc. 8.U(r) yxaoo oey peea pa U(r) c yo p r = r cyae yx ac (yxaoa oeya). Ha ax paccox peoaa c oaa, a a ox paccox peapye pee. p r = r c pe oaa ypaoea py pya. aee ep U(r) coox ac p r pao y, a ep opaoao cao cpyyp opaea U(r ) < 0. Ha ax paccox, e ac oaac, U(r) > 0. My U(r ) cooecye acao o acoo ee opaeo o ay ep aoec. B opaoa opo cpyyp ea pa oy po c Ba-ep-Baaca. O e epoay ppoy ca c aoece epecx oe cocex oeyax. Haoee pacpocpae cepcoe aoec ey oeya, oope e oaa oco o oea. ppoa x c oc aooexaec xapaep. ee epoa a aoo ac e oe ocao oo exaeco paeope, a ee "pa" xapaep. epo e oe oaa oopeeo cpoo opeee ae oopa (x) yca (p) (p = mv, poeee acc m a copoc v).

Heopeeeoc aex oopa x yca p ca coooee eopeeeoce xbp h (8.1) o a, o ocoo eoyeo coco cyecy cpe cee apa epoa o ooe paoec, a ceoaeo, oeye coco oo oc "oee" oe oe. oee aoo oea oo oeye ypye oee eo cocee oeye. Boae aoece yx cpoexc ox oeo, oope, a opao, caoc ca pac py pyy. ep pe yx oex oe, ep cepcooo aoec, cpo yae c paccoe U ~ (8.2) c poe cepcooo aoec ooo epocaecoe pee ey oco o opx oeyax. poe oo, cyecy ae yoe aoec, oope oa ey oco o oeo oo oeye aee oe cocee opyeo oeye.

Cyapoe a-ep-aacoo aoece yx oey ac o aa cex o ox aoec cocae o ee o 1,0 o ecox eco a/o. ox ooecx apooey ya epeecoo ya, coaaeoo a ce a-ep-aacooo pe, cocae 1 3 a/o, o o opy e cpao c eo eoo ep 0,a/o oey p oao eepaype (RT=2a.ʖ1 o1 300, =0,6 a.o1).

B pae oo ep ooo oeaa aoec a eoxoo yec e oo pee (U (r) ), o oaae a x paccox p r (U (r) ).

o r Coee x e ae A B U (r) =, (8.3) i,k ri k rik e A, B oca pe oaa, r paccoe ey i,k aoecy aoa (i k). p aax aex A B oo a aoe paccoe r ooee ya U(r ), a oopo ccea yx pax aoo eox aox py (CH, CH ) ycoa. Ta, ap aoo yepoa aoe 3 paccoe cocae 3,0 E, a H... H o ~ 2,0 E.

Hapy c ca Ba-ep-Baaca oy po caa ocpyyp pa oopoe c epocaece aoec ey ape op pya. Boopoe c, apep, capy opy cpyypy oex ee. B ep oopoo c a a epocaece aoec, pee oaae (8.3), a ae ep eoaa epoo. Be ep oopoo c co appy (3 8 a/o). Ta, oopoa c O-H... O oaae epe 8,6 a/o.

epocaece aoec aac opyo i U.ca qqk (8.4) =-, rik e q, q ap a aoax (i k), r paccoe ey aoa, i k i,k epeca ocoa ( eo ~ 3,5).

e aoe aee oopaoo cpyype apooey. ep x aoec aox py ac o pacco ey , oope co oepe ec p pae x py opy ex ce. p o pacooe aeo e cae ao aa oaac, oae opo epeec oea, pecy pae aox py. ep pae aox py opy ex ce ae ocoo a oy oopaoy ep oepo e.

Ha pc. 8.3 o, o oeya aa ee y oopaoo ep pacoopa acy coopa.

epeec apep, opo oea, epexoa oo Pc. 8.3. pa acoc oeao ep ypeeo pae ae o ya oopoa. ae yo 0, 120 .

. cooecy pac a 60, 180 .. coopa pacoopa pyy epe copy p oopoe opy C-C c a 120 pae~3 a/o. acoc oeaa ypeeo pae o ya oopoa aaec paee & U( )= (1 cos3 ), (8.5) e U coa apepa.

Oa oopaoa ep oepa ac o ax yo oopoo ee opy ex ce. ooa ccea, e ep cocax eeo ac o x aoec py c pyo, aaec ooepao.

opeeec ce a oex aoec ac o ep ypeeo pae oox ee aocox ocao opy ex ce. Oee cpoee oeo e pecaeo a pc. 8.4. a aec a ep , paee oox py oe pocxo opy cex ex ce: N C a yo, C C, a Pc. 8.4. Oee cpoee oeo e yo, Ci Ni+1 a yo. B o cyae aoe e ee p i i ee x ooe oe epeaac o e epe ooe co ce, oa a x oy oopaoy ep pyo yec. Oao a cao ee oo xapaep eo c C iO-Ni+ H pecye pae opy ee. O oycoe ooecee eoeeo ap 2 S2 epoo aoa aoa ey aoo yepoo. Bcece oo pocxo aae epoa yepoa oo c C=O oaa eo a copoe c ac pepaee c C=O ooy eoaa epoo ey aoa N, C, O po oy, o ea pya acao capyec, oa ee ao, a yepoe ao cocex aoco, pacooe oo ococ. ooy paee opy eo c C i=Ni +apyeo cy ee ooo xapaepa. M oe eep ya oo paee opy ce Ni C i (yo ) C i Ci (yo ), a i i a ao e ocycy cepece epep aoo ei o e c ( +2) ( 2) ea. coa, i i eo e ee eco oo oapoe ooepaoe aoece p pae opy ex ce, paeax ooy oy e yepooy aoy. aa apa yo ( ) oe i i paccapac eaco, a ooepaoc e aec opaaec aoece cocex ex e. oea ypeeo pae opy ex ce eca a ( 1,U a/o). Ceoaeo, y oex cpex coco, oax p ee yo , paee eco apepa. Oee paee oopaoo ep ee U U (, ) = (, )+ (1 cos 3 ) + (1cos3 )+ (8.6) U U i,k .ca U 2 e (, ) opeeec oeao (8.3) c paccoe, acU r i,k i,k o yo . aaec opyo (8.4). o poeeo U .ca opeeee oopaoo ep (8.6) pocex ocao eao N ae aoco (CH CONH CHR CONH CH ), e paa ooo e aocooo ocaa.

3 R Ha pc. 8.5 pecaea apaa oepxoc oopaoo ep y yo oey N ae L aaa.

B epe oac o ep c eyo ya 1 a/o. ae pacea cpyyp coaa c py cepea peyaa. Ta opao, oopa pocex paeo oeo e oe aea ye pacea.

oo eoxoo a xecy oceoaeoc aocox ocao oca ep eaex aoec x aoo aox py o opye (8.6). Haea peyae oopa aaec e opex ae yo oopoa aox py cooecyx pacco ey , p oopx oopaoa cyapa ep, aca o cex o oex aoec, ocae ax ae.

Pc. 8.5. apaa oeao oepxoc oey eaa N ae L aaa. p yaa ep oopa /o aeo oe co ocao, e oe aea a ye -a ox aeaecx pyoce. B o cyae ye e eocpeceo pacca opy e oee pey cpyypy ox yaco ea, a epy oceoaeoc. pee o poe ceac oyc pec eoo, oop ocoa a oocex cepeax ax o oppe ey opo cpyypo yaca ea eo epo aocoo oceoaeoc. Ha ocoa x oppe copypoa pcece p pocpaceoo cpoe ea paa copaa eo e c opaoae opo peo cpyyp.

Oa oopa eoo oy opeeec e, o ope py pacooe ocoo a oepxoc, a eope axoc yp oy opay ee poooe po. Ha oepxocx ocox eeo opo cpyyp cpae cpyyp ae ec ee pooe oac. BypoeyPc. 8.6. epapx cpyyp ea oceoaeoc eo copaa pe oopoe c ey e pya acao ace capy oyy.

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