IAOe?IIAEUeIA AEAAeAI?ss IAOE OE?A?IE
?INOEOOO O?CEEE IAI?A?IA?AeIEE?A
EE?IIA AIAOIE?E IEAEN?EIAE*
OAeE 621.315.592
AeII?OEIA? OeAIO?E A OA?OAAOIIO NAEAI?Ae? AAE?TH,
EAAIAAIIIO AAAeIE?I??I
01.04.07 – o?ceea oaa?aeiai o?ea
AAOI?AOA?AO
aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy
eaiaeeaeaoa o?ceei-iaoaiaoe/ieo iaoe
Ee?a-1999
Aeena?oaoe??th ? ?oeiien.
?iaioa aeeiiaia a ?inoeooo? o?ceee iai?ai?ia?aeiee?a IAI Oe?a?ie
Iaoeiaee ea??aiee: aeieoi? o?c.-iao. iaoe,
?uaiei Noai?neaa Noaiaiiae/,
?inoeooo o?ceee iai?ai?ia?aeiee?a IAI Oe?a?ie,
i?ia?aeiee iaoeiaee ni?a?ia?oiee
Io?oe?ei? iiiiaioe: aeieoi? o?c.-iao. iaoe,
Eeoia/aiei Aiaoie?e Noaiaiiae/,
?inoeooo aaio?i??, i?ia?aeia?? oa ?oaeiooai?aiiy IAI Oe?a?ie,
caa?aeoaa/ a?aeae?eii ?aae?iniaeo?ineii??
aeieoi? o?c.-iao. iaoe,
Iioeiee Oaae?? Aaneeueiae/,
?inoeooo o?ceee iai?ai?ia?aeiee?a IAI Oe?a?ie, i?ia?aeiee iaoeiaee
ni?a?ia?oiee.
I?ia?aeia onoaiiaa: ?inoeooo i?iaeai iaoa??aeiciaanoaa IAI Oe?a?ie, i.
Ee?a.
Caoeno a?aeaoaeaoueny “ 26 ” aeiaoiy 1999 ?ieo i 1615 ia can?aeaii?
niaoe?ae?ciaaii? a/aii? ?aaee E26.199.01 a ?inoeooo? o?ceee
iai?ai?ia?aeiee?a IAI Oe?a?ie (i?iniaeo Iaoee, 45, 03028, Ee?a,
Oe?a?ia).
C aeena?oaoe??th iiaeia iciaeiieoeny a a?ae?ioaoe? ?inoeoooo o?ceee
iai?ai?ia?aeiee?a IAI Oe?a?ie (i?iniaeo Iaoee, 45, 03028, Ee?a,
Oe?a?ia).
Aaoi?aoa?ao ?ic?neaiee “ 25 ” aa?aniy 1999 ?ieo.
A.i. a/aiiai nae?aoa?y
Niaoe?ae?ciaaii? ?aaee Oaeaoaac? ?.A.
CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE
Aeooaeuei?noue oaie. Aeine?aeaeaiiy iecueeiaei??ieo no?oeoo?
neeaaeathoue o nueiaiaeaii? aaaeeeaee ?icae?e o?ceee oaa?aeiai o?ea.
Iaeiei c yne?aaeo i?aaenoaaiee?a oeueiai eeano niieoe ? oa?oaao?
e?enoaee, o yeeo niinoa??aa?oueny iecea iiaeo oe?eaaeo aoaeo?a ? ye?
ciaoiaeyoue oe?iea i?aeoe/ia canoinoaaiiy.
Oa?aeoa?iith iciaeith oa?oaaoeo e?enoae?a ? ai?cio?ii?y o?i?/ieo
ca’yce?a. ?i i?eoaiaii? neeuei? eiiii-eiaaeaioi? ca’ycee i?ae aoiiaie a
oa?ao ? neaae? Aai-aea?-Aaaeuen?anuee? ca’ycee i?ae oa?aie. Iayai?noue
oaei? ai?cio?ii?? ii?iaeaeo? iniaeeaino? oiiiiiiai niaeo?o,
niaoeeo?/i?noue aeaoaeoiooai?aiiy, oaee? ca?yaeiai? ? ni?iiai? aonoeie
oa ?io? iacae/aei? yaeua, aaaaoi c yeeo ia iiyniaii aei oeueiai /ano.
Ia iniia? oa?oaaoeo iai?ai?ia?aeieeiaeo e?enoae?a noai?ai?
ia?aoai?thaa/? na?oea, aeaiaioe aeey caieno ?ioi?iaoe??, aeoioeyoi?e
aeaeo?e/ii? aia?a??, oa?iiaeaeo?e/i? i?eno?i?.
?nio? aaaaoi ?ia?o i?enay/aieo aea/aiith o?ce/ieo aeanoeainoae oa?oaaoeo
e?enoae?a ??ciiiai?oieie iaoiaeaie. Iaeiae a?aeiiino? i?i aeii?oeia?
oeaio?e, ?o i?inoi?iaa iieiaeaiiy, aca?iiae??, no?oeoo?o ioi/aiiy,
oa?aeoa? eiiiainaoe?? ca?yaeo aeey oa?oaaoeo e?enoae?a aeineoue
iaiaaeai?. A oie aea /an oaea ?ioi?iaoe?y aaaeeeaa, a ?? iaea?aeaiiy ?
aeooaeueiith caaea/ath, ai o?ce/i? aeanoeaino? ?aaeueieo e?enoae?a ?
oa?aeoa?enoeee noai?aieo ia ?o iniia? i?eeaae?a nooo?ai caeaaeaoue a?ae
aeaoaeo?a e?enoae?/ii? a?aoee. Aiae?c e?oa?aoo?e na?ae/eoue, ui aeey
ae??oaiiy aeacaieo i?iaeai iaaeinoaoiuei aeei?enoai? iaoiaee
?aae?iniaeo?ineii??. Cie?aia, a?aenooi? aeine?aeaeaiiy c aeei?enoaiiyi
iiaea?eiiai aeaeo?iiii-yaea?iiai ?aciiaino (IAss?). Ana oea ? iaoiiaeei
oaio aeaii? aeena?oaoe?eii? ?iaioe – aeaoaeueia aea/aiiy aeii?oeiaeo
oeaio??a o oa?oaaoiio e?enoae? iaoiaeaie aeaeo?iiiiai ia?aiaai?oiiai
?aciiaino (AI?) ? IAss?.
Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie, ieaiaie, oaiaie.
Aeena?oaoe?ei? aeine?aeaeaiiy aeeiioaaeenue ca?aeii c ieaiaie
iaoeiai-aeine?aeieo ?ia?o a?aeae?eo ?aae?iniaeo?ineii?? ?inoeoooo o?ceee
iai?ai?ia?aeiee?a IAIO. ?acoeueoaoe io?eiai? i?e aeeiiaii? oai,
caoaa?aeaeaieo I?aceae??th IAI Oe?a?ie: “Aeine?aeaeaiiy iaoiaeaie
?aae?iniaeo?ineii?? eieaeueieo oa?aeoa?enoee aeaoaeo?a o
iai?ai?ia?aeieeao ? ae?aeaeo?eeao c iaoith oi?aae?iiy aeanoeainoyie
iaoa??ae?a ? iie?ioaiiy ?o oaoiieia??” (1986-1990 ?.), “Iia?
iaai?oii-?aciiaini? iaoiaee ? aeine?aeaeaiiy ia ?oi?e iniia?
aeanoeainoae ?a/iaeie” (1990-1994 ?.), “I?e?ioaeeueiaa niaeo?ineii?y
iiaeo ? ia?niaeoeaieo iaoa??ae?a” (1995-1999 ?.).
Iaoa ? caaea/? aeine?aeaeaiue.
Iaoa aeaii? ?iaioe iieyaa? a iaea?aeaii? ca aeiiiiiaith AI? ? IAss?
a?aeiiinoae i?i i?e?iaeo, no?oeoo?o oa aca?iiae?th aeii?oeiaeo oeaio??a
o oa?oaaoiio e?enoae? GaSe (oei A3B6) eaaiaaiiio aaaeie?i??i. Aea??
ia’?eoa aeine?aeaeaiiy aoa iaoiiaeaiee oei, ui GaSe ? iaea?eueo
oa?aeoa?iei i?aaenoaaieeii oa?oaaoeo e?enoae?a ? noaa ii noo?
iiaeaeueiei ia’?eoii o o?ceoe? oa?oaaoeo nenoai. A iueiio
niinoa??aathoueny iacae/aei? aieueo-aiia?i? caeaaeiino?, a?ae’?iia
oioii?ia?aei?noue, aiiiae?? oiiiiieo niaeo??a, iathoue i?noea
??ciiiai?oi? aeii?oeia? oeaio?e, ui oa?aeoa?i? ia o?eueee aeey oeueiai
e?enoaeo, a e acaaae? oa?oaaoei no?oeoo?ai.
I?e aeeiiaii? ?iaioe ae??ooaaeeny oae? caaea/?:
1. Iaea?aeaiiy niaeo??a AI? ? IAss? aeii?oeiaeo oeaio??a oa ?o
eiiieaen?a, aeine?aeaeaiiy eooiaeo caeaaeiinoae.
2. ?icoeo?iaea niaeo??a, ?o oai?aoe/iee iien, aecia/aiiy
?aae?iniaeo?ineii?/ieo ia?aiao??a.
3. Niinoa?aaeaiiy IAss? a ioeueiaeo iaai?oieo iieyo (aaciieueiaiai
IAss?). Aea/aiiy eiai iniaeeainoae oa ?ioi?iaoe?eieo iiaeeeainoae.
4. Aeine?aeaeaiiy oaiia?aoo?ieo caeaaeiinoae eiinoaio oiiei? no?oeoo?e,
ui oa?aeoa?ecothoue aca?iiae?th ni?i?a c e?enoae?/iei iieai, ?o
iiyniaiiy.
5. ?ic?iaea ia iniia? iaea?aeaieo aeaieo iiaeaeae aeii?oeiaeo oeaio??a,
anoaiiaeaiiy iniaeeainoae aeaoaeoiooai?aiiy, c’ynoaaiiy aieeao aeii?oe?a
ia oiiiii? niaeo?e.
Iaoeiaa iiaecia ?iaioe.
1. Aia?oa aeey aeine?aeaeaiiy oa?oaaoeo iai?ai?ia?aeieeiaeo e?enoae?a
canoiniaaii iaoiae IAss?. C eiai aeiiiiiaith anoaiiaeai? iiaeae? e
aecia/ai? oa?aeoa?enoeee 8 iiaeo oeaio??a a e?enoae? GaSe:Gd.
2. Aia?oa ca?a?no?iaaiee IAss? o ioeueiaeo iaai?oieo iieyo, aea/ai? eiai
iniaeeaino? oa ?ioi?iaoe?ei? iiaeeeaino?.
3. Iaea?aeai? iia? a?aeiiino? i?i aieea aeii?oie ia oiiiiiee niaeo?
oa?oaaoiai e?enoaeo, aia?oa aeyaeaii aoaeo eieaeueii? o?eia??caoe??
oa?oaaoi? no?oeoo?e.
I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a.
Io?eiai? a aeena?oaoe?? ?acoeueoaoe ?icoe?ththoue oyaeaiiy i?i
aeaoaeoiooai?aiiy o oa?oaaoeo e?enoaeao ? iiaeooue aooe aeei?enoaieie a
oaoiieia?? aeey iaea?aeaiiy e?enoae?a c caaeaieie aeanoeainoyie,
iaiao?aeieie aeey ?o i?aeoe/iiai aeei?enoaiiy. ?ic?iaeaiee iaoiae
aaciieueiaiai IAss? aaaeeeaee aeey ?icoe?aiiy iiaeeeainoae
aeine?aeaeaiiy oaa?aeio?eueieo ia’?eo?a iaoiaeaie iiaea?eieo ?aciiain?a.
A?i aeicaiey? iaea?aeaoe ?ioi?iaoe?th i?i ia?aiaai?oi? oeaio?e,
iaaeinooiio ?ioei iaoiaeai. ?acoeueoaoe aeena?oaoe?? iiaeooue aooe
aeei?enoaieie a ?aae?iniaeo?ineii?/ieo eaai?aoi??yo, a oaeiae a
oaoiieia?/ieo i?ae?icae?eao i?e ae?iuoaaii? oa eaaoaaii? oa?oaaoeo
e?enoae?a.
Iniaenoee aianie aaoi?a iieyaa? a i?aeaioiaoe? ? i?iaaaeaii?
aenia?eiaio?a, o/ano? a oai?aoe/iiio iien? niaeo??a AI? ? IAss?,
?ic?aooieao ia AII, ?ioa?i?aoaoe?? iaea?aeaieo ?acoeueoao?a.
Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??.
Iniiai? ?acoeueoaoe aeena?oaoe?? aeiiia?aeaeenue ia eiioa?aioe?yo:
I?eiaiaiea iaaieoiiai ?aciiaina a ia?iaeiii oicyenoaa (Eacaiue, 1988),
IX Ananithciia niaauaiea ii niaeo?ineiiee e?enoaeeia, aeoeae?iaaiiuo
eiiaie ?aaeeicaiaeueiuo e ia?aoiaeiuo iaoaeeia (Eaieia?aae, 1990), XXIV
Congress AMPERE (Poznan, 1988).
Ioae?eaoe??.
Iaoa??aee aeena?oaoe?? iioae?eiaai? a 8 ?iaioao: 5 noaooyo o iaoeiaeo
oaoiaeo aeo?iaeao ? 3 oacao eiioa?aioe?e.
No?oeoo?a oa ianya ?iaioe.
Aeena?oaoe?y neeaaea?oueny ?c anooio, /ioe?ueio ?icae?e?a, aeniiae?a oa
nieneo aeei?enoaieo aeaea?ae c 92 iaeiaioaaiue, aiia aeeeaaeaia ia 111
noi??ieao, aeeth/ath/e 23 ?enoiee ? 7 oaaeeoeue.
INIIAIEE CI?NO ?IAIOE
O anooi? aeaia caaaeueia oa?aeoa?enoeea ?iaioe. Iaa?oioiaaia
aeooaeuei?noue oaie aeena?oaoe??, noi?ioeueiaaia iaoa ?iaioe oa
caaaeaiiy, ye? iio??aii ae??oeoe aeey ?? aeinyaiaiiy, iaoeiaa iiaecia ?
i?aeoe/ia oe?ii?noue io?eiaieo ?acoeueoao?a, i?eaaaeai? iniiai?
iieiaeaiiy, ui aeiinyoueny ia caoeno, ei?ioei aeeeaaeaii ci?no
aeena?oaoe?? ii ?icae?eai.
Ia?oee ?icae?e ia? iaeyaeiaee oa?aeoa?. A iueiio ?icaeyiooi iniaeeaino?
no?oeoo?e ? aeanoeainoae oa?oaaoeo e?enoae?a oeio A3B6, aei yeeo
a?aeiineoueny GaSe, iaaaaeai? a?aoee e?enoae?a ??cieo iie?oei?a. Iienai?
iniiai? ?acoeueoaoe AI? aeine?aeaeaiue aeii?oeiaeo oeaio??a o oa?oaaoeo
e?enoaeao. ?aae?iniaeo?ineii?/i? ia?aiao?e, ui oa?aeoa?ecothoue oe?
oeaio?e, caaaeai? o oaaeeoe?. I?iaaaeaii aiae?c aenia?eiaioaeueieo
aeaieo. A?aei?/a?oueny ?o iaiiaiioa, a oaeiae oa, ui na?aae ?icaeyiooeo
?aae?iniaeo?ineii?/ieo ?ia?o, i?enay/aieo oa?oaaoei e?enoaeai, iaia?
aeiaeii? ?iaioe ii IAss?, yeee ? iaeiei c iaea?eueo aoaeoeaieo iaoiae?a
aeey anoaiiaeaiiy iiaeaeae oeaio??a. Oea a cia/i?e i??? ca?aeith?
?aae?iniaeo?ineii?/i? aeai?. Oae na?aae ieo a?aenooi? a?aeiiino? i?i
no?oeoo?o ioi/aiiy aeii?oie, eiiiainaoi?e ca?yaeo, eaaae?oiieueio
aca?iiae?th. C?iaeaii aeniiaie i?i iaiao?aei?noue ?icoe?aiiy
aeine?aeaeaiue oa?oaaoeo e?enoae?a ?aae?iniaeo?ineii?/ieie iaoiaeaie,
cie?aia iaoiaeii IAss?. Aeaco?oueny, ui ana oea a cia/i?e i???
noeioethaaei iinoaiiaeo caaea/? aeaii? aeena?oaoe?eii? ?iaioe.
Iaa?oioiao?oueny aea?? ia’?eoa aeine?aeaeaiue – e?enoaea GaSe, yeee ?
oeiiaei i?aaenoaaieeii oa?oaaoeo niieoe. Aeae? ?icaeyiooi o?ce/i? iniiae
IAss? oa ?ic?aooiee a?aeiia?aeieo aia?aaoe/ieo ??ai?a ? ?aciiainieo
/anoio.
Ae?oaee ?icae?e i?noeoue a nia? ?acoeueoaoe aeine?aeaeaiue niaeo??a AI?
? IAss? ainueie iiaeo ia?aiaai?oieo oeaio??a, ye? aeyaeai? a oa?oaaoiio
naeai?ae? aae?th, eaaiaaiiio aaaeie?i??i. Ia ii/aoeo ?icae?eo iienaia
iaoiaeeea ? oaoi?ea aenia?eiaio?a, cie?aia, aeiaeaoeia? i?eno?i?, a
?ic?iaoe? yeeo i?eeiaa o/anoue aaoi? aeena?oaoe??.
Ca?a?no?iaaiee niaeo? AI? GaSe:Gd neeaaeaany c aeae?eueeio aeanyoe?a
e?i?e, na?aae yeeo aoee aeae?eai? a?oie, ui i?iyaeyee naaa iiae?aiei
/eiii. Aeaoaeueia aea/aiiy eooiaeo oa oaiia?aoo?ieo caeaaeiinoae
niaeo??a, a oaeiae aei??e a 3ni ? 8ii ae?aiaciiao oa i?e ??cieo IA*
iiooaeiinoyo aeicaieeee ?aeaioeo?eoaaoe ?aciiaini? e?i?? ? aecia/eoe
?aae?iniaeo?ineii?/i? oa?aeoa?enoeee oeaio??a. Aeey oai?aoe/iiai iieno
AI? ? IAss? niaeo??a aoa canoiniaaiee ni?i-aai?eueoii?ai:
(1)
yeee a?aoiao? aeaeo?iiio oa yaea?io ca?iai?anuee? aca?iiae?? (g, gn),
aca?iiae?th ni?i?a c e?enoae?/iei iieai (b20, b40, b60), iaaeoiieo oa
eaaae?oiieueio aca?iiae?? (a, b, Q). O aeoaeeao aeacai? a?aeiia?aei?
eiinoaioe a caaaeueii i?eeiyoeo iicia/aiiyo. O?noue a?oi AI? e?i?e, ii
n?i e?i?e o eiaei?e, aoee a?aeianai? aei oeaio??a Gd3+ c? ni?iii S=7/2.
AI? oa?aeoa?enoeee oeeo oeaio??a iaaaaeai? o oaae.1.
Oaaeeoey 1. AI? ia?aiao?e oeaio??a Gd3+ a GaSe
Iiia?b20b40b60oeaio?ag10-4ni-111.989–2250.30.821.989–1790.60.731.989–191
0.30.841.989–2370.40.851.989–481–0.10.761.989–460–0.30.7Aeey c’ynoaaiiy
i?e/ei aaeeei? e?eueeino? oeaio??a, no?oeoo?e ?o ioi/aiiy, iieiaeaiiy a
e?enoaeaa?e a?aooe? oa aecia/aiiy iaaeoiieeo oa eaaae?oiieueieo
ia?aiao??a aoee i?iaaaeai? aeine?aeaeaiiy niaeo??a IAss?. Niaeo?e
neeaaeaeenue c neaiae?a a?ae yaea? Ga69 ? Ga71, Se77, Li7, Na23. Inoaii?
iaeaaeaee ?iiai Li+ oa Na+, ye? aeeiioaaee ?ieue eiiiainaoi??a ca?yaeo ?
aoiaeeee a e?enoae ye iaeiio?ieueiaai? aeii?oee. Anoaiiaeaii, ui
iniiaith on?o oeaio??a ? Gd3+, yeee cai?uo? a a?aooe? GaSe eiaaeaioii
ca’ycaio ia?o Ga24+. Aeey 4 oeaio??a eiiiainaoi?aie ca?yaeo neoaeeee Li+
aai Na+, ui ?ici?uoaaeenue o aaeeeiio (w) aai iaeiio (v) ii ia’?io
non?aeiueiio i?aeaoce?. Ua 2 oeaio?e iaee aeaeueith eiiiainaoe?th. IAss?
oa?aeoa?enoeee 4 cacia/aieo aeua oeaio??a i?aaenoaaeai? a oaae.2.
Oaaeeoey 2. Ia?aiao?e niaeo??a IAss? Gd3+ a GaSe
NOeaio?ssae?i|a|, eAoeb, eAoeQ,
eAoe1Liw+Gd3+wGa1695212759125Ga1’695102609970Ga21563Ga3938Ga4517Ga1c6904
410380Se7780380Li7758862Liv+Gd3+v Li723705143Naw+Gd3+w
Na2314332804Liw+Gd3+v Li7125886Nenoaia iicia/aiue oeaio??a a?aeiia?aea?
?en.1. Oeeo?iaee ?iaeaen aieco ioia?o? noa?e yaea? aae?th o na?aaeei?
oa?o (n – aeaco? ia iaeaaei?noue noa?e aei non?aeiueiai oa?o).
?icuaieaiiy 1 noa?e aae?th ia Ga1 ? Ga1′ iaoiiaeaia iayai?noth Li.
Iioeaee ia?aiao??a Li ? Na ia ia?aaeuothoue 2eAoe, Ga1,1′ – 5%, Ga2-Ga4
? Se – 50%.
A?aei?oeii, ui niaeo? IAss? neeaaeaany c aeae?eueeio nioaiue e?i?e.
sse?nii aoea iiyniaia i?e?iaea on?o e?i?e. E?euee?niee aea iien aoa
i?iaaaeaiee aeey niaeo??a, aea iaae?eii i?inoaaeoaaeenue eooia?
caeaaeiino?.
Aiae?c niaeo??a AI? ? IAss? aeicaieea anoaiiaeoe aeaoaeuei? iiaeae?
oeaio??a, ye? iaaaaeai? ia ?en.1.
?en.1. Iiaeae? aeii?oeiaeo oeaio??a o e?enoae? GaSe:Gd.
1 – Se, 2 – Ga, 3 – Gd, 4 – Li aai Na. a,a – cia?aaeaiiy iaeaeeae/iai
ioi/aiiy ?iia Gd3+; a,a – aeaa oeie oeaio??a o -iie?oei? i?e iayaiino?
eiiiainaoi?a ca?yaeo; ae – oeaio? o iie?oei?. Ai?eciioaeuei? oo?eoia?
e?i?? aeacothoue iaaeo oa?o.
E??i ?icaeyiooeo oanoe aeaoaeo?a o GaSe:Gd aoee ca?a?no?iaai? niaeo?e
aeaio iacae/aeieo ia?aiaai?oieo oeaio??a, ye?, ye aoei anoaiiaeaii,
neeaaeaeeny c ?iia Gd3+ (S1=7/2) ? eieae?ciaaii? iiaeeco iueiai ae??ee
(S2=1/2), ca’ycaieo iai?iiith aca?iiae??th. Niaeo?e AI? oeeo oeaio??a
yaeyee niaith aea? a?oie e?i?e, ye? a?aeiia?aeaee noaiai noia?iiai ni?io
S=S1+S2, a niaeo?e IAss? aoee iiae?ai? niaeo?ai cae/aeieo oeaio??a Gd3+,
aea c a?eueo neeueiith aca?iiae??th c yae?aie Se77. Ciaeaeaii, ui ae??ea
ia? ?aae?on noaio 9A. Niaeo?e AI? iai?iii ca’ycaieo oeaio??a iienai?
ni?i-aai?eueoii?aiii (1) aei yeiai aoea aeiaaaeaia iai?iia aca?iiae?y
J(S1S2)+J20(3S1zS2z-S1S2). Ia?aiao?e ni?i-aai?eueoii?aio iaaaaeaii a
oaae.3. Aeine?aeaeai? ? iiyniai? oaiia?aoo?i? oa iioe/i? ia?aoai?aiiy
oeaio??a. C aeaieo IAss? anoaiiaeaii, ui ni?iiaa aeaeo?iiia aonoeia
aeii?oeiaiai oeaio?o a oa?oaaoiio e?enoae? cina?aaeaeaia a na?aaeei?
oa?o ? ia? aeoyaiooo acaeiaae iueiai oi?io. I?e ae?iuoaaii? GaSe c
aaaeie?i??i a?aenooi?noue o aeo?aeieo iaoa??aeao eoaeieo iaoae?a
i?ecaiaeeoue aei iiaaii? ?ic/eiiino? aaaeie?i?y. Aeiaaaeith eoaeieo
iaoae?a iiaeia noeioethaaoe aoiaeaeaiiy aaaeie?i?y a e?enoae ? ooai?aiiy
oeaio??a iaaiiai oeio.
Oaaeeoey 3. Ia?aiao?e ni?iiaiai aai?eueoii?aio iai?iii ca’ycaieo
aeaoaeo?a a GaSe (bn0 ? J20 a 10-4 ni–1, J – a ni–1)
Ia?aiao?hvGd3+vhwGd3+w vGd3+v wGd3+w a?eueia
ae??eag1||=g11.9880.0021.9880.0011.989±0.0011.989±0.001b20–5181–4981–481
1–460±1b40–0.5±0.6–0.70.2–0.1±0.1–0.30.1b600.8±0.50.80.30.70.30.70.3g2||
1.82±0.01 1.820.01 1.86 g21.43±0.011.430.011.60J2012241264J–2±1–21h –
aeaco? ia iayai?noue ae??ee, aeey ii??aiyiiy iaaaaeai? ia?aiao?e
aiaeia?/ieo oeaio??a aac ae??ee oa a?eueii? ae??ee.
Iaea?aeai? a?aeiiino? a?aee?eaathoue iia? iiaeeeaino? ia?aaeaa/oaaiiai
aaaaeaiiy aeii?oie ? iaea?aeaiiy iaoa??aeo c iaaieie aeanoeainoyie.
O?ao?e ?icae?e i?enay/aii aea/aiith IAss?, eiee noaea iaai?oia iiea
aei??aith? ioeth – oae caaiee aaciieueiaee AI IssA?. Oeae aeae
iiaea?eiiai ?aciiaino aoei ca?a?no?iaaii ? aeine?aeaeaii aia?oa. Aeey
niinoa?aaeaiiy AI IAss? o?aaa uia aeeiioaaeanue oe?ea iecea oiia,
cie?aia uia ?icuaieaiiy aeaeo?iiieo ni?iiaeo ??ai?a a ioeueiaiio
iaai?oiiio iie? iiiaaeaei a IA* ae?aiacii, uia niinoa??aaany iane/aiee
aaciieueiaee AI?, a ?* i?aena?oea aoaeoeaii ci?iaea oea iane/aiiy. On?
oe? oiiae aaeaeiny ?aae?coaaoe ia oeaio?? vGd3+v a oa?oaaoiio e?enoae?
GaSe. A?aecia/eii, ui aeey oni?oiiai i?iaaaeaiiy aeine?ae?a i?eeoeiny
?ic?iaeoe ?yae oaoi?/ieo i?eno?i?a, oaeeo ye eioooee aeey eiiiainaoe??
caeeoeiaiai iiey aeaeo?iiaai?oo, i?eno??e aeey ?icoe?aiiy ?iai/iai
ae?aiaciio IA* ?aciiaoi?a oiui, a oaeiae aeeiiaoe aaeeeee ianya ?ia?o ii
i?aeai?o i???ioaoe?e ci?iieo iie?a oa noi?uaiith IA* eaaioa c ??cieoeath
aeaeo?iiieo ??ai?a iaaiiai ia?aoiaeo.
Niaeo? AI IAss? neeaaeaany c neaiae?a a?ae aeaaiaaeoeyoe yaea? Ga c?
ni?iii I=3/2, ui aoee ?icoaoiaai? a iaeiiio oa?? c Gd3+ ia iaeiaeiaeo
a?ae iueiai a?aenoaiyo (I eii?aeeiaoe?eia noa?a). I?e H=0 ?aciiaini?
/anoioe oeeo aeaaiaaeoeyoe yaea? ni?aiaaeaee. Aeey iieno niaeo?o AI
IAss? aoa aeei?enoaiee aoaeoeaiee ni?i-aai?eueoii?ai:
, n = 0, 1, 2, p = x, y, z, (2)
z||N||6, xm, y||2 (a?oia neiao??? e?enoaeo P6m2).
Iaaeoiie? Azp oa eaaae?oiieuei? qn2 ia?aiao?e aoee aecia/ai? ?c
ni?anoaaeaiiy oai??? ? aenia?eiaioo: Azz=370,70,2; Azx=375,5±1;
q02=7658±10; q22=1018±20; Azyq12q-220. ?en.2 ?ethno?o? yaea?i?
aia?aaoe/i? ??ai?, ?ic?aoiaai? ca?aeii c (2) ca aeiiiiiaith oai???
cao?aiue, oa aenia?eiaioaeueiee niaeo? aaciieueiaiai IAss?.
?en.2. Niaeo? AI IAss? oa aia?aaoe/i? ??ai? yaea? Ga69, ?icoaoiaaieo
iiaeeco Gd3+ a e?enoae? GaSe. m – yaea?ia eaaioiaa /enei, ui i?eeia?
cia/aiiy 1/2 ? 3/2. Oaiia?aoo?a aei???a T=4,2 K.
Ia a?aei?io a?ae cae/aeiiai IAss? a niaeo?? aaciieueiaiai iiaea?eiiai
?aciiaino niinoa??aaeanue aiiiaeueii aaeeea ?ioaineai?noue “caai?iiaieo”
ia?aoiae?a c m=2,±3. Oeae aoaeo iiaeia iiynieoe ci?ooaaiiyi noai?a
iaaeoiieith aca?iiae??th i?e cia/i?e eaaae?oiieuei?e aca?iiae?? ?
i?aeneeaiiyi ?ie? ?aeaenaoe?eieo i?ioean?a M=1, m=2,3 ii??aiyii c
i?ioeanaie M=1, m =1.
Aenia?eiaioaeueii ciaeaeaii, ui niaeo? AI IAss? ii?ioeo GaSe ?aeaioe/iee
niaeo?o a?ae iiiie?enoaeo. Oea i?aeoaa?aeaeo? aeniiaie, ui aaciieueiaee
IAss? iiaea aooe oni?oii canoiniaaiei aeey aea/aiiy iie?e?enoae?/ieo
nenoai, aeine?aeaeaiiy yeeo cae/aeiei IAss? cia/ii oneeaaeiai?
i???ioaoe?eiei ona?aaeiaiiyi niaeo??a. Na?aae ?ioeo ia?aaaa AI IAss? ye
iiaiai iaoiaeo ?aae?iniaeo?ineii?? a?aecia/eii ni?iuaiiy niaeo??a,
iieaaoaiiy oai?aoe/iiai iieno, iaea?aeaiiy ?ioi?iaoe?? i?i iaaeoiieo ?
eaaae?oiieueio aca?iiae?? o “/enoiio” aeaeyae?. Ca aeiiiiiaith
aeine?aeaeaiue aaciieueiaiai IAss? aoee aecia/ai? iaaeoiie? ?
eaaae?oiieuei? ia?aiao?e oeaio?o vGd3+v a GaSe, ye? ia aaeaeiny ciaeoe
niinoa?aaeaiiyi cae/aeiiai IAss?.
A /aoaa?oiio ?icae?e? iienai? ?acoeueoaoe aeine?aeaeaiue oaiia?aoo?ieo
caeaaeiinoae niaeo??a AI? aeii?oeiaeo oeaio??a, ca?a?no?iaaieo o
GaSe:Gd. sse c’ynoaaeiny, oaiia?aoo?i? ci?uaiiy ?aciiainieo iie?a aoee
iaoiiaeai? ci?iith aaee/eie eiinoaioe b20, ui oa?aeoa?eco? aca?iiae?th
ni?i?a c aeneaeueiei e?enoae?/iei iieai. Oiio caaea/a caiaeeeany aei
aea/aiiy ? iiyniaiiy caeaaeiinoae b20 (T).
C iiia?aaei?o ?ia?o a?aeiii, ui o oa?oaaoeo e?enoaeao niinoa??aa?oueny
iacae/aeieo o?ae e?eaeo b20 (T). Aiiiae?y iieyaa? o iaaei??iiio
caoyaoaaii? e?i?eiiai o/anoea e?eai? a iaeanoue iecueeeo oaiia?aoo?
(cia/ii ieae/a oaiia?aoo?e Aeaaay D). Aoaeo iiyniaii iayai?noth o
oiiiiiiio niaeo?? oa?oaaoiai e?enoaeo iecueei/anoioieo eieeaaiue,
iia’ycaieo c neaaeeie ca’yceaie i?ae oa?aie. Iaie a oa?oaaoiio e?enoae?
GaSe ciaeaeaii ia?aiaai?oi? oeaio?e Gd3+, o yeeo eiiiainaoi?aie ca?yaeo
aoee ?iie Li+ aai Na+, ?icoaoiaai? o i?aeoa?iaiio i?inoi?? (aeea.
?icae.2). Ine?eueee i?e oaeiio ?icoaooaaii? Li+ ? Na+ “ooioothoue”
i?aeoa?iao aca?iiae?th, nooo?ai aieeaath/e ia iecueei/anoioi? iioe/i?
eieeaaiiy, oe?eaai aoei aeine?aeeoe ci?ie o oaiia?aoo?ieo caeaaeiinoyo
b20 (T) a oeueiio aeiaaeeo. ?acoeueoaoe oaiia?aoo?ieo aeine?aeaeaiue
iaaaaeai? ia ?en.3.
Aeey oai?aoe/iiai iieno e?eaeo 1 ? 2, ye? iaeaaeaoue oeaio?ai Gd3+,
anioe?eiaaiei c Li+, aoei aeei?enoaii ae?ac:
b20(T)=b02(0)+b02(1)-1cth(/2kT), (3)
aea – /anoioa iecueei/anoioiiai iioe/iiai eieeaaiiy, ui iaea?eueo
nooo?ai aieeaa? ia eiinoaioo b20 ? i?ecaiaeeoue aei aiiiae?e o
oaiia?aoo?ieo caeaaeiinoyo; b02(0) ? b02(1) – ia?aiao?e, ui caeaaeaoue
a?ae i?e?iaee oeaio?o oa eiai aca?iiae?? c e?enoae?/iei iieai ?
oiiiiaie.
?en.3. Oaiia?aoo?i? caeaaeiino? eiinoaioe b20 aeii?oeiaeo oeaio??a a
GaSe:Gd oa iiaeae?, ye? iiyniththoue aieea ??cieo oeaio??a ia
iecueei/anoioi? iioe/i? eieeaaiiy E”. Nooe?euei? e?i?? 1,2 ?ic?aoiaai?
ca?aeii c ae?acii (3), oi/ee – aenia?eiaioaeuei? aeai?. 1–Liw+Gd3+w, 2–
Liv+Gd3+v, 3– Naw+Gd3+w.
Aenia?eiaioaeuei? oaiia?aoo?i? caeaaeiino? 1,2 caaeia?eueii iienothoueny
ae?acii (3) i?e ne?aeoth/eo cia/aiiyo ia?aiao??a:
Liw+Gd3+w: b02(0) = 21810-4ni-1, b02(1) = 40610-4ni-2, = 58cm-1,
Liv+Gd3+v: b02(0) = 18410-4ni-1, b02(1) = 34910-4ni-2, = 60cm-1,
E?eaa 3, yea iaeaaeeoue oeaio?o Naw+Gd3+w, nooo?ai a?ae??ciy?oueny a?ae
e?eaeo 1,2. A i?e a?aenooiy e?i?ei?noue i?e iecueeeo oaiia?aoo?ao (aeey
GaSe D~300 E) ? aiia o oeueiio ieai? iiae?aia aei oaiia?aoo?ieo
caeaaeiinoae b20(O) aeey cae/aeieo (iaoa?oaaoeo) e?enoae?a. Oea
na?ae/eoue i?i a?aenooi?noue iecueei/anoioieo eieeaaiue o ?ac? oeaio?a
Gd3+, anioe?eiaaiiai c Na+. sse a?aeiii c iioe/ieo aei???a, a oa?oaaoiio
e?enoae? GaSe iathoue i?noea iecueei/anoioi? iioe/i? eieeaaiiy c 56 ni1
(iiaea E”), a yeeo aoiie ?ooathoueny acaeiaae oa??a. Oe? eieeaaiiy
aeaoi?iothoue iaeaeeae/a ioi/aiiy aeii?oeiaiai oeaio?o ? oiio neeueii
iiaeoeththoue eiinoaioo b20. Caaaeyee oeueiio aiie iiaeooue iiai?noth
aecia/aoe oaiia?aoo?iee o?ae b20(T), ui ? aoei aeyaeaii o iiia?aaei?o
?iaioao ? iaie aeey oeaio??a 1, 2. A -GaSe, yeee aeine?aeaeoaaany, a
i?aeoa?iaiio i?inoi?? ? aeaa oeie i?aeaocieueieo ionoio v ? w (ia’?i w
>> v). sse aeaeii c ?en.3, ?ici?uoth/enue a v ? w, Li+ ia aieeaa? ia
iecueei/anoioi? eieeaaiiy E”. Na+, yeee, caaaeyee ?ici??ai, iiaea
?ici?uoaaoenue o?eueee a w, ?iaeoue iaiiaeeeaeie eieeaaiiy E”, eieaeueii
o?eia?ecoth/e oa?oaaoo no?oeoo?o.
INIIAI? ?ACOEUeOAOE OA AENIIAEE
1. Ca?a?no?iaai? ? iiyniai? niaeo?e AI? ? IAss? ainueie iiaeo
ia?aiaai?oieo oeaio??a, ui ooai?ththoueny a oa?oaaoiio naeai?ae? aae?th,
eaaiaaiiio aaaeie?i??i. Aecia/ai? ia?aiao?e ni?i-aai?eueoii?aia, ui
iienothoue cacia/ai? niaeo?e, cai?iiiiiaai? iiaeae? oeaio??a.
Anoaiiaeaii, ui aeii?oeia? aoiie yaeythoue niaith ?iie Gd3+ ?
cai?uothoue o a?aooe? e?enoaea eiaaeaioii ca’ycai? ia?e Ga24+. Aeey
?yaeo oeaio??a i?ae oa?aie o iaeaeeae/iio i?aeaoce? iaoiaeii IAss?
aeyaeai? ?iie eoaeieo iaoae?a (Li+ aai Na+), ye? neoaeaoue
eiiiainaoi?aie ca?yaeo.
2. Ca aeaieie IAss? anoaiiaeaia iniaeea?noue ?iciiae?eo aeaeo?iiii?
ni?iiai? aonoeie oeaio?o Gd3+ o GaSe: aeaeo?iiia aonoeia cina?aaeaeaia
ana?aaeei? oa?o ? ia? aeoyaiooo acaeiaae iueiai oi?io.
3. Aeyaeai? ? aea/ai? iacae/aei? ia?aiaai?oi? eiiieaene, ui
neeaaeathoueny c ?iia Gd3+ ? eieae?ciaaii? iiaeeco iueiai ae??ee,
iia’ycaieo iai?iiith aca?iiae??th. Anoaiiaeaii, ui a iai?iiiio
eiiieaeniiio oeaio?? Gd3+, iiae?aii aei iaeeii/iiai oeaio?a, cai?uo?
ia?o Ga24+, a ae??ea ia? ?aae?on noaio 9A. Aea/ai? ? iiyniai? iioe/i? ?
oaiia?aoo?i? ia?aoai?aiiy oeeo oeaio??a. Iayai?noue aeaio oei?a iai?iieo
oeaio??a iiyniaia iaaea?aaeaioi?noth aoce?a o a?aooe? -GaSe.
4. Aia?oa aeyaeaiee ? aeine?aeaeaiee IAss? o ioeueiaiio iaai?oiiio iie?
– aaciieueiaee IAss?. Aea/ai? eiai iniaeeaino? ? caaaeuei?
caeiiii??iino?. Iieacaii, ui niaeo? aaciieueiaiai IAss? oe?eeii
aecia/a?oueny iaaeoiieith ? eaaae?oiieueiith aca?iiae?yie ? aeicaiey?
iaea?aeaoe ?ioi?iaoe?th i?i ieo a “/enoiio” aeaeyae?. Ia?aaaaith
aaciieueiaiai IAss? ?: ni?iuaiiy niaeo?o o ii??aiyii? c IAss? o
iaai?oiiio iie?, iieaaoaiiy oai?aoe/iiai iieno, a?aenooi?noue ooe?aiiy
e?i?e AI? oa IAss?, iia’ycaieo c i???ioaoe?eiei ona?aaeiaiiyi niaeo??a o
iaoii?yaeeiaaieo nenoaiao.
5. Aea/ai? oaiia?aoo?i? caeaaeiino? AI? niaeo??a o e?enoae? GaSe:Gd.
?oi? iniaeeaino? iiyniai? iayai?noth a oiiiiiiio niaeo?? oa?oaaoiai
e?enoaeo iecueei/anoioieo iioe/ieo eieeaaiue, oa?aeoa?ieo aeey
eaac?aeaiaei??ieo no?oeoo?. Aeey oeaio?o Gd3+(Na+) aeyaeaiee aoaeo
eieaeueii? o?eia??caoe?? oa?oaaoi? no?oeoo?e, ui i?iyaeyany a
iiaeaaeaii? iecueei/anoioieo iioe/ieo eieeaaiue.
IOAE?EAOe??
1. Euaiei N.N., Eeeiia A.A. Iniaaiiinoe oaiia?aoo?iuo caaeneiinoae YI?
niaeo?a a neienoii e?enoaeea GaSe:Gd // OOO. – 1998 – O.40. – ?1. –
N.63–65.
2. Euaiei N.N., A?a/aa A.A., Ieoeia N.I., Eeeiia A.A. Aaniieaaie
aeaieiie yeaeo?iiii-yaea?iue ?aciiain Gd3+ a GaSe // AEYOO. – 1987. –
O.93. – ?6. – N.2102–2108.
3. Eeeiia A.A., A?a/aa A.A., Euaiei N.N., Eiaaethe C.Ae., Ieoeia N.I.,
Oaneaiei A.A. Iiaeaee i?eianiuo oeaio?ia aaaeieeiey a neienoii GaSe //
OOO. – 1987. – O.29. – ?1. – N.28-32.
4. A?a/aa A.A., Euaiei N.N., Eeeiia A.A., Eiaaethe C.Ae., Ieoeia N.I.,
Oaneaiei A.A. Noaaeeueiua ia?aiaaieoiua eiiieaenu ec eiia aaaeieeiey e
aeu?ee a neienoii iieoi?iaiaeieea GaSe // OOO. – 1988. – O.30. – ?1. –
N.82–87.
5. Ei?aooye Ae.A., Eaaiee/oe I.O., Eeoia/aiei A.A., Euaiei N.N., Eeeiia
A.A., Eiaaethe C.Ae. Oioiethieianoeaioeey e YI? naeaieaea aaeeey,
eaae?iaaiiiai ?aaeeicaiaeueiuie yeaiaioaie // OOI. – 1983. – O.17. – ?9.
– N.1710–1713.
6. Eeeiia A.A., Euaiei N.N., A?a/aa A.A., Ieoeia N.I. Ia?aciaaiea
eiiieaeniuo oeaio?ia aaaeieeiey a neienoii iieoi?iaiaeieea GaSe e
auyniaiea eo i?e?iaeu n iiiiuueth YI? e AeYss? // Oacenu aeieeaaeia
Ananithciie eiioa?aioeee “I?eiaiaiea iaaieoiiai ?aciiaina a ia?iaeiii
oicyenoaa” – Eacaiue, 1988, /.II – N.163.
7. Euaiei N.N., A?a/aa A.A., Ieoeia N.I., Eeeiia A.A. Aaniieaaie AeYss?
eae iaoiae eco/aiey i?eianiuo oeaio?ia a iieee?enoaeee/aneeo e aii?oiuo
oaeao // Oacenu aeieeaaeia Ananithciie eiioa?aioeee “I?eiaiaiea
iaaieoiiai ?aciiaina a ia?iaeiii oicyenoaa” – Eacaiue, 1988, /.III –
N.114.
8. Ishchenko S.S., Grachev V.G., Okulov S.M., Klimov A.A. Zero field
ENDOR in GaSe:Gd // Magnetic Resonance and Related Phenomena (XXIV
Congress AMPERE) – Poznan, Poland, 29.08-03.09.1988 – P.B-104.
AIIOAOe?ss
Ee?iia A.A. Aeii?oeia? oeaio?e a oa?oaaoiio naeai?ae? aae?th, eaaiaaiiio
aaaeie?i??i. – ?oeiien.
Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa
o?ceei-iaoaiaoe/ieo iaoe ca niaoe?aeuei?noth 01.04.07 – o?ceea oaa?aeiai
o?ea. – ?inoeooo o?ceee iai?ai?ia?aeiee?a IAI Oe?a?ie, Ee?a, 1999.
Aeena?oaoe?y i?enay/aia aeaoaeueiiio aeine?aeaeaiith aeii?oeiaeo
oeaio??a o oa?oaaoiio e?enoae? GaSe:Gd iaoiaeaie AI? ? IAss?.
Ca?a?no?iaai? ? iiyniai? niaeo?e 8 iiaeo ia?aiaai?oieo oeaio??a.
Aecia/ai? ia?aiao?e ni?i-aai?eueoii?aia, ui iieno? AI? ? IAss? niaeo?e
oa cai?iiiiiaai? iiaeae? oeaio??a. Anoaiiaeaii, ui ?iie Gd3+
cai?uothoue o a?aooe? e?enoaeo eiaaeaioii ca’ycai? ia?e Ga24+. Aeey
?yaeo oeaio??a o i?aeoa?iaiio i?inoi?? aeyaeai? ?iie Li+ ? Na+, ye?
neoaeaoue eiiiainaoi?aie ca?yaeo. ??ciiiai?ooy oeaio??a iaoiiaeaia
iaaea?aaeaioi?noth aoce?a a?aoee oa?oaaoiai e?enoaeo, a?aei?ii?noth
i?e?iaee eiiiainaoi?a ca?yaeo oa ooai?aiiyi iai?iieo eiiieaen?a.
Iaea?aeai? a?aeiiino? i?i no?oeoo?o aeaoaeoo a yeiio iin?e ca?yaeo
(ae??ea) eieae?co?oueny iiaeeco aeii?oeiaiai ?iio. Ca?a?no?iaaii ?
aeine?aeaeaii IAss? o ioeueiaiio iaai?oiiio iie?. Aea/ai? eiai
iniaeeaino?, ia?aaaae ? caaaeuei? caeiiii??iino?. Oaiia?aoo?i?
caeaaeiino? AI? niaeo??a o e?enoae? GaSe:Gd iiyniai? iayai?noth a
oiiiiiiio niaeo?? oa?oaaoiai e?enoaeo iecueei/anoioieo iioe/ieo
eieeaaiue. Aeey oeaio?o Gd3+(Na+) aeyaeaiee aoaeo eieaeueii?
o?eia??caoe?? oa?oaaoi? no?oeoo?e.
Eeth/ia? neiaa: AI?, IAss?, oa?oaao? e?enoaee, aeii?oeia? oeaio?e,
ae??ea, eiiiainaoi?e ca?yaeo.
AIIIOAOeEss
Eeeiia A.A. I?eianiua oeaio?u a neienoii naeaieaea aaeeey, eaae?iaaiiii
aaaeieeieai. – ?oeiienue.
Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa
oeceei-iaoaiaoe/aneeo iaoe ii niaoeeaeueiinoe 01.04.07 – oeceea
oaa?aeiai oaea. – Einoeooo oeceee iieoi?iaiaeieeia IAI Oe?aeiu, Eeaa,
1999.
Aeenna?oaoeey iinayuaia aeaoaeueiiio eco/aieth i?eianiuo oeaio?ia a
neienoii e?enoaeea GaSe:Gd iaoiaeaie YI? e AeYss?, auyniaieth
ca?yaeiinoe oeaio?ia e eo iieiaeaiey a e?enoaeee/aneie ?aoaoea,
onoaiiaeaieth no?oeoo?u aeeaeaeoaai ie?oaeaiey, ii?aaeaeaieth
?aaeeiniaeo?ineiie/aneeo ia?aiao?ia, auyniaieth aeeyiey i?eiane ia
oece/aneea naienoaa neienoiai e?enoaeea. Iaia?oaeaii ainaiue iiauo
ia?aiaaieoiuo oeaio?ia. Onoaiiaeaii, /oi /aou?a ec ieo ninoiyo ec Gd3+ e
?aniieiaeaiiiai a aeeaeaeoai iaaeoceee eiia uaei/iiai iaoaeea (Li+ eee
Na+), neoaeauaai eiiiainaoi?ii ca?yaea. Oaeea eiiieaenu ecica?yaeii
caiauatho a ?aoaoea GaSe eiaaeaioiinaycaiiua ia?u Ga24+. Iaaethaeaeenue
oaeaea aeaa oeaio?a n aeaeueiae eiiiainaoeeae ca?yaea. Niaeanii aeaiiui
AeYss?, eii aaaeieeiey ?aniieiaeai a oeaio?a neiy, a ca?yaeiaue
eiiiainaoi? a iaaeneiaaii i?ino?ainoaa. Ii?aaeaeaiu
?aaeeiniaeo?ineiie/aneea oa?aeoa?enoeee oeaio?ia e aeaoaeueiay no?oeoo?a
eo aeeaeaeoaai ie?oaeaiey. Iaia?oaeaiiia iiiaiia?acea oeaio?ia iauyniaii
iayeaeaaeaioiinoueth oceia aaeeey a -iieeoeia, ioee/eai a i?e?iaea
eiiiainaoi?a ca?yaea eee aai ?acee/iui iieiaeaieai a ?aoaoea, a oaeaea
i?eianueth a iaeioi?uo ia?acoeao -iieeoeia. Ii aeaiiui AeYss?
onoaiiaeaia iniaaiiinoue ?ani?aaeaeaiey yeaeo?iiiie nieiiaie ieioiinoe
oeaio?a Gd3+ a GaSe: yeaeo?iiiay ieioiinoue nin?aaeioi/aia aioo?e neiy e
eiaao auoyioooth aaeieue iaai oi?io. Iaia?oaeaiu e eco/aiu aeaa
iaiau/iuo ia?aiaaieoiuo eiiieaena, ninoiyuea ec eiia Gd3+ (S1=7/2) e
eieaeeciaaiiie aaeece iaai aeu?ee (S2=1/2), naycaiiuo iaiaiiui
acaeiiaeaenoaeai J2ni–1. Niaeo? YI? oeaio?a ninoiye ec aeaoo a?oii
eeiee, niioaaonoaothueo ninoiyieyi noiia?iiai nieia S=S1+S2, a niaeo?
AeYss? aue iiaeiaai niaeo?o iaeeii/iiai oeaio?a Gd3+, ii n aieaa
neeueiui naa?ooiieei acaeiiaeaenoaeai n yae?aie Se77. Onoaiiaeaii, /oi a
iaiaiiii eiiieaeniii oeaio?a Gd3+, eae e a iau/iii oeaio?a, caiauaao
ia?o Ga24+, a aeu?ea eiaao ?aaeeon ninoiyiey 9A. Iaeaeaiiua ia?aiao?u
niei-aaieeueoiieaia ieacaeenue aeeceeie e ia?aiao?ai
iaacaeiiaeaenoaothueo Gd3+ e aeu?ee. Eco/aiu e iauyniaiu iioe/aneea e
oaiia?aoo?iua i?aia?aciaaiey oeaio?ia. Iaaethaeaaiua aeaa oeia iaiaiiuo
oeaio?ia oaeaea naycaiu n iayeaeaaeaioiinoueth oceia a ?aoaoea –GaSe.
Aia?aua iaia?oaeai e enneaaeiaai AeYss? a ioeaaii iaaieoiii iiea –
aaniieaaie AeYss?. Eco/aiu aai iniaaiiinoe e iauea caeiiiia?iinoe.
Aaniieaaie AeYss? iaaethaeaeny ia oeaio?ao Gd3+ n aeaeueiae
eiiiainaoeeae ca?yaea. Ca?aaeno?e?iaaia e iauyniaia aiiiaeueii aieueoay
eioaineaiinoue “cai?auaiiuo” ia?aoiaeia aeey yaea? aaeeey. Iieacaii, /oi
niaeo? aaniieaaiai AeYss? iieiinoueth ii?aaeaeyaony naa?ooiieei e
eaaae?oiieueiui acaeiiaeaenoaeyie e iicaieyao iieo/eoue eioi?iaoeeth i
ieo a “/enoii” aeaea. Aeinoieinoaii aaniieaaiai AeYss?, eae iiaiai
iaoiaea ?aaeeiniaeo?ineiiee, yaeythony: oi?iuaiea niaeo?a, ii n?aaiaieth
n AeYss? a iaaieoiii iiea, iaeaa/aiea oai?aoe/aneie ia?aaioee,
ionoonoaea ooe?aiee, naycaiiuo n i?eaioaoeeiiiui on?aaeiaieai niaeo?ia a
iaoii?yaei/aiiuo nenoaiao. Enneaaeiaaiu oaiia?aoo?iua caaeneiinoe
aeneaeueiuo eiinoaio b20, oa?aeoa?ecothueo oiieoth no?oeoo?o YI?
niaeo?ia Gd3+ a GaSe. A o?ao oeiao oeaio?ia, a eioi?uo Gd3+
annioeee?iaai n eiiaie Li+ eee Na+, eco/aii aeeyiea yoeo eiiia ia
oiiiiiue niaeo? e?enoaeea. Iieacaii, /oi eeoee ec-ca iaeuo ?acia?ia ia
ieacuaaao caiaoiiai aeeyiey ia iecei/anoioiua iioe/aneea eieaaaiey
(iiaea E”), eioi?ua ii?aaeaeytho oiae oaiia?aoo?iie e?eaie. Aeey oeaio?a
Gd3+(Na+) iaia?oaeai yooaeo eieaeueiie o?aoia?ecaoeee neienoie
no?oeoo?u, i?iyaeythueeny a iiaeaaeaiee iecei/anoioiuo iioe/aneeo
eieaaaiee iiaeu E”. b20 (O) aeey oeaio?ia, annioeee?iaaiiuo n Na+, eiaao
aeae oaiia?aoo?iie caaeneiinoe aeey iau/iuo (ianeienouo) e?enoaeeia,
aaea eeiaeiinoue iaaethaeaaony eeoue i?e oaiia?aoo?ao aieueoa
oaiia?aoo?u Aeaaay.
ABSTRACT
Klimov A.A. Impurity centres in layer gallium selenide doped by
gadolinium. – Manuscript.
Thesis for candidate degree by speciality 01.04.07 – solid state
physics. – The Institute of Semiconductor Physics of National Academy of
Sciences of Ukraine, Kiev, 1999.
The dissertation is devoted to detailed study of impurity centres in a
layer crystal GaSe:Gd by ESR and ENDOR techniques. Spectra of 8 new
paramagnetic centres are registered and interpreted. Parameters of a
spin–Hamiltonian describing the observed ESR and ENDOR spectra are
determined, and models of the centres are suggested. It is revealed that
Gd3+ ions substitute Ga24+covalent bound pairs in the crystal lattice.
For a number of centres the Li+ and Na+ ions compensating charge were
found in the intra-layer space. Obtained variety of the centres is
caused by lattice sites inequivalence in the layer crystal, distinction
in charge compensator natures, formation of complex exchange centres.
Information about the structure of defect caused by charge carrier
(hole) localization in the vicinity of impurity ion was obtained. ENDOR
in a zero magnetic field is found and studied. Its features, advantages
and general regularities are investigated. Temperature dependencies of
ESR spectra in GaSe:Gd crystal are explained by presence of
low-frequency optical oscillations in a phonon spectrum of the layer
crystal. It was found for Gd3+ (Na+) centre that the layer structure
locally behaves as a regular 3D crystal.
Key words: ESR, ENDOR, layer crystals, impurity centres, hole, charge
compensators.
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