{"created":"2021-03-01T06:43:44.149229+00:00","id":8347,"links":{},"metadata":{"_buckets":{"deposit":"5e496941-fd69-4614-a99a-566a4cb121f7"},"_deposit":{"id":"8347","owners":[],"pid":{"revision_id":0,"type":"depid","value":"8347"},"status":"published"},"_oai":{"id":"oai:tsukuba.repo.nii.ac.jp:00008347","sets":["3:233:254"]},"author_link":["34749"],"item_12_biblio_info_6":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2000","bibliographicIssueDateType":"Issued"}}]},"item_12_date_granted_46":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"2000-03-24"}]},"item_12_degree_grantor_44":{"attribute_name":"学位授与大学","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_language":"ja","subitem_degreegrantor_name":"筑波大学"},{"subitem_degreegrantor_language":"en","subitem_degreegrantor_name":"University of Tsukuba"}],"subitem_degreegrantor_identifier":[{"subitem_degreegrantor_identifier_name":"12102","subitem_degreegrantor_identifier_scheme":"kakenhi"}]}]},"item_12_degree_name_43":{"attribute_name":"取得学位","attribute_value_mlt":[{"subitem_degreename":"博士（理学）"},{"subitem_degreename":"Doctor of Philosophy in Science"}]},"item_12_description_4":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"本論文は，3次元的並進周期性を保持している結晶でありながら，結晶中のある自由度に関してのみ，これらの並進周期性と非有理数比の周期をもつ不整合結晶相(IC相)と呼ばれる特異な結晶相を有するCsMX4(M:Zn, Cd, Hg, X：ハロゲン)型結晶の相転位と構成原子の動的特性を論じたものである。　まず最初に，四面体構造を持つ[MX4]2-イオンの結晶中での配向角が不整合性をもつIC相の存在が報告されているCs2CdBr4, Cs2HgBr4, Cs2CdI4, Cs2HgCl4結晶の133Cs固体NMRのスピン格子緩和時問の温度及びLarmor周波数依存性を測定した。IC相で得られた緩和のデータは[MX4]2-イオンの配向運動の振幅及び位相変調によってよく説明され，IC相の存在を確認すると共に，IC相の動的構造を明らかに示した。また，高温相(N相)からIC相への相転移の機構はCs2CdBr4以外の化合物では3次元XYモデルで説明されたが，Cs2CdBr4については，古典的平均場モデルの適用を必要とすることを明らかにした。　次章においては，IC相形成機構を明らかにする目的で，上記のIC相を持つ結晶とIC相を持たない同型構造を持つCs2ZnX4と類似構造(Sr2GeS4型)を有するCs2MI4(M：Cd,Hg)について，133CsNMRの化学シフト及び緩和時間の温度依存症を測定して，IC相の有無との関係を調べている。その結果，これら全ての結晶中には結晶学的に異なる2種のCsイオンが存在し，それらの化学シフトに明瞭な違いを観測し，それらの差がCs･･･X間の電荷移動による共有結合性の違いとして説明されることを明らかにした。　最終章において，IC相を有する結晶中の不整合変調構造に関与しているCsイオンと関与していないCsイオンのCs･･･X共有結合性，および，β－K2SO4型構造結晶でIC相を持つ結晶と持たない結晶の比較を行い，IC相出現の機構を考察している。結晶構造とNMRの結果を比較すると，β－K2SO4型構造を持つCs2MX4化合物では，共有結合性が小さいCs(1)が不整合変調構造に関与しており，大きいCs(2)は関与していないことを見いだしている。Csの共有結合性の温度変化を比較して，Cs(2)の共有結合性はIC相の有無にかかわらず変化は小さいが，IC相を持つCs(1)では大きな温度依存性を見いだしている。以上の結果から，IC相出現の機構にCs(1)と陰イオンとの電荷移動が大きく影響していることを予測している。　結論として，Cs2MX4結晶では陽・陰イオン間の結合によって[MX4]2-イオンが同じ配向を取ろうとする相互作用と[MX4]2-イオン頂点のハロゲンイオン間の静電反発によって[MX4]2-イオンが互いにずれた配向を取ろうとする相互作用の拮抗によってIC相への転移が引き起こされるという解釈を提案している。 Translational lattice periodicity is one of the basic characteristics of the concept of crystal [1, 2]. It is known, however, that some kinds of crystals cannot be described by a single translational period but require two or more sublattices which have incommensurate lattice lengths with each other (Fig, 1.1.(b)). This structure is so-called incommensurate (IC). ...","subitem_description_language":"ja","subitem_description_type":"Abstract"}]},"item_12_description_45":{"attribute_name":"学位授与年度","attribute_value_mlt":[{"subitem_description":"1999","subitem_description_type":"Other"}]},"item_12_description_5":{"attribute_name":"内容記述","attribute_value_mlt":[{"subitem_description":"Includes bibliographical references","subitem_description_language":"en","subitem_description_type":"Other"},{"subitem_description":"On t.p. \"[133]\" is superscript","subitem_description_language":"en","subitem_description_type":"Other"}]},"item_12_dissertation_number_47":{"attribute_name":"報告番号","attribute_value_mlt":[{"subitem_dissertationnumber":"甲第2312号"}]},"item_access_right":{"attribute_name":"アクセス権","attribute_value_mlt":[{"subitem_access_right":"open 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