{"_buckets": {"deposit": "8c3dc878-cf87-4a30-9db6-e3264cf587bc"}, "_deposit": {"created_by": 1, "id": "252", "owners": [1], "pid": {"revision_id": 0, "type": "depid", "value": "252"}, "status": "published"}, "_oai": {"id": "oai:ir.soken.ac.jp:00000252", "sets": ["9"]}, "author_link": ["0", "0", "0"], "item_1_biblio_info_21": {"attribute_name": "書誌情報（ソート用）", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "2008-03-19", "bibliographicIssueDateType": "Issued"}, "bibliographic_titles": [{}]}]}, "item_1_creator_2": {"attribute_name": "著者名", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "白鳥, 和矢"}], "nameIdentifiers": [{"nameIdentifier": "0", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_creator_3": {"attribute_name": "フリガナ", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "シラトリ, カズヤ"}], "nameIdentifiers": [{"nameIdentifier": "0", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_date_granted_11": {"attribute_name": "学位授与年月日", "attribute_value_mlt": [{"subitem_dategranted": "2008-03-19"}]}, "item_1_degree_grantor_5": {"attribute_name": "学位授与機関", "attribute_value_mlt": [{"subitem_degreegrantor": [{"subitem_degreegrantor_name": "総合研究大学院大学"}]}]}, "item_1_degree_name_6": {"attribute_name": "学位名", "attribute_value_mlt": [{"subitem_degreename": "博士（理学）"}]}, "item_1_description_1": {"attribute_name": "ID", "attribute_value_mlt": [{"subitem_description": "2008010", "subitem_description_type": "Other"}]}, "item_1_description_12": {"attribute_name": "要旨", "attribute_value_mlt": [{"subitem_description": "　Electrochemical processes have historically been investigated in a wide range of\u003cbr\u003e interests in electrochemical cell, corrosion, membrane potential and analytical\u003cbr\u003e technique. Their importance has extensively been recognized in recent years, for\u003cbr\u003e example, in the context of energy conversion related to photoelectrochemical cells\u003cbr /\u003ebased on advanced fabrication technology. To analyze these electrochemical processes,\u003cbr /\u003eit is required to clarify electronic structures of a system in electrochemical\u003cbr\u003e environment. Nevertheless, it is computationally demanding to carry out\u003cbr /\u003efirst-principles calculations of such electronic states. This is simply because\u003cbr /\u003ereactant-solvent and reactant-electrode interactions, which are completely absent in\u003cbr /\u003eisolated molecular systems, play an important role. Therefore, the electrochemical\u003cbr\u003e processes have so far been studied within various numerical models at different levels\u003cbr /\u003eof theory. The problems in the electrochemical processes can be classified into two\u003cbr /\u003eparts. The first problem is difficulty in carrying out electronic structure calculations of\u003cbr /\u003ethe reactant molecule at a constant chemical potential \u0026#181, and the other one is how to\u003cbr /\u003eappropriately describe the reactant-solvent and the reactant-electrode interactions. \u003cbr /\u003e　The conventional \u003ci\u003eab initio\u003c/i\u003e calculations are directed toward obtaining electronic\u003cbr /\u003estructures at a constant number of electrons, \u003ci\u003eN\u003c/i\u003e . Such \u003ci\u003eab initio\u003c/i\u003e calculations cannot be\u003cbr /\u003estraightforwardly applied to electronic structure calculations at a constant \u0026#181, in \u003cbr /\u003ewhich the number of electrons is not a suitable variable. Although several studies have\u003cbr /\u003ebeen devoted to development of the methods calculating electronic structures at a\u003cbr /\u003econstant \u0026#181, their methods are still substantially based on the constant \u003ci\u003eN\u003c/i\u003e\u003cbr /\u003ecalculations. Therefore, it is desirable to develop an alternative method to directly\u003cbr /\u003ecalculate electronic structures at a constant \u0026#181. Finite-temperature density functional\u003cbr /\u003etheory (FTDFT) treats a system in a grand canonical ensemble average and thus one\u003cbr /\u003ecan propose a numerical method based on FTDFT to describe electrochemical\u003cbr /\u003eprocesses. \u003cbr /\u003e　In addition to the requirement for the electronic structure calculation at a constant\u003cbr /\u003e\u0026#181, reactant-solvent and reactant-electrode interactions should be considered in \u003cbr /\u003eelectrochemical processes, as mentioned above. He primarily focuses on developing the FTDFT method of electronic structure calculation of reactant molecules at a constant\u003cbr /\u003e\u0026#181. Therefore, he approximates the solvent effects in terms of a simple continuum\u003cbr /\u003emodel and limit electrochemical processes to outer-sphere ones in which the electrode\u003cbr /\u003eis treated as a reservoir with \u0026#181. It should be noted that the development of the\u003cbr /\u003eelectronic structure calculation has nothing to do with the treatment of the\u003cbr /\u003ereactant-solvent interaction, so that the present FTDFT method can be\u003cbr /\u003estraightforwardly improved by employing more sophisticated procedures describing\u003cbr /\u003ethe solvent effects. \u003cbr /\u003e　In this thesis, he develops a method of the FTDFT ab initio quantum chemistry\u003cbr /\u003ecalculations combined with a continuum solvent model and discuss the electronic\u003cbr /\u003eproperties of molecules in electrochemical environment. The actual calculations are\u003cbr /\u003ecarried out by solving the finite-temperature Kohn-Sham (KS) equation with the\u003cbr /\u003eGAMESS package of quantum chemistry programs in which the present numerical\u003cbr /\u003emethodology of FTDFT is implemented. The KS orbitals are expanded in terms of\u003cbr /\u003eDunning\u0027s augmented correlation-consistent basis set (aug-cc-pVDZ). \u003cbr /\u003e　He applies the present method to the electrochemical reaction,NO\u003csup\u003e+\u003c/sup\u003e+e\u003csup\u003e-\u003c/sup\u003e\u0026harr; NO . The \u003cbr /\u003eBecke three-parameter hybrid exchange functional with the Lee-Yang-Parr correlation \u003cbr /\u003efunctional   (B3LYP) is used as the exchange-correlation potential. He does not\u003cbr /\u003econsider the temperature dependence of the exchange-correlation potential although\u003cbr /\u003ethe potential in the FTDFT approach should depend on temperature in a narrow sense.\u003cbr /\u003eThe solvent effects are treated at the level of conductor-like polarizable continuum\u003cbr /\u003emodel (C-PCM), assuming the equilibrium condition between the solute and the\u003cbr /\u003esolvent. He gives the size of the cavity in C-PCM as a function of the molecular charge.\u003cbr /\u003eThe calculation is carried out at the chemical potentials \u0026#181 -3.40, -5.40, and -7.40 eV.\u003cbr /\u003eThese values correspond to the electrode potentials \u003ci\u003ev\u003c/i\u003e = -0.84, 1.16, and 3.16 V vs\u003cbr /\u003eSHE (standard hydrogen electrode), respectively. It has successfully been\u003cbr /\u003edemonstrated that the grand potential curve depends on \u0026#181, i.e., the electrode \u003cbr /\u003epotential. The calculation showed that the charge is a function of the chemical \u003cbr /\u003eotential and the internuclear distance of NO. The FTDFT/C-PCM approach has\u003cbr /\u003eproved to be a useful computational tool for electronic structure calculations at a\u003cbr /\u003econstant \u0026#181 of a molecule interacting with solvent molecules.\u003cbr /\u003e　Although the FTDFT/C-PCM method has succeeded in giving the reasonable results,\u003cbr /\u003ethere are two problems to be addressed: the B3LYP functional is used uncritically and\u003cbr /\u003ethe nonequilibrium solvation effect is not taken into account. These unsettled \u003cbr /\u003eproblems might give rise to serious disadvantages in analysis of electrochemical\u003cbr /\u003ekinetics. Thus, he improves the FTDFT approach further by employing a different\u003cbr /\u003efunctional and a different continuum solvent model, as mentioned bellow. This \u003cbr /\u003eimproved FTDFT method is also applied to the electrochemical reaction\u003cbr /\u003eof NO\u003csup\u003e+\u003c/sup\u003e+e\u003csup\u003e-\u003c/sup\u003e\u0026harr;NO. \u003cbr /\u003e　In the extension of the Hohenberg-Kohn theorem to the system with a fractional\u003cbr /\u003enumber of electrons \u003ci\u003eN\u003c/i\u003e by Perdew \u003ci\u003eet al\u003c/i\u003e., they demonstrated that the energy\u003cbr /\u003ecalculated by using DFT should show derivative discontinuity with respect to \u003ci\u003eN\u003c/i\u003e .\u003cbr /\u003eHowever, it is known that the B3LYP functional does not reproduce the derivative\u003cbr /\u003ediscontinuity condition. He alternatively employs the Becke exchange and\u003cbr /\u003eLee-Yang-Parr correlation functional with a long-range correction (LC-BLYP). The\u003cbr /\u003eresult obtained by using the LC-BLYP functional depends on the parameter \u0026omega; that\u003cbr /\u003edivides the Coulomb operator into short-range and long-range parts. It has been found\u003cbr /\u003ethat the B3LYP functional completely fails to describe the grand potential surface\u003cbr /\u003ewhereas the LC-BLYP functional gives a proper grand potential surface if an\u003cbr /\u003eappropriate value of \u0026omega; is taken. This is because the result of the LC-BLYP functional\u003cbr /\u003ewith the optimal value of \u0026omega; satisfies the requirement of the derivative discontinuity\u003cbr /\u003ewith respect to \u003ci\u003eN\u003c/i\u003e. \u003cbr /\u003e　To treat the nonequilibrium solvation effect, he uses the extended self-consistent\u003cbr /\u003ereaction field (SCRF) model. This model allows considering the nonequilibrium\u003cbr /\u003esolvation effect by dividing solvent polarization into long-lived and short-lived\u003cbr /\u003ecomponents. The calculated activation free energy, 12 kcal/mol, was in good agreement\u003cbr /\u003ewith an experimental result, 11 kcal/mol, whereas the result obtained by using the\u003cbr /\u003econventional SCRF model (i.e., not taking account of the nonequilibrium solvation\u003cbr /\u003eeffect) gave considerably lower value, 3 kcal/mol. He has clearly shown that the\u003cbr /\u003enonequilibrium solvation effect has a great influence on the electrochemical process\u003cbr /\u003eand the extended SCRF model significantly improves the calculated activation free\u003cbr /\u003eenergy.\u003cbr /\u003e　In summary, he has developed a computational method based on FTDFT combined\u003cbr /\u003ewith a continuum solvent model to analyze electrochemical processes. The FTDFT\u003cbr /\u003emethod allows calculating the electronic structures as a function of the chemical \u003cbr /\u003epotential. To apply the method to the studies of electrochemical kinetics, use of a\u003cbr /\u003enonequilibrium solvation model and an exchange-correlation potential satisfying the \u003cbr /\u003ederivative discontinuity is crucially important. This study provides a powerful and \u003cbr /\u003eintuitive approach to analysis of electrochemical reactions.\u003cbr /\u003e", "subitem_description_type": "Other"}]}, "item_1_description_7": {"attribute_name": "学位記番号", "attribute_value_mlt": [{"subitem_description": "総研大甲第1117号", "subitem_description_type": "Other"}]}, "item_1_select_14": {"attribute_name": "所蔵", "attribute_value_mlt": [{"subitem_select_item": "有"}]}, "item_1_select_8": {"attribute_name": "研究科", "attribute_value_mlt": [{"subitem_select_item": "物理科学研究科"}]}, "item_1_select_9": {"attribute_name": "専攻", "attribute_value_mlt": [{"subitem_select_item": "07 構造分子科学専攻"}]}, "item_1_text_10": {"attribute_name": "学位授与年度", "attribute_value_mlt": [{"subitem_text_value": "2007"}]}, "item_creator": {"attribute_name": "著者", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "SHIRATORI, Kazuya", "creatorNameLang": "en"}], "nameIdentifiers": [{"nameIdentifier": "0", "nameIdentifierScheme": "WEKO"}]}]}, "item_files": {"attribute_name": "ファイル情報", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2016-02-17"}], "displaytype": "simple", "download_preview_message": "", "file_order": 0, "filename": "甲1117_要旨.pdf", "filesize": [{"value": "387.7 kB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_11", "mimetype": "application/pdf", "size": 387700.0, "url": {"label": "要旨・審査要旨", "url": "https://ir.soken.ac.jp/record/252/files/甲1117_要旨.pdf"}, "version_id": "cb4f7aac-ac23-455d-9ac6-ba0867b8e23f"}]}, "item_language": {"attribute_name": "言語", "attribute_value_mlt": [{"subitem_language": "eng"}]}, "item_resource_type": {"attribute_name": "資源タイプ", "attribute_value_mlt": [{"resourcetype": "thesis", "resourceuri": "http://purl.org/coar/resource_type/c_46ec"}]}, "item_title": "Finite-temperature density functional approach to electrochemical reaction", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "Finite-temperature density functional approach to electrochemical reaction"}, {"subitem_title": "Finite-temperature density functional approach to electrochemical reaction", "subitem_title_language": "en"}]}, "item_type_id": "1", "owner": "1", "path": ["9"], "permalink_uri": "https://ir.soken.ac.jp/records/252", "pubdate": {"attribute_name": "公開日", "attribute_value": "2010-02-22"}, "publish_date": "2010-02-22", "publish_status": "0", "recid": "252", "relation": {}, "relation_version_is_last": true, "title": ["Finite-temperature density functional approach to electrochemical reaction"], "weko_shared_id": 1}