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水は電極電解液界面でどう振る舞うであろうか これは電気化学で最も基本的でかつ重要な研究課題の一つであるHelmholtzによる1853年の電気二重層の提案から始まった電極界面構造の研究は, 1960年代になって, 水は界面の電場に沿って配列し, 電位表面電荷によってその配向を変化させる, という現在一般的に受け入れられているモデルに到達したしかし, これを直接確認する手段がなく, 詳細は永年不明のままであった最近の計算化学と電極界面のその場測定方法の進展により, 電極界面を分子レベルでより詳細に検討することが可能になり, 新しい知見が得られるようになってきている本稿では, 表面増強赤外分光SEIRASによる解析を中心として, 最近の進展の一端を紹介するHow do water molecules behave at the electrochemical interface (the charged electrode-electrolyte interface)? This is one of the most fundamental and important questions in electrochemistry, and has been discussed extensively since the first proposal of the electric double layer model by Helmholtz in 1853. In the 1960s, a general consensus was reached that water molecules orient along the electric field at the interface and change the orientation depending on the applied potential (i.e., surface charge). However, details had long been unclear. Recent developments of computational theoretical chemistry and in situ surface analytical techniques have enabled a further detailed study of the interface at a molecular level and renewed our understanding. Recent progresses has been reviewed in the manuscript by focusing on experimental data provided by surface-enhanced infrared absorption spectroscopy (SEIRAS)

Structure and Behavior of Water at the Electrochemical Interface Studied by Surface-Enhanced Infrared Absorption Spectroscopy