C10H8の潜在エネルギー表面でのE/Zイソメリゼーションを紫外線集団移転スペクトロスコピーで探知する
Josh J Newby1, Christian W Müller, Ching-Ping Liu
1Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, USA.
Journal of the American Chemical Society
|January 14, 2010
まとめ
フェニルビニラセチレン (PVA) のイソマーは,非放射性プロセスにより,より高いエネルギーで光性が低下しています. このプロセスは,おそらくピ・シグマ状態を含んでいるが,直接的にイソメリゼーションを引き起こすわけではないが,基底状態での内部変換後の変換が起こる.
科学分野:
- フォトケミストリーとフォト物理学
- 化学ダイナミクス 化学ダイナミクス
- スペクトル顕微鏡検査です.
背景:
- フェニルビニラセチレン (PVA) イソマー (EとZ) は,複雑な興奮状態ダイナミクスを持っています.
- 非放射性分解経路を理解することは,光化学反応の制御に極めて重要です.
研究 の 目的:
- フェニルビニラセチレン (PVA) 同性体の興奮状態ダイナミクスを研究する.
- 光解消とイソメリゼーションのメカニズムを解明する.
- PVAの光化学におけるピ・シグマ状態の役割を決定する.
主な方法:
- レーザー誘発光スペクトロスコピー
- 紫外線の枯渇スペクトロスコピーは,紫外線の枯渇スペクトロスコピーを用います.
- 紫外線集団移転光譜検査による紫外線集団移転光譜検査
- Ab initioと密度関数理論による計算
- 共振-2-フォトンのイオン化スペクトロスコピーは,共振-2-フォトンのイオン化スペクトロスコピーを用います.
主要な成果:
- EとZのPVAイソマーは,興奮エネルギーが増加するにつれて,光強度の有意な減少を示します.
- 特定のエネルギー値を超えて開始される非放射性プロセスは,光の滅に責任があります.
- 計算によると,ππ*とπシグマ*の状態の相互作用が非放射性衰退を誘発している.
- イソメリゼーションの量子産量は,光消火にもかかわらず一定であり,イソメリゼーションは内部変換後に発生することを示しています.
結論:
- PVAにおける非放射性プロセスは,直接的にイソメリゼーションにつながらない.
- イソメリゼーションは,内部変換後に基底状態の潜在エネルギー表面で発生すると仮定されています.
- 基底状態でのイソメリゼーションと冷却の間の競争は,最終製品の分布に影響します.
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