Multireference electronic structure theory used for computing rate constants of nonradiative decay and proton transfer reactions

2023 Fiscal Year Final Research Report

• Project/Area Number: 21H01881
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 32010:Fundamental physical chemistry-related
• Research Institution: Nagoya University
• Principal Investigator: Yanai Takeshi 名古屋大学, 理学研究科(WPI), 教授 (00462200)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: 多参照理論 / 失活速度定数 / 密度行列繰込群 / 解析的微分

Outline of Final Research Achievements

The density matrix renormalization group (DMRG) method, a highly accurate and efficient multiple configuration wavefunction theory, is extended to develop an analytical gradient method for reliably calculating the structure of excited states, reaction paths, and interstate coupling constants in reaction processes involving state transitions. We have also implemented a method to evaluate the rate constants of internal conversion and intersystem crossing by numerical calculation of Fermi's golden rule from the information of highly accurate energy surfaces and inter-state coupling constants. Theoretical analysis of the radiation-free deactivation process of fluorescent bioprobes of the phosphole oxide skeleton and rate analysis simulations of the inverse term-crossing of thermally activated delayed fluorescence were achieved.

Free Research Field

量子化学

Academic Significance and Societal Importance of the Research Achievements

密度行列繰り込み群(DMRG)の解析的微分法は励起状態の構造・反応経路探索や状態間結合定数を頼性高く計算するのに重要な役割を担う。ホスホールオキシド骨格の無輻射失活過程の理論解析は光耐性高機能蛍光バイオプローブの開発の基盤となると考えられる。熱活性化遅延蛍光の逆項間交差に関する速度解析シミュレーションは次世代型有機EL分子材料の設計に重要な指針を与えるものと考えられる。