在超稳定状态的光酸中揭示光异构化动态
Ying-Zhong Ma1, Uvinduni I Premadasa1, Vyacheslav S Bryantsev1
1Chemical Sciences Division, Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831, USA. may1@ornl.gov.
Physical chemistry chemical physics : PCCP
|January 15, 2024
概括
在超稳态光酸 (mPAHs) 中研究光异构是困难的. 这项研究使用时间解析光和TDDFT计算来揭示印达mPAH中的光异构化动态.
科学领域:
- 摄影化学的使用.
- 频谱学是一种光谱学.
- 计算化学计算化学
背景情况:
- 在超稳态光酸 (mPAHs) 中直接访问跨cis光异构化具有挑战性.
- 竞争激发状态放松通路和过渡异构体的重叠光谱使分析复杂化.
研究的目的:
- 为了揭示印达mPAH中的光异构化动态.
- 克服研究mPAHs中的光异构化的挑战.
主要方法:
- 时间分辨率光学 (TRF) 光谱.时间分辨率光学 (TRF).
- 使用一种mPAH,它只能从转变异构体中光.
- 时间依赖密度函数理论 (TDDFT) 的计算.
主要成果:
- 在英达mPAH中成功观察到光异构化动态.
- TRF光谱学为转变异构体的行为提供了一个独特的窗口.
- TDDFT计算支持了实验发现.
结论:
- 这项研究提供了对mPAHs中跨cis光异构化的机制性洞察.
- 综合光谱和计算方法对于研究复杂的光异构化过程是有效的.
相关概念视频
Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.8K
Deactivation Processes: Jablonski Diagram
666
Luminescence, the emission of light by a substance that has absorbed energy, is a process that involves the interaction of molecules with light. The energy-level diagram, or Jablonski diagram, is a graphical representation of these interactions, illustrating the various states and transitions a molecule can undergo. In a typical Jablonski diagram, the lowest horizontal line represents the ground-state energy of the molecule, which is usually a singlet state. This state represents the energies...
666
Thermal and Photochemical Electrocyclic Reactions: Overview
2.3K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.3K
Keto–Enol Tautomerism: Mechanism
5.4K
The keto and enol forms are known as tautomers and they constantly interconvert (or tautomerize) between the two forms under acid or base catalyzed conditions. Both the reactions involve the same steps—protonation and deprotonation— although in the reverse order.
5.4K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.4K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
8.4K
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
3.1K
Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
3.1K


