Fernández-González Miguel Ángel, Rivero Daniel, García-Iriepa Cristina, Sampedro Diego, Frutos Luis Manuel
Química Física, Universidad de Alcalá , E-28871 Alcalá de Henares, Madrid, Spain.
Departamento de Química, Centro de Investigación en Síntesis Química (CISQ) , Madre de Dios, 53, E-26006 Logroño, Spain.
J Chem Theory Comput. 2017 Feb 14;13(2):727-736. doi: 10.1021/acs.jctc.6b01020. Epub 2017 Jan 24.
Control of absorption spectra in chromophores is a fundamental aspect of many photochemical and photophysical processes as it constitutes the first step of the global photoinduced process. Here we explore the use of mechanical forces to modulate the light absorption process. Specifically, we develop a computational formalism for determining the type of mechanical forces permitting a global tuning of the absorption spectrum. This control extends to the excitation wavelength, absorption bands overlap, and oscillator strength. The determination of these optimal forces permits us to rationally guide the design of new mechano-responsive chromophores. Pyrene has been chosen as the case study for applying these computational tools because significant absorption spectra information is available for the chromophore as well as for different strained derivatives. Additionally, pyrene presents a large flexibility, which makes it a good system to test the inclusion of force probes as the strategy to exert forces on the system.
发色团中吸收光谱的控制是许多光化学和光物理过程的一个基本方面，因为它构成了整体光诱导过程的第一步。在这里，我们探索利用机械力来调节光吸收过程。具体而言，我们开发了一种计算形式，用于确定允许对吸收光谱进行整体调谐的机械力类型。这种控制扩展到激发波长、吸收带重叠和振子强度。确定这些最佳力使我们能够合理地指导新型机械响应发色团的设计。芘被选作应用这些计算工具的案例研究，因为对于该发色团以及不同的应变衍生物，有大量的吸收光谱信息可用。此外，芘具有很大的灵活性，这使其成为测试将力探针作为对系统施加力的策略的一个良好体系。
