Computational Inorganic Photochemistry: From Ultrafast Photodissociation to Photostereochemistry

计算无机光化学：从超快光解离到光立体化学

• 批准号: EP/F01709X/1
• 负责人: Martin Paterson
• 金额: $ 26.24万
• 依托单位: Heriot-Watt University
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2007
• 资助国家: 英国
• 起止时间: 2007 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FF01709X%2F1
• 关键词: Computational; Inorganic; Photochemistry; Ultrafast; Photodissociation

The interaction between light and molecules containing a transition metal center gives rise to a fascinating multitude of chemistry in many different fields, from biochemistry to semi-conductor technology. Some fundamental reactions within this field of inorganic photochemistry will be investigated using state of the art computational techniques. This will allow us to understand the basic processes at the level of the electrons and atomic nuclei after light absorption. For example when a transition metal carbonyl absorbs a photon it may dissociate a carbonyl ligand in the order of a few tens of femtoseconds. It then relaxes in such a way that only certain motions of the atomic nuclei are observed in cutting-edge spectroscopic experiments. In order to model such phenomena we need to use quantum mechanics at both the level of electrons and the nuclei. We evaluate the electronic wavefunctions and related potential energy surfaces on which nuclear motion takes place, including appropriate coupling to allow the molecules to 'switch' surfaces. The nuclear wavefunction is then propagated and this simulates the actual dynamics induced by light absorption. Transition metal complexes can contain many atoms and modelling the motion of multiple vibrational modes, over several coupled potential energy surfaces is a real challenge. However such realistic modelling is essential if we are to understand the basic processes with a view to designing materials with specific applications in mind.In this proposal we aim to study two fundamental classes of inorganic photochemical reactions from first-principles using high-level electronic structure theory combined with advanced methods of nuclear dynamics. One proptotypical system is transition metal carbonyl photodissociation, an extremely important photoinduced process. In particular the photodissociation dynamics of Fe(CO)5 will be studied; this system is expected to show the importance of coupling between 3 or more potential energy surfaces and a significant number of vibrational modes. The other type of effect to be investigated is the photostereochemistry of certain open-shell Chromium(III) complexes. These systems have different stereo-isomers, which can be created (or interchanged) via the application of light. If we understand such processes we can then design complexes for use in applications such as fast light-switching and solar energy conversion. Such complexes have an odd number of electrons and therefore spin-orbit coupling between states with different spin-multiplicites is expected to be important.In summary we wish to use state of the art computational techniques to investigate what happens after certain inorganic molecules absorb light. We plan to study both the electronic rearrangements after absorption and the subsequent (ultrafast) nuclear motion using advanced methods that will give us a detailed understanding of inorganic photochemistry at the molecular level.

光与含有过渡金属中心的分子之间的相互作用在许多不同的领域产生了许多迷人的化学，从生物化学到半导体技术。无机光化学领域内的一些基本反应将使用最先进的计算技术进行研究。这将使我们能够理解光吸收后电子和原子核水平的基本过程。例如，当过渡金属羰基吸收光子时，其可以几十飞秒的量级解离羰基配体。然后它以这样一种方式弛豫，即在尖端的光谱实验中只能观察到原子核的某些运动。为了模拟这种现象，我们需要在电子和原子核两个层面上使用量子力学。我们评估的电子波函数和相关的势能表面上的核运动发生，包括适当的耦合，使分子的“开关”表面。然后传播核波函数，这模拟了光吸收引起的实际动力学。过渡金属配合物可以包含许多原子，并且在几个耦合的势能面上模拟多个振动模式的运动是一个真实的挑战。然而，这种现实的建模是必不可少的，如果我们要了解的基本过程，以期设计材料与具体的应用minutes.In本提案中，我们的目标是研究两个基本类的无机光化学反应的第一原理使用高级电子结构理论结合先进的核动力学方法。过渡金属羰基化合物的光解是一个非常重要的光诱导过程。特别是光解离动力学的Fe（CO）5将进行研究，该系统预计将显示3个或更多的势能面和大量的振动模式之间的耦合的重要性。另一种类型的影响是研究某些开壳铬（III）配合物的光立体化学。这些系统具有不同的立体异构体，它们可以通过应用光来产生（或互换）。如果我们理解了这些过程，我们就可以设计出用于快速光开关和太阳能转换等应用的复合物。这种复合物具有奇数个电子，因此具有不同自旋多重子的状态之间的自旋轨道耦合预计是重要的。总之，我们希望使用最先进的计算技术来研究某些无机分子吸收光后会发生什么。我们计划使用先进的方法研究吸收后的电子重排和随后的（超快）核运动，这将使我们在分子水平上详细了解无机光化学。

项目成果

Photoisomerization in a Platinum-Amido Pincer Complex: An Excited-State Reaction Pathway Controlled by Localized Ligand Photochemistry

铂-氨基钳配合物中的光异构化：局域配体光化学控制的激发态反应途径

• DOI: 10.1021/jz100156p
• 发表时间: 2010
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Zurek J

Investigation of challenging spin systems using Monte Carlo configuration interaction and the density matrix renormalization group.

使用蒙特卡罗构型相互作用和密度矩阵重正化群研究具有挑战性的自旋系统。

• DOI: 10.1002/jcc.25057
• 发表时间: 2017
• 期刊: Journal of computational chemistry
• 影响因子: 3
• 作者: Coe JP

Excited electronic states of MnO4-: Challenges for wavefunction and density functional response theories

MnO4- 的激发电子态：波函数和密度泛函响应理论的挑战

• DOI: 10.1016/j.chemphys.2014.11.011
• 发表时间: 2015
• 期刊: Chemical Physics
• 影响因子: 2.3
• 作者: Almeida N

The Jahn-Teller Effect - Fundamentals and Implications for Physics and Chemistry

扬-特勒效应 - 物理和化学的基础知识和启示

• DOI: 10.1007/978-3-642-03432-9_11
• 发表时间: 2009
• 作者: McKinlay R

Excited-State Dynamics of a Two-Photon-Activatable Ruthenium Prodrug.

• DOI: 10.1002/cphc.201501075
• 发表时间: 2016-01-18
• 期刊: Chemphyschem : a European journal of chemical physics and physical chemistry
• 作者: Greenough SE;Horbury MD;Smith NA;Sadler PJ;Paterson MJ;Stavros VG
• 通讯作者: Stavros VG