The hole mass in Car-Parrinello molecular dynamics: insights into the dynamics of excitation

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Sherif Abdulkader Tawfik, Tiffany R Walsh
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Abstract

In the Car-Parrinello molecular dynamics (CPMD) formalism, orbitals can be assigned different effective masses according to whether the orbital is occupied by a hole or an electron, and such masses affect the response of the orbitals to their environment. Inspired by this, we introduce and implement a novel modification of CPMD, HoleMass CPMD, in which a hole, which is a partially empty orbital, is assigned a fictitious mass that is different from fully occupied orbitals. Despite the simplicity of the approach, we find that it solves a key problem in first principles molecule dynamics simulation: for a set of carefully assigned mass values, the method is able to successfully simulate photoinduced chemical reactions, exemplified here by the ring-opening reaction in oxirane within a few femtoseconds, and cyclobutene, within a few picoseconds. Our method can reproduce the CO ring-opening of oxirane, and the correct isomerization sequence for cyclobutene: when the ring opens, the first isomer that forms is the cis isomer, followed by the trans isomer. Our method has been implemented in the Car-Parrinello package of QuantumEspresso and is available as an open-source contribution. The HoleMass CPMD method provides a new quantum chemistry tool for the simulation of excitation dynamics in molecules, and can also be applied for modelling charge localization effects in materials systems.
Car-Parrinello分子动力学中的空穴质量:激发动力学的洞见
在Car-Parrinello分子动力学(CPMD)的形式中,轨道的有效质量可以根据轨道上是否被空穴或电子占据而被赋予不同的有效质量,而这些有效质量会影响轨道对周围环境的响应。受此启发,我们引入并实现了一种新的改进CPMD, HoleMass CPMD,其中一个部分空轨道的空穴被赋予不同于完全占据轨道的虚拟质量。尽管方法简单,但我们发现它解决了第一线原理分子动力学模拟中的一个关键问题:对于一组仔细指定的质量值,该方法能够成功地模拟光诱导化学反应,例如在几飞秒内的氧烷开环反应,以及在几皮秒内的环丁烯反应。我们的方法可以再现氧环烷的CO开环过程,以及环丁烯的正确异构化顺序:当环开环时,首先形成的异构体是顺式异构体,其次是反式异构体。我们的方法已经在QuantumEspresso的Car-Parrinello包中实现,并且可以作为开源贡献。HoleMass CPMD方法为分子激发动力学模拟提供了一种新的量子化学工具,也可用于模拟材料系统中的电荷局域化效应。
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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