Bromley S T, Goumans T P M, Herbst E, Jones A P, Slater B
Departament de Química Física and Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, E-08028 Barcelona, Spain.
Phys Chem Chem Phys. 2014 Sep 21;16(35):18623-43. doi: 10.1039/c4cp00774c.
Studies aiming to understand the physicochemical properties of interstellar dust and the chemical reactions that occur on and in it have traditionally been the preserve of astronomical observation and experimental attempts to mimic astronomically relevant conditions in the laboratory. Increasingly, computational modelling in its various guises is establishing a complementary third pillar of support to this endeavour by providing detailed insights into the complexities of interstellar dust chemistry. Inherently, the basis of computational modelling is to be found in the details (e.g. atomic structure/composition, reaction barriers) that are difficult to probe accurately from observation and experiment. This bottom-up atom-based theoretical approach, often itself based on deeper quantum mechanical principles, although extremely powerful, also has limitations when systems become too large or complex. In this Perspective, after first providing a general background to the current state of observational-based knowledge, we introduce a number of computational modelling methods with reference to recent state-of-the-art studies, in order to highlight the capabilities of such approaches in this field. Specifically, we first outline the use of computational chemistry methods for dust nucleation, structure, and individual reactions on bare and icy dust surfaces. Later, we review kinetic modelling of networks of reactions relevant to dust chemistry and how to take into account quantum tunnelling effects in the low temperature reactions in the interstellar medium. Finally, we point to the future challenges that need to be overcome for computational modelling to provide even more detailed and encompassing perspectives on the nature and reaction chemistry of interstellar dust.
旨在了解星际尘埃的物理化学性质以及在其表面和内部发生的化学反应的研究，传统上一直是天文观测以及在实验室中模拟天文相关条件的实验尝试的领域。越来越多的各种形式的计算建模正在通过对星际尘埃化学的复杂性提供详细见解，为这一努力建立起一个互补的第三支柱。本质上，计算建模的基础在于那些难以通过观测和实验准确探测的细节（例如原子结构/组成、反应势垒）。这种自下而上的基于原子的理论方法，通常本身基于更深层次的量子力学原理，虽然极其强大，但当系统变得太大或太复杂时也有局限性。在这篇综述文章中，我们首先提供基于观测的知识现状的一般背景，然后参考最近的前沿研究介绍一些计算建模方法，以突出此类方法在该领域的能力。具体来说，我们首先概述计算化学方法在裸尘和冰尘表面的尘埃成核、结构以及单个反应中的应用。随后，我们回顾与尘埃化学相关的反应网络的动力学建模，以及如何在星际介质的低温反应中考虑量子隧穿效应。最后，我们指出计算建模为了能对星际尘埃的性质和反应化学提供更详细和全面的观点而需要克服的未来挑战。
