Manzhos Sergei, Ihara Manabu
School of Materials and Chemical Technology, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8552, Japan.
Phys Chem Chem Phys. 2022 Jun 29;24(25):15158-15172. doi: 10.1039/d2cp01389d.
Interactions of molecules with solid surfaces are responsible for key functionalities in a range of currently actively pursued technologies, including heterogeneous catalysis for synthesis or decomposition of molecules, sensitization, surface functionalization and molecular doping, Modeling of such interactions is important, in particular, for the assignment of species and assignment and design of reaction pathways and ultimately for rational design of better functional materials for a range of applications. Key types of calculations involve calculations of adsorption structures and energies, electronic structures, charge transport, vibrational and optical spectra, and reaction dynamics. While some of these calculations are routinely doable for small-size models, other types of calculations, including anharmonic vibrational spectroscopy, accurate optical spectroscopy, quantum reaction dynamics, and calculations on large systems, are still too difficult to be routinely doable. In this Perspective, we specifically focus on issues related to computing accurate vibrational spectra including quantum effects and anharmonicity and coupling of key degrees of freedom. Vibrational spectroscopies are widely used for species assignment on surfaces but computations of vibrational spectra are still dominated by the harmonic approximation. We discuss approaches that can make accurate quantum anharmonic computational spectroscopy easier and enable its wider deployment in applications. We describe advantages and disadvantages of different techniques including perturbation theory, variational, vibrational self-consistent field and vibrational configuration interaction, as well as collocation which we argue has significant potential in this application, allowing computing accurate spectra directly from non-expensive data and with modest CPU cost. Examples of applications of anharmonic techniques to molecule-surface systems are given.
分子与固体表面的相互作用是一系列当前正在积极探索的技术中关键功能的基础，这些技术包括用于分子合成或分解的多相催化、敏化、表面功能化和分子掺杂。对这种相互作用进行建模非常重要，特别是对于确定物种、确定和设计反应途径，以及最终合理设计适用于一系列应用的性能更优的功能材料而言。关键的计算类型包括吸附结构和能量、电子结构、电荷传输、振动和光学光谱以及反应动力学的计算。虽然其中一些计算对于小尺寸模型来说可以常规进行，但其他类型的计算，包括非谐振动光谱、精确光学光谱、量子反应动力学以及对大型系统的计算，仍然太难而无法常规进行。在这篇综述中，我们特别关注与计算精确振动光谱相关的问题，包括量子效应、非谐性以及关键自由度的耦合。振动光谱广泛用于表面物种的确定，但振动光谱的计算仍然主要基于简谐近似。我们讨论了可以使精确的量子非谐计算光谱更简便并能在应用中更广泛应用的方法。我们描述了不同技术的优缺点，包括微扰理论、变分法、振动自洽场和振动组态相互作用，以及配置法，我们认为配置法在该应用中具有巨大潜力，它能够直接从成本不高的数据以适度的CPU成本计算出精确光谱。文中给出了非谐技术在分子 - 表面系统中的应用实例。
