Vibrational spectroscopy by means of first‐principles molecular dynamics simulations

Abstract

Vibrational spectroscopy is one of the most important experimental techniques for the characterization of molecules and materials. Spectroscopic signatures retrieved in experiments are not always easy to explain in terms of the structure and dynamics of the studied samples. Computational studies are a crucial tool for helping to understand and predict experimental results. Molecular dynamics simulations have emerged as an attractive method for the simulation of vibrational spectra because they explicitly treat the vibrational motion present in the compound under study, in particular in large and condensed systems, subject to complex intramolecular and intermolecular interactions. In this context, first‐principles molecular dynamics (FPMD) has been proven to provide an accurate realistic description of many compounds. This review article summarizes the field of vibrational spectroscopy by means of FPDM and highlights recent advances made such as the simulation of Infrared, vibrational circular dichroism, Raman, Raman optical activity, sum frequency generation, and nonlinear spectroscopies. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Theoretical and Physical Chemistry > Spectroscopy Molecular and Statistical Mechanics > Molecular Mechanics Electronic Structure Theory > Density Functional Theory

Computational vibrational spectroscopy of molecule–surface interactions: what is still difficult and what can be done about it

“…Raman spectra and sum-frequency generation (SFG) spectra can also be computed based on the time-dependent polarizability tensor along the MD trajectory. 35 While MD includes effects of anharmonicity and environment, the accuracy is low due to the neglect of quantum effects and the scope is also very limited as overtones are neglected. The former point is important for a range of practically important reactions involving hydrogen atoms (including reactions of interest to hydrogen and direct alcohol fuel cells and for industrial synthesis of many economically important molecules, including fuels).…”

“…47 The classical MD approach is mostly used to compute spectra in liquids and for large molecules. 35 It has also been used to evaluate different machine learning (ML)-based methods to construct PESs. 48 It has been applied in a limited way to compute spectra at solid interfaces, for example (liquid) water on CaF 2 , 49 hydroxylated and (deuterated) water-covered alumina surface.…”

“…This drawback is particularly important in the presence of light atoms such as H, which includes a large fraction of practically important reactions (hydrocarbon synthesis, reactions important for fuel cells etc.). A PES is also necessary in this case unless the system is small enough and available CPU resources are substantial enough that ab initio MD (AIMD) 34,35 can be performed.…”

“…). A PES is also necessary in this case unless the system is small enough and available CPU resources are substantial enough that ab initio MD (AIMD) 34,35 can be performed.…”

The Local Vibrational Mode Theory and Its Place in the Vibrational Spectroscopy Arena

“…Over the past two decades, vibrational spectroscopy has developed into an important tool with ample applications in chemistry and beyond. − The number of available high precision measured and calculated vibrational spectra is constantly increasing thanks to rapidly advancing technologies and computational methods. To demonstrate this, in the following, some recent experimental and theoretical advances will be highlighted rather than giving a complete overview of this dynamic and complex field in all its breadth, which would be far beyond the scope of a feature article.…”