Issue 36, 2021

The necessity of periodic boundary conditions for the accurate calculation of crystalline terahertz spectra

Abstract

Terahertz vibrational spectroscopy has emerged as a powerful spectroscopic technique, providing valuable information regarding long-range interactions – and associated collective dynamics – occurring in solids. However, the terahertz sciences are relatively nascent, and there have been significant advances over the last several decades that have profoundly influenced the interpretation and assignment of experimental terahertz spectra. Specifically, because there do not exist any functional group or material-specific terahertz transitions, it is not possible to interpret experimental spectra without additional analysis, specifically, computational simulations. Over the years simulations utilizing periodic boundary conditions have proven to be most successful for reproducing experimental terahertz dynamics, due to the ability of the calculations to accurately take long-range forces into account. On the other hand, there are numerous reports in the literature that utilize gas phase cluster geometries, to varying levels of apparent success. This perspective will provide a concise introduction into the terahertz sciences, specifically terahertz spectroscopy, followed by an evaluation of gas phase and periodic simulations for the assignment of crystalline terahertz spectra, highlighting potential pitfalls and good practice for future endeavors.

Graphical abstract: The necessity of periodic boundary conditions for the accurate calculation of crystalline terahertz spectra

Supplementary files

Article information

Article type
Perspective
Submitted
03 ጁን 2021
Accepted
08 ሴፕቴ 2021
First published
08 ሴፕቴ 2021

Phys. Chem. Chem. Phys., 2021,23, 20038-20051

Author version available

The necessity of periodic boundary conditions for the accurate calculation of crystalline terahertz spectra

P. A. Banks, L. Burgess and M. T. Ruggiero, Phys. Chem. Chem. Phys., 2021, 23, 20038 DOI: 10.1039/D1CP02496E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements