These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
main.pdf (9.18 MB)

The Necessity of Periodic Boundary Conditions for the Accurate Calculation of Crystalline Terahertz Spectra

submitted on 21.12.2020, 20:01 and posted on 24.12.2020, 10:52 by Peter Banks, Luke burgess, Michael Ruggiero
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.


American Chemical Society Petroleum Research Fund 61794-DNI10


Email Address of Submitting Author


University of Vermont


United States of America

ORCID For Submitting Author


Declaration of Conflict of Interest

No conflicts to declare