Automated Construction of Potential Energy Surfaces Suitable to Describe Van Der Waals Complexes with Highly Excited Nascent Molecules: The Rotational Spectra of Ar-CS(V) and Ar-SiS(V)


Some reactions produce extremely hot nascent products which nevertheless can form sufficiently long-lived van der Waals (vdW) complexes - with atoms or molecules from a bath gas - as to be observed via microwave spectroscopy. Theoretical calculations of such unbound resonance states can be much more challenging than ordinary bound-state calculations depending on the approach employed. One encounters not just the floppy, and perhaps multiwelled potential energy surface (PES) characteristic of vdWs complexes, but in addition, one must contend with excitation of the intramolecular modes and its corresponding influence on the PES. Straightforward computation of the (resonance) rovibrational levels of interest, involves the added complication of the unbound nature of the wave function, often treated with techniques such as introducing a complex absorbing potential. Here, we have demonstrated that a simplified approach of making a series of vibrationally effective PESs for the intermolecular coordinates - one for each reaction product vibrational quantum number of interest - can produce vdW levels for the complex with spectroscopic accuracy. This requires constructing a series of appropriately weighted lower-dimensional PESs for which we use our freely available PES-fitting code AUTOSURF. The applications of this study are the Ar-CS and Ar-SiS complexes, which are isovalent to Ar-CO and Ar-SiO, the latter of which we considered in a previously reported study. Using a series of vibrationally effective PESs, rovibrational levels and predicted microwave transition frequencies for both complexes were computed variationally. A series of shifting rotational transition frequencies were also computed as a function of the diatom vibrational quantum number. The predicted transitions were used to guide and inform an experimental effort to make complementary observations. Comparisons are given for the transitions that are within the range of the spectrometer and were successfully recorded. Calculations of the rovibrational level pattern agree to within 0.2% with experimental measurements.



Research Center/Lab(s)

Center for High Performance Computing Research


U.S. Department of Energy, Grant CHE-1566266

International Standard Serial Number (ISSN)

1089-5639; 1520-5215

Document Type

Article - Journal

Document Version


File Type





© 2020 American Chemical Society (ACS), All rights reserved.

Publication Date

04 Jun 2020

PubMed ID