A full-dimensional ab initio intermolecular potential energy surface and rovibrational spectra for OC–HF and OC–DF

• Published in: The Journal of chemical physics 2021-08, Vol.155 (8), p.084302-084302
• Main Authors: Liu, Qiong, Liu, Lu, An, Feng, Huang, Jing, Zhou, Yanzi, Xie, Daiqian
• Format: Article
• Language: English
• Subjects: Algorithms; Clusters; Configurations; Coupling (molecular); Dipole moments; Eigenvectors; Energy of dissociation; Error correction; Free energy; Gaussian process; Heat of formation; Mathematical analysis; Multipoles; Potential energy; Representations
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0061291

We present a full-dimensional ab initio intermolecular potential energy surface (IPES) for the OC–HF van der Waals complex. 3167 ab initio points were computed at the frozen-core (FC) explicitly correlated coupled cluster [FC-CCSD(T)-F12b] level, with the augmented correlation-consistent polarized valence quadruple-zeta basis set plus bond functions. Basis set superposition error correction was also considered by the full counterpoise procedure. Gaussian process regression (GPR) was used to map out the potential energy surface, while a multipole expansion method was employed to smooth the ab initio noise of intermolecular potential in the long range. The global minimum of −1248.364 cm−1 was located at the linear configuration with the C atom pointing toward the H atom of the HF molecule. In addition, a local minimum of −602.026 cm−1 was found at another linear configuration with the O atom pointing toward the H atom of the HF molecule. The eigenstates were calculated on the vibrational averaged four-dimensional IPESs with the mixed radial discrete variable representation/angular finite basis representation method and Lanczos propagation algorithm. The dissociation energy D0 was calculated to be 701.827 cm−1, well reproducing the experimental value of 732 ± 2 cm−1. The dipole moment surfaces were also fitted by GPR from 3132 ab initio points calculated using the coupled cluster method [CCSD(T)] with AVTZ basis set plus bond functions. The frequencies and relative line intensities of rovibrational transitions in the HF (DF) and CO stretching bands were further calculated and compared well with the experimental results. These results indicate the high fidelity of the new IPES.