High Accuracy Ab Initio Potential Energy Curves and Dipole Moment Functions for the X 1Σ+ and a 3Π Spin States of the CF+ Diatomic Molecule

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-01, Vol.128 (3), p.539-547
• Main Authors: McCarver, Gavin A., Hinde, Robert J.
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.3c04517

Potential energy curves and dipole moment functions constructed using high-accuracy ab initio methods allow for an in-depth examination of the electronic structure of diatomic molecules. Ab initio computations serve as a valuable complement to experimental data, offering insights into the nature of short-lived molecules such as those encountered within the interstellar medium (ISM). While laboratory experiments provide critical groundwork, the ISM’s conditions often permit longer lifetimes for lower stability molecules, enabling unique observations. The CF+ diatomic molecule is one such molecule that has been observed spectroscopically in the ISM. Previous experimental and theoretical work have examined different spectroscopic aspects of the CF+ molecule, but the development of newer, more complete potential energy curves and dipole moment functions allows for even greater insight. We constructed both potential energy curves and dipole moment functions for the ground X 1Σ+ and first excited a 3Π states of CF+ for both the 12C and 13C isotopologues. The potential energy curves were constructed using coupled cluster with single, double, and perturbative triple excitations (CCSD­(T)) at the complete basis set limit with corrections from full triple, quadruple, quintuple, and hextuple excitations within a finite-basis coupled cluster wave function as well as corrections from full configuration interaction and relativistic effects. Rovibrational wave functions were calculated using a vibrational Hamiltonian matrix, which moves beyond the harmonic oscillator approximation. The equilibrium bond length, vibrational constant, and rotational constant were reproduced to within 0.00013 Å, 0.28 cm–1, and 0.00045 cm–1, respectively, of experimental values. Experimental transition energies from rovibrational spectra were reproduced with an error of no larger than 0.63 cm–1. The triplet excited state (a 3Π) was found to have a longer equilibrium bond length at 1.21069 Å, a vibrational constant of 1611.29 cm–1, and a rotational constant of 1.56376 cm–1. Rovibrational line lists for the 12C and 13C isotopologues for both the X 1Σ+ and the excited a 3Π states were generated.