Performance of W4 theory for spectroscopic constants and electrical properties of small molecules

TL;DR

This study demonstrates that W4 and post-W4 quantum chemical theories can accurately predict spectroscopic constants and electrical properties of small molecules, with systematic improvements from higher-order excitations.

Contribution

The paper provides comprehensive validation of W4 theory's accuracy for small molecules and explores the effects of higher-order excitations on spectroscopic and electrical properties.

Findings

W4 theory achieves near-spectroscopic accuracy for diatomic molecules.

Higher-order connected quadruple excitations significantly affect predicted properties.

Post-CCSD(T) effects are crucial for electrical property predictions.

Abstract

Accurate spectroscopic constants and electrical properties of small molecules are determined by means of W4 and post-W4 theories. For a set of 28 first- and second-row diatomic molecules for which very accurate experimental spectroscopic constants are available, W4 theory affords near-spectroscopic or better predictions. Specifically, the root-mean-square deviations (RMSD) from experiment are 0.04 pm for the equilibrium bond distances (r_e), 1.03 cm^{-1} for the harmonic frequencies (\omega_e), 0.20 cm^{-1} for the first anharmonicity constants (\omega_e x_e), 0.10 cm^{-1} for the second anharmonicity constants (\omega_e y_e), and 0.001 cm^{-1} for the vibration-rotation coupling constants (\alpha_e). Higher-order connected triples, \hat{T}_3-(T), improve agreement with experiment for the hydride systems, but their inclusion (in the absence of \hat{T}_4) tends to worsen agreement with experiment for the nonhydride systems. Connected quadruple excitations, \hat{T}_4, have significant and systematic effects on r_e, \omega_e, and \omega_e x_e, in particular they universally increase r_e (by up to 0.5 pm), universally reduce \omega_e (by up to 32 cm^{-1}), and universally increase \omega_e x_e (by up to 1 cm^{-1}). Connected quintuple excitations, \hat{T}_5, are spectroscopically significant for \omega_e of the nonhydride systems, affecting \omega_e by up to 4 cm^{-1}. The triatomic molecules H_2O, CO_2, and O_3, as well as the pathologically multireference BN and BeO diatomics, are also considered. The asymmetric stretch of ozone represents a severe challenge to W4 theory, in particular the connected quadruple contribution converges very slowly with the basis set size. Finally, the importance of post-CCSD(T) correlation effects for electrical properties, namely dipole moments (\mu), polarizabilities (\alpha), and first hyperpolarizabilities (\beta) is evaluated.