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arXiv · 1008.4163

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

Amir Karton·Jan M. L. Martin
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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 (ω_e), 0.20 cm^{-1} for the first anharmonicity constants (ω_e x_e), 0.10 cm^{-1} for the second anharmonicity constants (ω_e y_e), and 0.001 cm^{-1} for the vibration-rotation coupling constants (α_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, ω_e, and ω_e x_e, in particular they universally increase r_e (by up to 0.5 pm), universally reduce ω_e (by up to 32 cm^{-1}), and universally increase ω_e x_e (by up to 1 cm^{-1}). Connected quintuple excitations, \hat{T}_5, are spectroscopically significant for ω_e of the nonhydride systems, affecting ω_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 (μ), polarizabilities (α), and first hyperpolarizabilities (β) is evaluated.

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Amir Karton, Jan M. L. Martin. 2010-08-24. Performance of W4 theory for spectroscopic constants and electrical properties of small molecules. https://doi.org/10.1063/1.3489113

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