High-level ab initio predictions for the ionisation energy, bond dissociation energies and heats of formation of zirconium oxide and its cation (ZrO/ZrO+)

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Detail(s)

Original languageEnglish
Pages (from-to)2709-2718
Journal / PublicationMolecular Physics
Volume116
Issue number19-20
Online published1 Mar 2018
Publication statusPublished - 2018

Abstract

The ionisation energy (IE) of ZrO, the bond dissociation energies (D0s) and the heats of formation at 0 K (ΔHf  0K ) and 298 K (ΔH 298K ) for ZrO/ZrO+ are predicted by the coupled cluster methods utilizing upto single, double, triple and quadruple excitations and complete basis set limit approximation (CCSDTQ/CBS). The CCSDTQ/CBS approach also includes the zero-point vibrational energy, high-order correlation, core-valence (CV) electronic and spin-orbit coupling corrections while the scalar relativistic contribution is handled by employing pseudopotential basis sets. The present calculations yield IE(ZrO) = 6.794 eV and D0(Zr+–O) − D0(Zr–O) = −0.193 eV which are in good agreement with the respective experimental values of 6.81272(10) eV and −0.1788(1) eV determined in a two-colour laser-pulsed field ionisation-photoelectron study. The CCSD(T) and multireference configuration interaction (MRCI) methods with CV correlations included give equally remarkable predictions of the harmonic frequencies and the bond lengths for ZrO/ZrO+. This study together with the previous investigations has demonstrated that, with pseudopotential basis sets, the CCSDTQ/CBS protocol can be readily extended to investigate 4d-transition metal-containing diatomic molecules to yield comparable accuracy (±20 meV) to that achieved in the IE and D0 predictions of 3d-transition metal-containing species.

Research Area(s)

  • Ab initio, bond dissociation energy, heat of formation, ionisation energy, thermochemical

Citation Format(s)

High-level ab initio predictions for the ionisation energy, bond dissociation energies and heats of formation of zirconium oxide and its cation (ZrO/ZrO+). / Lam, Chow-Shing; Lau, Kai-Chung; Ng, Cheuk-Yiu.

In: Molecular Physics, Vol. 116, No. 19-20, 2018, p. 2709-2718.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review