Multi-isotopologue analyses of new vibration–rotation and pure rotation spectra of ZnH and CdH

Shayesteh, Alireza; Roy, Robert J. Le; Varberg, Thomas D.; Bernath, Peter F.

doi:10.1016/j.jms.2006.03.004

Cited by 22 publications

(8 citation statements)

References 57 publications

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“…The electronic structure of ZnH and CdH has been investigated both experimentally − and theoretically. , Here, the vertical excitation energies (VEEs) of ZnH and CdH were calculated at their experimental equilibrium bond distances ( R e ) of 1.593478 Å and 1.7805 Å, respectively. The aug-cc-pVTZ-DK , and AVTZ , basis sets were used for ZnH and CdH, respectively, to describe the excited states with Rydberg characters.…”

Section: Resultsmentioning

confidence: 99%

Performance of TD-DFT for Excited States of Open-Shell Transition Metal Compounds

Suo

Shen

et al. 2017

J. Phys. Chem. A

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Time-dependent density functional theory (TD-DFT) has been very successful in accessing low-lying excited states of closed-shell systems. However, it is much less so for excited states of open-shell systems: unrestricted Kohn-Sham based TD-DFT (U-TD-DFT) often produces physically meaningless excited states due to heavy spin contaminations, whereas restricted Kohn-Sham based TD-DFT often misses those states of lower energies. A much better variant is the explicitly spin-adapted TD-DFT (X-TD-DFT) [J. Chem. Phys. 2011, 135, 194106] that can capture all the spin-adapted singly excited states yet without computational overhead over U-TD-DFT. While the superiority of X-TD-DFT over U-TD-DFT has been demonstrated for open-shell systems of main group elements, it remains to be seen if this is also the case for open-shell transition metal compounds. Taking as benchmark the results by MS-CASPT2 (multistate complete active space second-order perturbation theory) and ic-MRCISD (internally contracted multireference configuration interaction with singles and doubles), it is shown that X-TD-DFT is indeed superior to U-TD-DFT for the vertical excitation energies of ZnH, CdH, ScH, YH, YO, and NbO. Admittedly, there exist a few cases where U-TD-DFT appears to be better than X-TD-DFT. However, this is due to a wrong reason: the underestimation (due to spin contamination) and the overestimation (due to either the exchange-correlation functional itself or the adiabatic approximation to the exchange-correlation kernel) happen to be compensated in the case of U-TD-DFT. As for [Cu(CH)], which goes beyond the capability of both MS-CASPT2 and ic-MRCISD, X-TD-DFT revises the U-TD-DFT assignment of the experimental spectrum.

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Section: Resultsmentioning

confidence: 99%

Performance of TD-DFT for Excited States of Open-Shell Transition Metal Compounds

Suo

Shen

et al. 2017

J. Phys. Chem. A

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“…In many cases, incorrect ground states are predicted at the Hartree-Fock level, but inclusion of electron correlation effects at the CCSD͑T͒ level reverses the ordering and yields the correct known ground states. For each hydride, Table VII compares the optimized bond length to experiment [50][51][52][53][54][55][56][57][58][59] at both the CCSD͑T͒/G3Large and BD͑T͒/G3Large ͑both with and without the inclusion of scalar relativistic effects͒ levels of theory. The table also lists ͗S 2 ͘ values.…”

Section: Geometriesmentioning

confidence: 99%

Toward accurate thermochemical models for transition metals: G3Large basis sets for atoms Sc–Zn

Mayhall

Raghavachari

Redfern

et al. 2008

The Journal of Chemical Physics

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An augmented valence triple-zeta basis set, referred to as G3Large, is reported for the first-row transition metal elements Sc through Zn. The basis set is constructed in a manner similar to the G3Large basis set developed previously for other elements (H-Ar, K, Ca, Ga-Kr) and used as a key component in Gaussian-3 theory. It is based on a contraction of a set of 15s13p5d Gaussian primitives to 8s7p3d, and also includes sets of f and g polarization functions, diffuse spd functions, and core df polarization functions. The basis set is evaluated with triples-augmented coupled cluster [CCSD(T)] and Brueckner orbital [BD(T)] methods for a small test set involving energies of atoms, atomic ions, and diatomic hydrides. It performs well for the low-lying s-->d excitation energies of atoms, atomic ionization energies, and the dissociation energies of the diatomic hydrides. The Brueckner orbital-based BD(T) method performs substantially better than Hartree-Fock-based CCSD(T) for molecules such as NiH, where the starting unrestricted Hartree-Fock wavefunction suffers from a high degree of spin contamination. Comparison with available data for geometries of transition metal hydrides also shows good agreement. A smaller basis set without core polarization functions, G3MP2Large, is also defined.

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“…A number of zinc-containing molecules have been studied with gas-phase high-resolution spectroscopy. ZnH has been investigated using electronic, vibrational, and rotational methods (see [3] and references therein). Vibrational transitions of HZnCl [4] and ZnH 2 [5] have been measured, and ZnCH 3 [6] has been studied with electronic spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

The pure rotational spectrum of ZnCl (X2Σ+): Variations in zinc halide bonding

Tenenbaum

Flory

Pulliam

et al. 2007

Journal of Molecular Spectroscopy

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Multi-isotopologue analyses of new vibration–rotation and pure rotation spectra of ZnH and CdH

Cited by 22 publications

References 57 publications

Performance of TD-DFT for Excited States of Open-Shell Transition Metal Compounds

Performance of TD-DFT for Excited States of Open-Shell Transition Metal Compounds

Toward accurate thermochemical models for transition metals: G3Large basis sets for atoms Sc–Zn

The pure rotational spectrum of ZnCl (X2Σ+): Variations in zinc halide bonding

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