The pure rotational spectrum of ZnS (X1Σ+)

Zack, Lindsay N.; Ziurys, L. M.

doi:10.1016/j.jms.2009.08.009

Cited by 16 publications

(9 citation statements)

References 49 publications

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“…49. We then consider the independently selected best experimental values in the work of Dixon and co-workers, 23 67 Papakondylis, who used various theoretical methods to calculate the D e of ZnS, 68 pointed out that the aforementioned experimental papers used outdated values for the equilibrium bond lengths and frequencies as compared to more recent measurements, 69,70 bringing the older experimental measurements into doubt. Therefore, more experimental investigation into ZnS should be done to see if indeed the calculations are correct.…”

Section: Selection Of Best Values and Comparisons Of Ph-afqmc With Dfmentioning

confidence: 99%

“…For ZnS, the BDEs computed with QMC/MP2cbs, QMC/ CCcbs, and MR-CCSD(T) are all in excellent agreement, with a value roughly 15 kcal/mol below experiment, which is 49.1 ± 3 kcal/mol as suggested by de Oliveira-Filho and co-workers 7 and derived from the work of Marquat and Berkowitz 66 and de Maria et al 67 This experimental value is in stark contrast to the value of 34.3 ± 1.0 kcal/mol suggested by Truhlar and coworkers. 22 The latter value, as pointed out by de Oliveira-Filho and co-workers, 7 is derived from a thermochemical analysis by von Szentpaly, 68 which used theoretical, not experimental, values provided by Peterson et al 69 Papakondylis, who used various theoretical methods to calculate the D e of ZnS, 70 pointed out that the aforementioned experimental papers used outdated values for the equilibrium bond lengths and frequencies as compared to more recent measurements, 71,72 bringing the older experimental measurements into doubt. Therefore, more experimental investigation into ZnS should be done to see if indeed the calculations are correct.…”

Section: ■ Selection Of Best Values and Comparisons Of Ph-afqmc With ...mentioning

confidence: 99%

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On Achieving High Accuracy in Quantum Chemical Calculations of 3d Transition Metal-Containing Systems: A Comparison of Auxiliary-Field Quantum Monte Carlo with Coupled Cluster, Density Functional Theory, and Experiment for Diatomic Molecules

Shee

Rudshteyn

Arthur

et al. 2019

J. Chem. Theory Comput.

117

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The bond dissociation energies of a set of 44 3d transition metal-containing diatomics are computed with phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) utilizing a correlated sampling technique. We investigate molecules with H, N, O, F, Cl, and S ligands, including those in the 3dMLBE20 database first compiled by Truhlar and co-workers with calculated and experimental values that have since been revised by various groups. In order to make a direct comparison of the accuracy of our ph-AFQMC calculations with previously published results from 10 DFT functionals, CCSD(T), and icMR-CCSD(T), we establish an objective selection protocol which utilizes the most recent experimental results except for a few cases with well-specified discrepancies. With 1 arXiv:1901.09464v1 [physics.chem-ph] 27 Jan 2019 the remaining set of 41 molecules, we find that ph-AFQMC gives robust agreement with experiment superior to that of all other methods, with a mean absolute error (MAE) of 1.4(4) kcal/mol and maximum error of 3(3) kcal/mol (parenthesis account for reported experimental uncertainties and the statistical errors of our ph-AFQMC calculations).In comparison, CCSD(T) and B97, the best performing DFT functional considered here, have MAEs of 2.8 and 3.7 kcal/mol, respectively, and maximum errors in excess of 17 kcal/mol for both methods. While a larger and more diverse data set would be required to demonstrate that ph-AFQMC is truly a benchmark method for transition metal systems, our results indicate that the method has tremendous potential, exhibiting unprecedented consistency and accuracy compared to other approximate quantum chemical approaches.

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Section: Selection Of Best Values and Comparisons Of Ph-afqmc With Dfmentioning

confidence: 99%

Section: ■ Selection Of Best Values and Comparisons Of Ph-afqmc With ...mentioning

confidence: 99%

On Achieving High Accuracy in Quantum Chemical Calculations of 3d Transition Metal-Containing Systems: A Comparison of Auxiliary-Field Quantum Monte Carlo with Coupled Cluster, Density Functional Theory, and Experiment for Diatomic Molecules

Shee

Rudshteyn

Arthur

et al. 2019

J. Chem. Theory Comput.

117

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“…where A is Avogadro's number, ρ a is the atmospheric mass density, M a is the mean molecular weight of the atmosphere, Ω c is the collision integral of the condensing species with the main atmospheric components and is of order unity, and d is the collision diameter of the condensing species. We estimate the collision diameters for KCl and ZnS to be 2.67 Å and 2.0464 Å, respectively, from their equilibrium bond lengths (Sanderson 1976;Zack & Ziurys 2009). Abundances of the condensates, KCl and ZnS, are assumed to correspond to those of K and Zn at the designated metallicities, as they are both the limiting element in their molecules.…”

Section: Microphysical Properties Of Kcl and Znsmentioning

confidence: 99%

Microphysics of KCl and ZnS Clouds on GJ 1214 b

Gao

Benneke

2018

ApJ

106

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Clouds in the atmospheres of exoplanets confound characterization efforts by reducing, eliminating, and distorting spectral signatures of molecular abundances. As such, interpretations of exoplanet spectra strongly depend on the choice of cloud model, many of which are highly simplified and lack predictive power. In this work, we use a cloud model that treat microphysical processes to simulate potassium chloride (KCl) and zinc sulfide (ZnS) clouds in the atmosphere of the super Earth GJ 1214 b and how they vary as a function of the strength of vertical mixing and the atmospheric metallicity. Microphysical processes control the size and spatial distribution of cloud particles, allowing for the computation of more physical cloud distributions than simpler models. We find that the mass and opacity of KCl clouds increase with mixing strength and metallicity, with the particle size and spatial distribution defined by nucleation, condensation, evaporation, and transport timescales. ZnS clouds cannot form without the presence of condensation nuclei, while heterogeneous nucleation of ZnS on KCl reduces particle sizes compared to pure KCl cases. In order to explain the flat transmission spectrum of GJ 1214b with homogeneously nucleated KCl clouds, the atmospheric metallicity must be at least 1000 × solar, and the eddy diffusivity must be at least 10 10 cm 2 s −1 . We predict that JWST observations of GJ 1214 b may reveal the presence of methane, carbon monoxide, and water, allowing for constraints to be placed on atmospheric metallicity and C/O ratio.

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“…The r m As shown in the table, the zinc-sulfur bond length is ∼0.2 Å longer than that of ZnS, which has r e = 2.0464(1) Å. 37 The presence of the unpaired electron in ZnSH, which, as will be discussed, resides principally on the zinc nucleus, appears to lengthen the metal-sulfur bond. This result suggests that the unpaired electron in ZnSH is added to a partly antibonding orbital.…”

Section: A Structure Of Znshmentioning

confidence: 90%

Examining transition metal hydrosulfides: The pure rotational spectrum of ZnSH (X̃2A′)

Bucchino

Adande

Halfen

et al. 2017

The Journal of Chemical Physics

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The pure rotational spectrum of the ZnSH (X̃A') radical has been measured using millimeter-wave direct absorption and Fourier transform microwave (FTMW) methods across the frequency range 18-468 GHz. This work is the first gas-phase detection of ZnSH by any spectroscopic technique. Spectra of the ZnSH,ZnSH, and ZnSD isotopologues were also recorded. In the mm-wave study, ZnSH was synthesized in a DC discharge by the reaction of zinc vapor, generated by a Broida-type oven, with HS; for FTMW measurements, the radical was made in a supersonic jet expansion by the same reactants but utilizing a discharge-assisted laser ablation source. Between 7 and 9 rotational transitions were recorded for each isotopologue. Asymmetry components with K = 0 through 6 were typically measured in the mm-wave region, each split into spin-rotation doublets. In the FTMW spectra, hyperfine interactions were also resolved, arising from the hydrogen or deuterium nuclear spins of I = 1/2 or I = 1, respectively. The data were analyzed using an asymmetric top Hamiltonian, and rotational, spin-rotation, and magnetic hyperfine parameters were determined for ZnSH, as well as the quadrupole coupling constant for ZnSD. The observed spectra clearly indicate that ZnSH has a bent geometry. The r structure was determined to be r = 2.213(5) Å, r = 1.351(3) Å, and θ = 90.6(1)°, suggesting that the bonding occurs primarily through sulfur p orbitals, analogous to HS. The hyperfine constants indicate that the unpaired electron in ZnSH primarily resides on the zinc nucleus.

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The pure rotational spectrum of ZnS (X1Σ+)

Cited by 16 publications

References 49 publications

On Achieving High Accuracy in Quantum Chemical Calculations of 3d Transition Metal-Containing Systems: A Comparison of Auxiliary-Field Quantum Monte Carlo with Coupled Cluster, Density Functional Theory, and Experiment for Diatomic Molecules

On Achieving High Accuracy in Quantum Chemical Calculations of 3d Transition Metal-Containing Systems: A Comparison of Auxiliary-Field Quantum Monte Carlo with Coupled Cluster, Density Functional Theory, and Experiment for Diatomic Molecules

Microphysics of KCl and ZnS Clouds on GJ 1214 b

Examining transition metal hydrosulfides: The pure rotational spectrum of ZnSH (X̃2A′)

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