The sub-millimeter and Fourier transform microwave spectrum of HZnCl (X 1Σ+)

Pulliam, R. L.; Sun, Ming; Flory, M. A.; Ziurys, L. M.

doi:10.1016/j.jms.2009.07.001

Cited by 6 publications

(7 citation statements)

References 20 publications

(36 reference statements)

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“…Among these systems, compounds containing a metal−carbon bond, like Grignard reagents, are of high preparative value as they can functionalize C−H or C−F bonds. Whereas, in the gas phase, Grignard reagents have not been observed, except for a similar compound H−Zn−Cl, , inserted transition metal ions have been prepared and characterized . Also, insertion mechanisms have often been shown to drive direct reactions of halogen-containing compounds with metals …”

Section: Introductionmentioning

confidence: 99%

Reactions of Laser-Ablated Zirconium Atoms within a Supersonic Expansion: Insertion versus Radical Mechanism

Soorkia¹,

Pothier²,

Mestdagh³

et al. 2010

J. Phys. Chem. A

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In a laser ablation type microreactor followed by supersonic expansion, zirconium atoms have been reacted with methyl fluoride, CH(3)F (MeF), and mixtures of MeF and dimethylether, CH(3)-O-CH(3) (DME) seeded in He. With both mixtures, only a number of simple fluorinated products are formed, and they have been identified by one-photon ionization. All products can be linked to radical reactions either with F atoms, CH(3), or ZrF(1, 2, 3) radicals. No insertion products of the Grignard reagent type, F -Zr-CH(3) could be identified with or in the absence of DME. On the other hand, evidence has been found for the presence of organometallic compounds of the type ZrC(2)H(n=2, 4, 6), which could result from radical attack. Thus, even in conditions where intense solvation is at work, induced by clustering with polar DME molecules, which can act as stabilizing agents, a direct insertion mechanism into the C-F bond involving barrier suppression is not at work in our conditions. The reactivity due to radicals is very effective in this type of reactor, and the products that are efficiently formed can be quickly stabilized in the expansion. The radical attack supersedes, in the case of zirconium solvated by DME, the metastable mechanism with Zr(4d)(3)(5s)(1), that is certainly energetically impossible in the absence of strong reaction barrier suppression by a solvent. High level ab initio calculations performed at the CASPT2 level of theory are used for characterizing the electronic and geometric structure of the inserted products. They also reveal striking features of the reaction mechanism that support the absence of observation of inserted products within solvated clusters of zirconium.

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Section: Introductionmentioning

confidence: 99%

Reactions of Laser-Ablated Zirconium Atoms within a Supersonic Expansion: Insertion versus Radical Mechanism

Soorkia¹,

Pothier²,

Mestdagh³

et al. 2010

J. Phys. Chem. A

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“…The rotational constant B 000 ) 0.3540 cm -1 , from variational calculations, is coherent with B e ) 0.3561 cm -1 from the calculated equilibrium geometry. These values are twice larger than B 000 ) 0.162 031 25 and 0.163 397 060 cm -1 for H 64 Zn 35 Cl measured by Yu et al 12 and Pulliam et al, 13 respectively.…”

Section: Comparison Between Hznf and Hznclmentioning

confidence: 58%

“…The electronic structure and spectroscopic properties of the ground state of HZnF have been revealed for the first time in this study, based on its potential energy surface obtained at the MRCI+Q and CCSD(T) levels. Our results have been compared with those of the close system HZnCl, which were reported in recent works. − Even though we focus on the X 1 Σ + electronic ground state, many excited states should be included in the MCSCF calculations. For this ionic molecule, it is essential to take into account the interactions between the close lying states for an accurate description, indeed, this process has required many computational efforts.…”

Section: Discussionmentioning

confidence: 97%

“…Our results have been compared with those of the close system HZnCl, which were reported in recent works. [12][13][14] Even though we focus on the X 1 Σ + electronic ground state, many excited states should be included in the MCSCF calculations. For this ionic molecule, it is essential to take into account the interactions between the close lying states for an accurate description, indeed, this process has required many computational efforts.…”

Section: Discussionmentioning

confidence: 99%

“… a Taken from ref , calculated at the RCCSD(T)/cc-pVTZ level. b Taken from ref , from the rotational spectrum. c Taken from ref , from high resolution infrared emission spectrum. d Taken from ref , extrapolated D 0 value. e Taken from ref , extrapolated D 0 value. f Taken from ref . g Taken from ref , calculated at the MRCI+Q level, using the atomic pseudopotentials for Zn and F with the associated aug-cc-pVQZ basis sets. h Taken from ref , from the rotational spectrum. i Taken from ref , from the rotational spectrum. …”

Section: Discussionmentioning

confidence: 99%

See 2 more Smart Citations

Ab initio Study of HZnF

2009

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On the basis of highly correlated ab initio calculations, an accurate determination of the electronic structure and of the rovibrational spectroscopy has been performed for the electronic ground state of the HZnF system. Using effective core pseudopotentials for the Zn and F atoms and associated aug-cc-pVQZ basis sets, we have calculated, at the multireference configuration interaction level including the Davidson correction, the three-dimensional potential energy surface of the X(1)Sigma(+) ground state. The rovibrational energy levels have been obtained variationally, and the results have been discussed and compared with existing experimental data on the ground state of the close system HZnCl, which exhibits a complicated vibration-rotation spectrum. Our analysis shows that the nature of the H-ZnF bond is quite similar to that of the H-ZnCl bond, according to their bond lengths, harmonic frequencies of the H-Zn stretching mode, and dissociation energies into H and ZnF/ZnCl. The ab initio study of the electronic ground and excited states of ZnH and ZnH(+) are also presented using similar level of calculations. Characteristic constants are given for the first bounded electronic states correlating to the first two dissociation asymptotes of the neutral and ionic diatomics.

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Inorganic Molecules without Carbon Atoms

Vogt

2019

Structure Data of Free Polyatomic Molecules

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The sub-millimeter and Fourier transform microwave spectrum of HZnCl (X 1Σ+)

Cited by 6 publications

References 20 publications

Reactions of Laser-Ablated Zirconium Atoms within a Supersonic Expansion: Insertion versus Radical Mechanism

Reactions of Laser-Ablated Zirconium Atoms within a Supersonic Expansion: Insertion versus Radical Mechanism

Ab initio Study of HZnF

Inorganic Molecules without Carbon Atoms

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