Effects of relativity on the NiCO, PdCO, and PtCO bonding mechanism: a constrained space orbital variation analysis of density functional results

Chung, Sai‐Cheong; Krüger, Sven; Ruzankin, Sergey Ph.; Pacchioni, Gianfranco; Rösch, Notker

doi:10.1016/0009-2614(95)01273-7

Cited by 37 publications

(27 citation statements)

References 26 publications

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“…In the first place, r(PdC) is much larger than r(PtC) in PtCO. This was predicted 6,13 and is the result of relativistic effects on Pt in PtCO. A parallel phenomenon occurs in OCAgX and OCAuX (X ) F, Cl, and Br), where r(AgC) > r(AuC), this time because of relativistic effects on Au in OCAuX.…”

Section: Ground-state Average (R Z ) and Estimated Equilibrium (Rmentioning

confidence: 80%

“…Because I( 105 Pd) ) 5 / 2 , the transitions of 105 PdCO showed hyperfine structure arising from nuclear quadrupole coupling and nuclear spin-rotation coupling. No hyperfine structure attributable to 13 C was observed. In total, data were collected from three J′-J′′ transitions for 15 isotopomers.…”

Section: Assigned Spectra and Analysismentioning

confidence: 85%

“…The intensity of the observed spectral lines was found to be uniform over this concentration range. In order that experiments could be conducted on complexes containing 18 O and/or 13 C isotopes, isotopically enriched samples of 13 CO and C 18 O were employed.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…2 The interactions within gas-phase PdCO are prototypes for those between a Pd surface and CO, and consequently, the PdCO molecule has been the subject of many theoretical studies. [3][4][5][6][7][8][9][10][11][12][13][14][15] The infrared spectrum of PdCO isolated in krypton was reported by Darling et al 16 in 1973. Following this work, many groups have applied theoretical methods to examine aspects of the electronic structure of PdCO.…”

Section: Introductionmentioning

confidence: 99%

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Microwave Spectrum, Geometry, and Hyperfine Constants of PdCO

2002

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The pure rotational spectrum of palladium monocarbonyl, PdCO, has been measured between 6000 and 24 000 MHz using a cavity pulsed jet Fourier transform microwave spectrometer. The molecules were prepared by laser ablation of Pd in the presence of CO contained in an Ar backing gas. The spectra of 15 isotopomers have been used to determine the molecular geometry from the measured rotational constants. Centrifugal distortion constants are in good agreement with those calculated from a literature harmonic force field. A nuclear quadrupole coupling constant and nuclear spin-rotation constant have been determined for 105 Pd. Nuclear shielding parameters have been evaluated from the measured spin-rotation constant. The geometry is discussed with reference to theoretical data and to other molecules containing an M-CO bond.

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Section: Ground-state Average (R Z ) and Estimated Equilibrium (Rmentioning

confidence: 80%

Section: Assigned Spectra and Analysismentioning

confidence: 85%

Section: Experimental Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Microwave Spectrum, Geometry, and Hyperfine Constants of PdCO

2002

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“…Such an approach has been validated within the framework of DFT, [104,[109][110][111][112] and has recently been extended to pseudopotential calculations on monohydrate cations of heavy elements. [29,55] With such an energy decomposition, it can a priori be clearly established what is the dominant origin of the complexation energy; this makes then possible to characterize the complex as a covalent (E 2 is the largest component in this case) or as an electrostatic (E 1 is the largest component) species.…”

Section: Wherementioning

confidence: 99%

Understanding Lead Chemistry from Topological Insights: The Transition between Holo‐ and Hemidirected Structures within the [Pb(CO)_n]²⁺ Model Series

Gourlaouen

Gérard

Piquemal

et al. 2008

Chemistry A European J

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In this contribution, we focus to the currently unknown [Pb(CO)(n)](2+) model series (n=1 to 10), a set of compounds which allows us to investigate in-depth the holo- and hemidirectional character that lead complexes can exhibit. By means of DFT computations performed using either relativistic four-component formalisms coupled to all-electron basis sets for [Pb(CO)](2+), [Pb(OC)](2+) and [Pb(CO)(2)](2+), or scalar relativistic pseudopotentials for higher n values, the structure and the energetics of these species are investigated. The results are complemented by Constrained Space Orbital Variations (CSOV) and Electron Localization Function (ELF) comprehensive analyses in order to get better insights into the poorly documented chemical fundamentals of the Pb(2+) cation. Whereas the discrimination between holo- and hemidirected structures is usually done according to the geometry, we here provide a quantitative indicator grounded on (V(Pb)), the mean charge density of the valence monosynaptic V(Pb) ELFic basin associated to the metal cation. Free-enthalpy relying discussions show, moreover, that those gas-phase complexes having n=7, 8 or 9 may be experimentally instable and should dissociate into [Pb(CO)(6)](2+) and a number of CO ligands. According to second-order differences in energy, it is anticipated that the n=3 or 6 structures should be the most probable structures in the gas phase. Gathering all data from the present theoretical study allows us to propose some concepts that the versatile structural chemistry of Pb(2+) complexes could rely on.

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Scalar-relativistic LCGTO DFT calculations for atoms using the Douglas-Kroll transformation

Boettger

1997

Int. J. Quant. Chem.

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ABSTRACT:Haberlen and Rosch HR demonstrated Chem. Phys. Lett. 199, 491Ž.x Ž . 1992 the feasibility of performing scalar-relativistic, density functional theory DFT Ž . linear combination of Gaussian-type orbitals᎐fitting function LCGTO-FF calculations on clusters of atoms using an ''incomplete'' Douglas᎐Kroll transformation. Some of the approximations used in their multiatom calculations have not yet been fully explored for isolated atoms, especially the neglect of matrix elements involving vector products of the momentum and the use of fitting functions. In this investigation, scalar-relativistic Ž . LCGTO calculations without fitting functions were carried out at four levels of approximation, including that employed by HR, for four atoms: Ce, Au, Pb, and Pu. The results of these calculations suggest that the HR approximation should be applicable to atoms through the light actinides, so long as spin᎐orbit effects are unimportant. A comparison of very large basis-set results with results obtained using ordinary-size basis Ž . sets indicates that the valence bonding states from scalar-relativistic LCGTO-FF calculations should be no more sensitive to the orbital basis-set size than are their nonrelativistic counterparts.

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Effects of relativity on the NiCO, PdCO, and PtCO bonding mechanism: a constrained space orbital variation analysis of density functional results

Cited by 37 publications

References 26 publications

Microwave Spectrum, Geometry, and Hyperfine Constants of PdCO

Microwave Spectrum, Geometry, and Hyperfine Constants of PdCO

Understanding Lead Chemistry from Topological Insights: The Transition between Holo‐ and Hemidirected Structures within the [Pb(CO)_n]²⁺ Model Series

Scalar-relativistic LCGTO DFT calculations for atoms using the Douglas-Kroll transformation

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Effects of relativity on the NiCO, PdCO, and PtCO bonding mechanism: a constrained space orbital variation analysis of density functional results

Cited by 37 publications

References 26 publications

Microwave Spectrum, Geometry, and Hyperfine Constants of PdCO

Microwave Spectrum, Geometry, and Hyperfine Constants of PdCO

Understanding Lead Chemistry from Topological Insights: The Transition between Holo‐ and Hemidirected Structures within the [Pb(CO)n]2+ Model Series

Scalar-relativistic LCGTO DFT calculations for atoms using the Douglas-Kroll transformation

Contact Info

Product

Resources

About

Understanding Lead Chemistry from Topological Insights: The Transition between Holo‐ and Hemidirected Structures within the [Pb(CO)_n]²⁺ Model Series