Théorie du champ de ligands | EPFL Graph Search

La théorie du champ de ligands ou modèle du champ de ligands décrit la liaison chimique, l'arrangement des orbitales et certaines autres caractéristiques de complexes de coordination impliquant un ion d'un métal de transition. Ce concept a été introduit en 1957 par Griffith et Orgel comme une description des complexes de métaux de transition plus exacte que celle proposée par la théorie du champ cristallin. Il applique cette dernière aux ions de métaux de transition en solution et fait appel à la théorie de l'orbitale moléculaire pour expliquer les différences d'interactions métal-ligand, et notamment la levée de dégénérescence des orbitales atomiques d dans de tels complexes. L'article de Griffith et Orgel explique les différences de couleurs des complexes de métaux de transition par l'occupation différente des orbitales de la sous-couche d incomplète : dans la mesure où les orbitales inoccupées participent aux liaisons avec les ligands, ces liaisons ont une influence sur les longueur

Organometallics versus P4 Complexes of Group 11 Cations: Periodic Trends and Relativistic Effects in the Involvement of (n-1)d, ns, and np Orbitals in Metal-Ligand Interactions

Hui-Chung Tai

The nature of the bonding in ethylene and h2-P4 complexes, M(C2H4)2+ and M(h2-P4)2+, of group 11 metal cations (M = Cu, Ag, Au) has been explored by d. functional calcns. On the basis of the evaluation of symmetry orbitals, the contributions from the interactions of ligand orbitals with metal ns, np, and (n-1)d orbitals have been investigated. The anal. shows that the metal-ligand bonds in the organometallics and phosphorus complexes fit to a unified scheme, whereas traditional concepts such as the isolobality principle would hardly predict such a bonding analogy between C2H4 and P4 complexes. Bond energies increasing in the order Ag < Cu < Au have been predicted. The stronger metal-ligand bonds in the gold(I) compds. compared to those in the silver(I) compds. can be elucidated by the relativistic stabilization of the orbital interactions, particularly of those involving 6s and 5d orbitals. The stronger metal-ligand bonds in Cu(h2-P4)2+ compared to those in the exptl. known Ag(h2-P4)2+ can be attributed partly to the strong back-donation from metal 3d orbitals to vacant ligand orbitals. This result stands in sharp contrast to the common belief that first-row transition metals form weaker bonds to ligands than do their second-row analogs because of a comparably small overlap between ligand orbitals and metal 3d orbitals. [on SciFinder (R)]

2004

Crystalline and correlated phases in two-dimensional transition metal dichalcogenides

Diego José Pasquier

This thesis is dedicated to the study of various aspects of the electronic structure of two-dimensional transition metal dichalcogenides (TMDs) of chemical composition MX

_2

(where M is a transition metal atom and X= S, Se, Te), using a combination of \textit{ab inito} density-functional methods. We first address the relative stability of the

1T

and

1H

phases of two-dimensional TMDs as a function of the column of the transition metal atom in the periodic table. Using a Wannier-function approach, we calculate crystal field and ligand field parameters for a broad range of members of this family of materials. Taking TaS

_2

as an example, we show how the splitting of the

d

electron states arises from an interplay of electrostatic effects and hybridization with the ligands'

s

p

and

d

states. We show that the ligand field alone cannot explain the stabilization of the

1H

polymorph for

d^1

and

d^2

TMDs, and that band structure effects are dominant. We present trends of the calculated parameters across the periodic table, and argue that these allow developing simple chemical intuition. Secondly, we study the occurrence of charge density wave phases and periodic lattice distortion in metallic

1T

transition metal dichalcogenides. The phonon dispersion and fermiology of representative examples with different

d

electron counts are studied as a function of doping. Two qualitatively different behaviours are found as a function of the filling of the

t_{2g}

subshell. We argue that away from half-filling, weak-coupling nesting arguments are a useful starting point for understanding, whereas closer to half-filling a strong-coupling real-space picture is more correct. Using Wannier functions, it is shown that strong metal-metal bonds are formed and that simple bond-counting arguments apply. Thirdly, the recently synthesized

1T

phase of NbSe

_2

, in monolayer form, is investigated from first principles. We find that

1T

-NbSe

_2

is unstable towards the formation of an incommensurate charge density wave phase, whose periodicity can be understood from the Fermi surface topology. We investigate different scenarios for the experimentally observed superlattice and insulating behaviour, and conclude that the star-of-David phase is the most stable commensurate charge density wave phase. We study the electronic properties of the star-of-David phase at various levels of theory and confirm its Mott insulating character, as speculated and in analogy with TaS

_2

. The Heisenberg exchange couplings are found to be ferromagnetic, which suggests a parallel with the so-called flat-band ferromagnetism in certain multiband Hubbard models. Finally, we address the possibility of the occurrence of the excitonic insulator phase in single-layer TiSe

_2

. The relative role of electron-electron and electron-phonon interactions in driving the charge density wave in layered and two-dimensional TiSe

_2

has been disputed and is still unresolved. We calculate the electronic structure and finite-momentum exciton spectrum from hybrid density functional theory. We find that in a certain range of parameters, excitonic effects are strong and the material is close to a pure excitonic insulator instability. A possible necessary condition for the physical realization of a pure excitonic insulator is proposed.

EPFL2019

Crystal field, ligand field, and interorbital effects in two-dimensional transition metal dichalcogenides across the periodic table

Diego José Pasquier, Oleg Yazyev

Two-dimensional (2D) transition metal dichalcogenides (TMDs) exist in two polymorphs, referred to as 1T and 1H, depending on the coordination sphere of the transition metal atom. The broken octahedral and trigonal prismatic symmetries lead to different crystal and ligand field splittings of the d electron states, resulting in distinct electronic properties. In this work, we quantify the crystal and ligand field parameters of 2D TMDs using a Wannier-function approach. We adopt the methodology proposed by Scaramucci et al (2015 J. Phys.: Condens. Matter 27 175503) that allows to separate various contributions to the ligand field by choosing different manifolds in the construction of the Wannier functions. We discuss the relevance of the crystal and ligand fields in determining the relative stability of the two polymorphs as a function of the filling of the d-shell. Based on the calculated parameters, we conclude that the ligand field, while leading to a small stabilizing factor for the 1H polymorph in the d(1) and d(2) TMDs, plays mostly an indirect role and that hybridization between different d orbitals is the dominant feature. We investigate trends across the periodic table and interpret the variations of the calculated crystal and ligand fields in terms of the change of charge-transfer energy, which allows developing simple chemical intuition.

IOP PUBLISHING LTD2019