CRYSTAL FIELD THEORY:

Isomer, Magnetic Properties and Colour.

A mini project of chemistry-I ( Paper Code: BS-CH-101 )

B.Tech, 1st Year, 1st Session 2018-19
Branch: Electrical (II)

Submitted By

RAJEEV KUMAR CLASS ROLL No. : 79

RAMASHISH CHOUDHARY CLASS ROLL No. : 80
RISHITA NANDI CLASS ROLL No. : 81
RITIK RAJ CLASS ROLL No. : 82
RITWIK SAMANTA CLASS ROLL No. : 83

Haldia Institute of Technology, Haldia, West Bengal, India

Maulana Abul Kalam Azad University of Technology (MAKAUT)
West Bengal, India
 CONTENT

1. Topic
2. Abstract
3. Introduction
4. Report on literature Survey
5. Conclusion
6. References
 TOPIC:

Crystal Field Theory:

Isomer, Magnetic Properties and Colour.

 ABSTRACT:
Crystal field theory (CFT) predicts that crystal field acting on an transition-metal (TM)
ion complex of cubic symmetry varies as R−5, where R is the TM-ligand distance. Yet
simple and old-fashioned, CFT is used extensively since it provides excellent results in
most TM ion-bearing systems, although no direct and thorough validation has been
provided so far. Here we investigate the evolution of the electronic and crystal
structures of two archetypal Co2+ compounds by optical absorption and X-ray
diffraction under high pressure. Both the electronic excited states and crystal-field
splitting, Δ = 10Dq, between 3d(eg + t2g) orbitals of Co2+ as a function of volume, V,
and Co−F bond length, R, in 6-fold octahedral (oct) and 8-fold hexahedral (cub)
coordination in compressed CoF2 have been analyzed. We demonstrated that Δ scales
with R in both co-ordinations as R−n, with n close to 5 in agreement with CFT
predictions. The pressure-induced rutile to fluorite structural phase transition at 15 GPa
in CoF2 is associated with an increase of R due to the 6 → 8 coordination change. The
experimental Δ(oct)/ Δ(cub) = −1.10 for the same R-values is close to −9/8, in
agreement with CFT. A similar R-dependence is observed in KCoF3 in which the
CoF6 Oh coordination is maintained in the 0− 80 GPa pressure range.
 INTRODUCTION:
The Crystal Field Theory (CFT) is a model for the bonding interaction between
transition metals and ligands. It describes the effect of the attraction between the
positive charge of the metal cation and negative charge on the non-bonding
electrons of the ligand. When the ligands approach the central metal ion, the
degeneracy of electronic orbital states, usually d or f orbitals, are broken due to the
static electric field produced by a surrounding charge distribution. CFT
successfully accounts for some magnetic properties, colors, and hydration energies
of transition metal complexes, but it does not attempt to describe bonding.
The electrons in the d orbitals of the central metal ion and those in the ligand repel
each other due to repulsion between like charges. Therefore, the d electrons closer
to the ligands will have a higher energy than those further away, which results in
the d orbitals splitting in energy. This splitting is affected by:
 the nature of the metal ion

 the metal’s oxidation state (a higher oxidation state leads to a larger splitting)
 the arrangement of the ligands around the metal ion
 the nature of the ligands surrounding the metal ion

All of the d orbitals have four lobes of electron density, except for the d z2 orbital,
which has two opposing lobes and a doughnut of electron density around the
middle. The d orbitals can also be divided into two smaller sets. The d x2–y2 and dz2
all point directly along the x, y, and z axes. They form an eg set. On the other hand,
the lobes of the dxy, dxz, and dyz all line up in the quadrants, with no electron
density on the axes. These three orbitals form the t2g set. In most cases, the d
orbitals are degenerate, but sometimes they can split, with the eg and t2g subsets
having different energy.

 Crystal field splitting (isomers)-

a) Crystal field splitting in octahedral coordination entities:
In an octahedral coordination entity with six ligands surrounding the metal
atom/ion, there will be repulsion between the electrons in metal d orbitals and the
electrons (or negative charges) of the ligands. Such a repulsion is more when the
metal d orbital is directed towards the ligand than when it is away from the ligand.
Thus, the 2 2 x y −d and 2 z d orbitals which point towards the axes along the
direction of the ligand will experience more repulsion and will be raised in energy;
and the dxy, dyz and dxz orbitals which are directed between the axes will be
 lowered in energy relative to the average energy in the spherical crystal field. Thus,
the degeneracy of the d orbitals has been removed due to ligand electron-metal
electron repulsions in the octahedral complex to yield three orbitals of lower energy,
t2g set and two orbitals of higher energy, eg set. This splitting of the degenerate
levels due to the presence of ligands in a definite geometry is termed as crystal field
splitting and the energy separation is denoted by ∆o (the subscript o is for
octahedral) (Fig.9.8). Thus, the energy of the two eg orbitals will increase by (3/5)
∆o and that of the three t2g will decrease by (2/5)∆o. The crystal field splitting, ∆o,
depends upon the field produced by the ligand and charge on the metal ion. Some
ligands are able to produce strong fields in which case, the splitting will be large
whereas others produce weak fields and consequently result in small splitting of d
orbitals. In general, ligands can be arranged in a series in the order of increasing
field strength as given below:
I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O < NCS– < edta4–
< NH3 < en < CN– < CO

b) Crystal field splitting in tetrahedral coordination entities:

In tetrahedral coordination entity formation, the d orbital splitting (Fig. 9.9) is
inverted and is smaller as compared to the octahedral field splitting. For the
same metal, the same ligands and metal-ligand distances, it can be shown that
∆t = (4/9) ∆0. Consequently, the orbital splitting energies are not sufficiently
large for forcing pairing and, therefore, low spin configurations are rarely
observed. The ‘g’ subscript is used for the octahedral and square planar
complexes which have centre of symmetry. Since tetrahedral complexes lack
symmetry, ‘g’ subscript is not used with energy levels.
 REPORT ON LITERATURE SURVEY: