Crystal Field Theory1

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<h1 id="title">Crystal Field Theory</h1>
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<aside id="mt-toc-container" data-title="Table of contents" data-col
lapsed="true">
<nav class="mt-toc-content mt-collapsible-section">
<ol><li><a href="" rel="internal">Basic Concept</a></li><li>
<a href="" rel="internal">Electrons in Orbitals</a></li><li><a href="" rel="inte
rnal">Description of d-Orbitals </a><ol><li><a href="" rel="internal">Octah
edral Complexes</a></li><li><a href="" rel="internal">Tetrahedral Complexes</a><
/li><li><a href="" rel="internal">Square Planar Complexes</a></li></ol></li><li>
<a href="" rel="internal">References</a></li><li><a href="" rel="internal">Probl
ems</a></li><li><a href="" rel="internal">Answers</a></li><li><a href="" rel="in
ternal">Contributors</a></li></ol>
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<section class="mt-content-container">
<p style="text-align: justify;">Crystal field theory (CFT) descr
ibes the breaking of orbital degeneracy in <a title="xApproaches/VVV Demos/Addit
ional Demos/Transition Metal Complexes" class="mt-disabled" rel="broken">transit
ion metal complexes</a> due to the presence of <a title="Inorganic Chemistr
y/Coordination Chemistry/Ligands" href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7Q
anJj20ir2Od6oMLaWY2%2FIhjYlXgj4kO8xJnkJ5qykBCyY7NEFq0bOu4TVFUsw4NT723F9DTFfU7pB7
&b=5" rel="internal">ligands</a>. CFT qualitatively describes the strength o
f the metal-ligand bonds. Based on the strength of the metal-ligand bonds,
the energy of the system is altered. This may lead to a change in <a title=
"Wikitexts/UCD Chem 2A/ChemWiki Module Topics/The Periodic Table/Magnetic Proper
ties" href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj20ir2Od7MKO6SW2f0ksZV8jz
YgIctPlRQGgD8dECEzNn9OyrOw2wRZXsQiGSXi%2Bj1uUUTQ8ttJYGbIrhM%2Fk%2FiOeydPe%2FwsdN
iWClrgO0NHQrH1BRIjn3GMWhJ9M84mMuYXgHGtiNe3M%2FI%3D&b=5" rel="internal">magne
tic properties</a> as well as <a title="Inorganic Chemistry/Crystal Fi
eld Theory/Colors of Coordination Complexes" href="/browse.php?u=7DIUBTALs7n4t9A
iDJtTEDcK7QanJj20ir2Od6oMLaWY2%2FIhjYlXgj4kO8xJnkJ5qzQXCjYzNn9Y0bms2il5X8Q%2BNDO
r5h9jSkLG35tuS0rKqAIEm%2FiLUANPecYMbtmHFGDILF8%3D&b=5" rel="internal">color<
/a>. This theory was developed by Hans Bethe and John Hasbrouck van Vleck [
3].</p> <div title="Core/Inorganic_Chemistry/Crystal_Field_Theory/Crystal_Field_
Theory" class="mt-section" id="section_1"><span id="Basic_Concept"></span><h3 cl
ass="editable">Basic Concept</h3> <p class="c1" style="text-align: justify;">In
Crystal Field Theory, it is assumed that the ions are <strong>simple point charg
es</strong> (a simplification). When applied to alkali metal ions containing a s
ymmetric sphere of charge, calculations of bond energies are generally quite suc
cessful. The approach taken uses classical potential energy equations that take
into account the attractive and repulsive interactions between charged particles
(that is, Coulomb's Law interactions).</p> <p class="c1" style="text-align: cen
ter;">\[E \propto \dfrac{q_1 q_2}{r}\]</p> <p class="c1">with</p> <ul> <li>$E$
the bond energy between the charges and</li> <li>$q_1$ and $q_2$ are the ch
arges of the interacting ions and</li> <li>$r$ is the distance separating them
.</li> </ul> <p style="text-align: justify;">This approach leads to the correct
prediction that large cations of low charge, such as $K^+$ and $Na^+$, shoul
d form few coordination compounds. For transition metal cations that contain var
ying numbers of d electrons in orbitals that are NOT spherically symmetric, howe
ver, the situation is quite different. The shape and occupation of these d-orbit
als then becomes important in an accurate description of the bond energy and pro
perties of the transition metal compound.</p> <p style="text-align: justify; ">W
hen examining a single transition metal ion, the five <a title="Physical Ch
emistry/Quantum Mechanics/Virtual: Atomic Orbitals/D Orbitals" class="mt-disable
d" rel="broken"><em>d</em>-orbitals</a> have the same energy. When ligands
approach the metal ion, some experience more opposition from the <em>d</em>-orbi
tal electrons than others based on the geometric structure of the molecule. Sinc
e ligands approach from different directions, not all <em>d-</em>orbitals intera
ct directly. These interactions, however, create a splitting due to the electros
tatic environment.</p> <p style="text-align: justify; ">For example, consider a
molecule with octahedral geometry. Ligands approach the metal ion along the $x\
), \(y$, and $z$ axes. Therefore, the electrons in the <span style="text-alig
n: justify;">$d_{z^2}$ and</span> $d_{x^2-y^2}$ orbitals (which lie alo
ng these axes) experience greater repulsion. It requires more energy to have an
electron in these orbitals than it would to put an electron in one of the other
orbitals. This causes a splitting in the energy levels of the <em>d</em>-orbital
s. This is known as <strong>crystal field splitting</strong>. For octahedral com
plexes, crystal field splitting is denoted by $\Delta_o$ (or $\Delta_{oct}$)
. The energies of the $d_{z^2}$ and $d_{x^2-y^2}$ orbitals increase due to g
reater interactions with the ligands. The $d_{xy}$, $d_{xz}$, and $d_{
yz}$<span style="line-height: 1.5;"> orbitals decrease with respect to this nor
mal energy level and become more stable. </span></p> <p style="text-align:
justify; "> </p> <p style="text-align: center;"><img alt="Figure 2a.jpg" c
lass="internal default" height="365" width="623" src="/browse.php?u=7DIUBTALs7n4
t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4Y4wS0X0%2FjzMcHB1gOw50yLv%2FzBNbXt
I4KSS5lA%3D%3D&b=5" /></p> <p style="text-align: center;"><em><strong>Figure
1: </strong>(a) Distributing a charge of −6 uniformly over a spherical su
rface surrounding a metal ion causes the energy of all five d orbitals to increa
se due to electrostatic repulsions, but the five d orbitals remain degenerate. P
lacing a charge of −1 at each vertex of an octahedron causes the d orbital
s to split into two groups with different energies: the </em><nobr><em>d<sub>x<s
up>2</sup>−y<sup>2</sup></sub></em></nobr><em> and </em><nobr><em>d<sub>z<
sup>2</sup></sub></em></nobr><em> orbitals increase in energy, while the, d<sub>
xy</sub>, d<sub>xz</sub>, and d<sub>yz</sub> orbitals decrease in energy. The av
erage energy of the five d orbitals is the same as for a spherical distribution
of a −6 charge, however. Attractive electrostatic interactions between the
negatively charged ligands and the positively charged metal ion (far right) cau
se all five d orbitals to decrease in energy but does not affect the splittings
of the orbitals. (b) The two e<sub>g</sub> orbitals (left) point directly at the
six negatively charged ligands, which increases their energy compared with a sp
herical distribution of negative charge. In contrast, the three t<sub>2g</sub> o
rbitals (right) point between the negatively charged ligands, which decreases th
eir energy compared with a spherical distribution of charge.</em></p> </div><div
title="Core/Inorganic_Chemistry/Crystal_Field_Theory/Crystal_Field_Theory" clas
s="mt-section" id="section_2"><span id="Electrons_in_Orbitals"></span><h3 class=
"editable">Electrons in Orbitals</h3> <p style="text-align: justify;">According
to the <a title="Inorganic Chemistry/Electronic Configurations/Aufbau Principle"

href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj20ir2Od7MKO6SW2f0ksZV8jzYgIct
PlRQThCMNDTA9NEl954%2B0zANOQ9QjIxXrwy9OUV%2FY86tpem36ih8Ml%2FWfSA9TONwjZNeDCmreI
E9oZKzvCh43xU6MSRV3KdRqLMMDjWC9pfOsP%2B8y1Tuu0g%3D%3D&b=5" rel="internal">Au
fbau principle</a>, electrons are filled from lower to higher energy orbitals. F
or the octahedral case above, this corresponds to the d<sub>xy</sub>, d<sub>xz</
sub>, and d<sub>yz</sub> orbitals. Following <a title="Inorganic Chemistry/Elect
ronic Configurations/Hund's Rules" href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7
QanJj20ir2Od7MKO6SW2f0ksZV8jzYgIctPlRQThCMNDTA9NEl954%2B0zANOQ9QjIxXrwy9OUV%2FY8
6tpem36ih8Ml%2FWfSA9TONwjZNeDCmreIE9oZKzvCh43xU6MSRV3KdRqJcMLiya7pfGrOuQi&b=
5" rel="internal">Hund's rule</a>, electrons are filled in order to have the hig
hest number of unpaired electrons. For example, if one had a d<sup>3</sup>
complex, there would be three unpaired electrons. If one were to add an electron
, however, it has the ability to fill a higher energy orbital (<span style="line
-height: 1.5;"> d</span><sub>z² </sub>or<span style="line-height: 1.5;
"> </span><span style="line-height: 1.5;">d</span><sub>x²-y²</sub
><span style="line-height: 1.5;">) or pair with an electron residing in the&nbsp
;</span><span style="line-height: 1.5;">d</span><sub>xy</sub><span style="line-h
eight: 1.5;">, </span><span style="line-height: 1.5;">d</span><sub>xz</sub><span
style="line-height: 1.5;">, or </span><span style="line-height: 1.5;">d</span><
sub>yz</sub><span style="line-height: 1.5;"> orbitals</span><span style="li
ne-height: 1.5;">. </span><span style="line-height: 1.5;">This pairing of t
he electrons requires energy (</span><a style="line-height: 1.5;" title="Inorgan
ic Chemistry/Electronic Configurations/Spin Pairing Energy" href="/browse.php?u=
7DIUBTALs7n4t9AiDJtTEDcK7QanJj20ir2Od7MKO6SW2f0ksZV8jzYgIctPlRQThCMNDTA9NEl954%2
B0zANOQ9QjIxXrwy9OUV%2FY86tpem36ih8Ml%2FWfSA9TONwjZNeDCmreIE9oZKzvCh43xU6MSRV3Kd
RqPsYMgV6Ym8qsP%2B824w6s0q%2BqgA%3D%3D&b=5" rel="internal">spin pairing ener
gy</a>)<span style="line-height: 1.5;">. If the pairing energy is less than the
crystal field splitting energy, ∆₀, then the next electron will go i
nto the </span><span style="line-height: 1.5;">d</span><sub>xy</sub><span style=
"line-height: 1.5;">, </span><span style="line-height: 1.5;">d</span><sub>xz</su
b><span style="line-height: 1.5;">, or </span><span style="line-height: 1.5;">d<
/span><sub>yz</sub><span style="line-height: 1.5;"> orbitals due to stability. T
his situation allows for the least amount of unpaired electrons, and is known as
</span><a style="line-height: 1.5;" title="Inorganic Chemistry/Crystal Field Th
eory/High Spin and Low Spin" href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj2
0ir2Od6oMLaWY2%2FIhjYlXgj4kO8xJnkJ5qzQXCjYzNn9Y0bms2il5X8Q%2BNDOr7RloTW%2Fm8J1mS
2jLoy8sneG1dxpJecYMbtmHFGDILF8%3D&b=5" rel="internal">low spin</a><span styl
e="line-height: 1.5;">. If the pairing energy is greater than ∆₀, th
en the next electron will go into the </span><span style="line-height: 1.5;">d</
span><sub>z</sub><span style="line-height: 1.5;">²</span><span style="lineheight: 1.5;"> or </span><span style="line-height: 1.5;">d</span><sub>x</sub><sp
an style="line-height: 1.5;">²-</span><sub>y</sub><span style="line-height:
1.5;">²</span><span style="line-height: 1.5;"> orbitals as an unpaired ele
ctron. This situation allows for the most number of unpaired electrons, and is k
nown as </span><a style="line-height: 1.5;" title="Inorganic Chemistry/Crystal F
ield Theory/High Spin and Low Spin" href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK
7QanJj20ir2Od6oMLaWY2%2FIhjYlXgj4kO8xJnkJ5qzQXCjYzNn9Y0bms2il5X8Q%2BNDOr7RloTW%2
Fm8J1mS2jLoy8sneG1dxpJecYMbtmHFGDILF8%3D&b=5" rel="internal">high spin</a><s
pan style="line-height: 1.5;">. Ligands that cause a transition metal to have a
small crystal field splitting, which leads to high spin, are called weak-field l
igands. Ligands that produce a large crystal field splitting, which leads to low
spin, are called <em>strong field ligands</em>. </span></p> <p style="text
-align: justify;"> </p> <p style="text-align: center;"><img alt="" class="i
nternal" height="241" width="264" src="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7Qa
nJj23hL%2BCd4cHKb7Q3PUki6U722J4YocS0Qg0xiweHn0gP1Z3y7Wv0Esc&b=5" /> &nb
sp; <img alt="" class="internal" height="206" width="208
" src="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4Y
oYS0Qg3xiweHn0gP1Z3y7Wv0Esc&b=5" /></p> <p style="text-align: center;">&nbsp
; Low Spin, Strong Field (&#871
0;<sub>o</sub>˃P) &
nbsp; High Spin, Weak Field (∆<sub>o</sub>˂P)</p> <p st
yle="text-align: center;"><em><strong>Figure 2:</strong> Splitting for a $d^4$
complex under a strong field (left) and a weak field (right). The strong field
is a low spin complex, while the weak field is a high spin complex.</em></p> <p
style="text-align: justify;">As mentioned above, CFT is based primarily on symme
try of ligands around a central metal/ion and how this anisotropic (properties d
epending on direction) ligand field affects the metal's atomic orbitals; the ene
rgies of which may increase, decrease or not be affected at all. Once the ligand
s' electrons interact with the electrons of the <em>d</em>-orbitals, the electro
static interactions cause the energy levels of the d-orbital to fluctuate depend
ing on the orientation and the nature of the ligands. For example, the <a t
itle="Analytical Chemistry/Electrochemistry/Redox Chemistry/Oxidation State" hre
f="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj20ir2Od6IMI7uGzvUrj7pLqTMsP9ZOmEk
vxwMCHCEmKE990Lmt1wVZRdh%2BFC%2FgyghQZljQ7Z17YHvc6D8Ym%2FKLUANPecYcddWDHQ%3D%3D&
amp;b=5" rel="internal">oxidation state</a> and the strength of the ligands
determine splitting; the higher the oxidation state or the stronger the ligand,
the larger the splitting. Ligands are classified as strong or weak based on the
spectrochemical series:</p> <p style="text-align: center;">I<sup>- </sup>&
lt; Br<sup>- </sup>< Cl<sup>- </sup>< <u>S</u>CN<sup>- </su
p>< F<sup>- </sup>< OH<sup>- </sup>< ox<sup>2-</sup>< <u>O
</u>NO<sup>- </sup>< H<sub>2</sub>O < SC<u>N</u><sup>- </sup>&lt
; EDTA<sup>4</sup><sup>-</sup> < NH<sub>3</sub> < en < <u>N</
u>O<sub>2</sub><sup>-</sup> < CN<sup>-</sup></p> <p style="text-align: j
ustify;">Note that SCN<sup>-</sup> and NO<sub>2</sub>- ligands are represented t
wice in the above spectrochemical series since there is two different Lewis base
sites (e.g., free electron pairs to share) on each ligand (e.g., for SCN<sup>-<
/sup> the electron pair on the sulfur or the oxygen can form the <a title="Coord
inate (Dative Covalent) Bonding" href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7Qa
nJj20ir2Od7cKJ7iN3%2Bghjbd4tRghN9JUn08kkWktESc%2FM0N%2F1IOC0RhJXs82aQ3hyxV9RFzq0
IZhemrMtxwFgcmFQjVjf%2FwiaNeWFFryJkJTTq3mQzQ%2F306JVBJ5M8IaRfIEm2i%2Bn%2FydOfcw0
C6sw%2FSSu%2FAhuizxnA%3D%3D&b=5" rel="internal">coordinate covalent bond</a>
to a metal). The specific atom that binds in such ligands is underlined.</p> <p
style="text-align: justify;">In addition to octahedral complexes, two common ge
ometries observed are that of tetrahedral and square planar. These complexes dif
fer from the octahedral complexes in that the orbital levels are raised in energ
y due to the interference with electrons from ligands. For the tetrahedral compl
ex, the d<sub>xy</sub>, d<sub>xz</sub>, and d<sub>yz</sub> orbitals are raised i
n energy while the d<sub>z²</sub>, d<sub>x²-y²</sub> orbitals are
lowered. For the square planar complexes, there is greatest interaction with th
e d<sub>x²-y²</sub> orbital and therefore it has higher energy. The ne
xt orbital with the greatest interaction is d<sub>xy</sub>, followed below by d<
sub>z²</sub>. The orbitals with the lowest energy are the d<sub>xz</sub> an
d d<sub>yz</sub> orbitals. There is a large energy separation between the d<sub>
z²</sub> orbital and the d<sub>xz</sub> and d<sub>yz</sub> orbitals, meanin
g that the crystal field splitting energy is large. We find that the square plan
ar complexes have the greatest crystal field splitting energy compared to all th
e other complexes. This means that most square planar complexes are low spin, st
rong field ligands.</p> </div><div title="Core/Inorganic_Chemistry/Crystal_Field
_Theory/Crystal_Field_Theory" class="mt-section" id="section_3"><span id="Descri
ption_of_d-Orbitals"></span><h3 class="editable">Description of <em>d</em>-Orbit
als </h3> <p>To understand CFT, one must understand the description of the
lobes:</p> <ul> <li>d<sub>xy</sub>: lobes lie in-between the x and the y axes.</
li> <li>d<sub>xz</sub>: lobes lie in-between the x and the z axes.</li> <li>d<su
b>yz</sub>: lobes lie in-between the y and the z axes.</li> <li>d<sub>x<sup>2</s
up>-y<sup>2</sup></sub>: lobes lie on the x and y axes.</li> <li>d<sub>z</sub><s
up><sub>2</sub></sup>: there are two lobes on the z axes and there is a donut sh
ape ring that lies on the xy plane around the other two lobes.</li> </ul> <p sty
le="text-align: center;"><img alt="" class="internal" style="width: 657.997px; h
eight: 158.991px;" width="657.997px" height="158.991px" src="/browse.php?u=7DIUB
TALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4Yo4S0V5j23dWQCc2PEMo2enw30A
VAZA0dHu0k0U8ElHWuZY7OmPVoE8Sl%2BCDVwNPeaR9&b=5" /></p> <p style="text-align
: center;"><em><strong>Figure 3:</strong> Spatial arrangement of ligands in the
an octahedral ligand field with respect to the five d-orbitals.</em></p> <div ti
tle="Core/Inorganic_Chemistry/Crystal_Field_Theory/Crystal_Field_Theory" class="
mt-section" id="section_4"><span id="Octahedral_Complexes"></span><h4 class="edi
table">Octahedral Complexes</h4> <p style="text-align: justify;">In an <a title=
"Inorganic Chemistry/Crystal Field Theory/Metals, Tetrahedral and Octahedral" hr
ef="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj20ir2Od6oMLaWY2%2FIhjYlXgj4kO8xJ
nkJ5qzQXCjYzNn9Y0bms2il5X8Q%2BNDOr6BV7RFzGpcZLS13AswIBmvOOVgtMSPghZeu4G3HRIUlTVa
Lt&b=5" rel="internal">octahedral complex</a>, there are six ligands attache
d to the central transition metal. The d-orbital splits into two different level
s. The bottom three energy levels are named $d_{xy}$, $d_{xz}$, an
d $d_{yz}$ (collectively referred to as $t_{2g}$). The two upper energy
levels are named $d_{x^²-y^²}$, and $d_{z^²}$ (collecti
vely referred to as $e_g$).</p> <p style="text-align: center;"><img alt="" cla
ss="internal" height="180" width="189" src="/browse.php?u=7DIUBTALs7n4t9AiDJtTED
cK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4Yo0S0Qp4gjYJRjA3LElt0bOug0c%3D&b=5" /></
p> <p style="text-align: center;"><em><strong>Figure 4</strong>: Splitting of th
e degenerate d-orbitals (without a ligand field) due to an octahedral ligand fie
ld shown in Figure 3.</em></p> <p style="text-align: justify;">The reason they s
plit is because of the electrostatic interactions between the electrons of the l
igand and the lobes of the d-orbital. In an octahedral, the electrons are a
ttracted to the axes. Any orbital that has a lobe on the axes moves to a higher
energy level. This means that in an octahedral, the energy levels of $e_g$&nbs
p;are higher (0.6∆<sub>o</sub>) while $t_{2g}$ is lower (0.4∆<sub>
o</sub>).<span style="line-height: 1.5;"> The distance that the electrons h
ave to move from </span> $t_{2g}$<span style="line-height: 1.5;"> from </
span>$e_g$<span style="line-height: 1.5;"> and it dictates the energy that the
complex will absorb from white light, which will determine the <a title="Inorga
nic Chemistry/Crystal Field Theory/Colors of Coordination Complexes" href="/brow
se.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj20ir2Od6oMLaWY2%2FIhjYlXgj4kO8xJnkJ5qzQXC
jYzNn9Y0bms2il5X8Q%2BNDOr5h9jSkLG35tuS0rKqAIEm%2FiLUANPecYMbtmHFGDILF8%3D&b=
5" rel="internal">color</a>. W</span><span style="line-height: 1.5;">hether the
complex is <a title="Inorganic Chemistry/Descriptive Chemistry/Periodic Table of
the Elements/Magnetic Properties" href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7
QanJj20ir2Od7MKO6SW2f0ksZV8jzYgIctPlRQGgD8dECEzNn9OyrOw2wRZXsQiGSXi%2Bj1uUUTQ8tt
JYGbIrhM%2Fk%2FiOeydPe%2FwsdNiWClrgO0NHQrH1BRIjn3GMWhJ9M84mMuYXgHGtiNe3M%2FI%3D&
amp;b=5" rel="internal">paramagnetic or diamagnetic</a> will be determined by th
e spin state. If there are unpaired electrons, the complex is paramagnetic; if a
ll electrons are paired, the complex is diamagnetic.</span></p> </div><div title
="Core/Inorganic_Chemistry/Crystal_Field_Theory/Crystal_Field_Theory" class="mtsection" id="section_5"><span id="Tetrahedral_Complexes"></span><h4 class="edita
ble">Tetrahedral Complexes</h4> <p style="text-align: justify;">In a tetrahedral
complex, there are four ligands attached to the central metal. The d orbit
als also split into two different energy levels. The top three consist of the $
d_{xy}$, $d_{xz}$, and $d_{yz}$ orbitals. The bottom two consist of the $d
_{x^2-y^2}$ and $d_{z^2}$ orbitals. The reason for this is due to poor orbita
l overlap between the metal and the ligand orbitals. The orbitals are directed o
n the axes, while the ligands are not.</p> <p style="text-align: center;"><img a
lt="" class="internal" style="width: 610.994px; height: 240.994px;" width="610.9
94px" height="240.994px" src="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj23hL%2
BCd4cHKb7Q3PUki6U72WxxYo8S0XUzn3RAEzI1ZVJ7zrWz1xlDCpA%3D&b=5" /></p> <p styl
e="text-align: center;"><strong>Figure 5</strong>: (a) Tetraheral ligand field s
urrounding a central transition metal (blue sphere). (b) Splitting of the
degenerate d-orbitals (without a ligand field) due to an octahedral ligand field
(left diagram) and the tetrahedral field (right diagram).</p> <p style="text-al
ign: center;">The difference in the splitting energy is tetrahedral splitting co
nstant ($\Delta_{t}$), which less than ($\Delta_{o}$) for the same ligands:<
/p> <p style="text-align: center;">\[\Delta_{t} = 0.44\,\Delta_o \tag{1}\]</p> <
p style="text-align: justify;">Consequentially, $\Delta_{t}$ is typically smal

ler than the <a title="Spin Pairing Energy" href="/browse.php?u=7DIUBTALs7n4t9Ai
DJtTEDcK7QanJj20ir2Od7MKO6SW2f0ksZV8jzYgIctPlRQThCMNDTA9NEl954%2B0zANOQ9QjIxXrwy
9OUV%2FY86tpem36ih8Ml%2FWfSA9TONwjZNeDCmreIE9oZKzvCh43xU6MSRV3KdRqPsYMgV6Ym8qsP%
2B824w6s0q%2BqgA%3D%3D&b=5" rel="internal">spin pairing energy</a>, so tetra
hedral complexes are usually <strong>high spin</strong>.</p> </div><div title="C
ore/Inorganic_Chemistry/Crystal_Field_Theory/Crystal_Field_Theory" class="mt-sec
tion" id="section_6"><span id="Square_Planar_Complexes"></span><h4 class="editab
le">Square Planar Complexes</h4> <p style="text-align: justify;">In a square pla
nar, there are four ligands as well. However, the difference is that the electro
ns of the ligands are only attracted to the $xy$ plane. Any orbital in th
e xy plane has a higher energy level. There are four different energy levels for
the square planar (from the highest energy level to the lowest energy level): d
<sub>x<sup>2</sup></sub><sub>-y<sup>2</sup></sub>, d<sub>xy</sub>, d<sub>z<sup>2
</sup></sub>, and both d<sub>xz</sub> and d<sub>yz</sub>.</p> <p style="text-ali
gn: center; "><img alt="" class="internal" height="256" width="252" src="/browse
.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4YooS0Qk3xiweHn0
gP1Z3y7Wv0Esc&b=5" /><img alt="" class="internal" height="262" width="200" s
rc="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4YokS
0Qk0xiweHn0gP1Z3y7Wv0Esc&b=5" /></p> <p style="text-align: center;"><strong>
Figure 6</strong>: Splitting of the degenerate d-orbitals (without a ligand fiel
d) due to an square planar ligand field.</p> <p style="text-align: center;">&nbs
p;</p> <p style="text-align: justify;">The splitting energy (from highest orbita
l to lowest orbital) is $\Delta_{sp}$ and tends to be larger then $\Delta_{o}
$</p> <p style="text-align: center;">\[\Delta_{sp} = 1.74\,\Delta_o \tag{2}\]</
p> <p style="text-align: justify;">Moreover, $\Delta_{sp}$ is also larger than
the pairing energy, so the square planar complexes are usually <strong>low spin
</strong> complexes.</p> <div> <div id="example"> <p class="boxtitle" style="vis
ibility: visible;">Example</p> <p style="text-align: justify;">For the complex i
on [Fe(Cl)<sub>6</sub>]<sup>3- </sup>determine the number of d electrons for Fe,
sketch the d-orbital energy levels and the distribution of d electrons amo
ng them, list the number of lone electrons, and label whether the complex i
s paramagnetic or diamagnetic.</p> <p><strong>SOLUTION</strong></p> <ul> <li>Ste
p 1: Determine the oxidation state of Fe. Here it is Fe<sup>3</sup><sup>+</sup>.
Based on its electron configuration, Fe<sup>3+</sup> has <strong>5 d-electrons<
/strong>.</li> <li>Step 2: Determine the geometry of the ion. Here it is an octa
hedral which means the energy splitting should look like:</li> </ul> <p style="t
ext-align: center;"> <img alt="" class="internal" height="158" width="166"
src="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4Yo0
S0Qp4gjYJRjA3LElt0bOug0c%3D&b=5" /></p> <ul> <li style="text-align: justify;
">Step 3: Determine whether the ligand induces is a strong or weak field spin by
looking at the<a title="Spectrochemical Series" href="/browse.php?u=7DIUBTALs7n
4t9AiDJtTEDcK7QanJj20ir2Od6oMLaWY2%2FIhjYlXgj4kO8xJnkJ5pzQJGCw9N0Vq2bCs1xVydMk0K
yP30QJ2Cnzc55VmcFbnrh4Em%2FiNewNOSNogbsaTEWvRPUVYSZzCAxog3FmVWA83FNcgDsIXgGKgn86
3NeA94xinxbSoig%3D%3D&b=5" rel="internal"> spectrochemical series</a>. Cl<su
p>-</sup> is a weak field ligand (i.e., it induces high spin complexes). Therefo
re, electrons fill all orbitals before being paired.</li> </ul> <p style="text-a
lign: center;"><img alt="" class="internal" height="191" width="264" src="/brows
e.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4Y44S0X0z23RAEz
I1ZVJ7zrWz1xlDCpA%3D&b=5" /></p> <ul> <li>Step four: Count the number of lon
e electrons. Here, there are <strong>5 electrons</strong>.</li> <li>Step five: T
he five unpaired electrons means this complex ion is <strong>paramagnetic</stron
g> (and strongly so).</li> </ul> </div> </div> <div> <div id="example"> <p class
="boxtitle" style="visibility: visible;">Example 2</p> <p>A <em>tetrahedral </em
>complex absorbs at 545 nm. What is the respective octahedral crystal field spli
tting ($\Delta_o$)? What is the color of the complex? </p> <p><strong>SOL
UTION</strong></p> <p style="text-align: center;">\[\Delta_t = \dfrac{hc}{\
lambda}\]</p> <p style="text-align: center;">\[\Delta_t = \dfrac{ (6.626 \times
10^{-34} J \cdot s)(3 \times 10^8 m/s)}{545 \times 10^{-9} m}=3.65 \times 10^{-1
9}\; J \]</p> <p>However, the <em>tetrahedral </em>splitting ($\Delta_t$) is ~
4/9 that of the <em>octahedral </em>splitting ($\Delta_o$).</p> <p style="text

-align: center;">\[\Delta_t = 0.44\Delta_o \]</p> <p style="text-align: cen
ter;">\[\Delta_o = \dfrac{\Delta_t}{0.44} = \dfrac{3.65 \times 10^{-19} J}
{0.44} = 8.30 \times 10^{-18}J\]</p> <p>This is the energy needed to promote <em
>one </em>electron in <em>one </em>complex. Often the crystal field splitting is
given per mole, which requires this number to be multiplied by Avogadro's Numbe
r ($6.022 \times 10^{23}$).</p> <p>This complex appears red, since it absorbs
in the complementary green color (determined via the color wheel).</p> </div> </
div> <p style="text-align: center;"> <span id="d8nbI0M5" class="mt-media"><
a href="/browse.php?u=7DIUES8Z8PbwsdA1R4xZBWwerEayJGaRia6YMJMOI66ayA%3D%3D&b
=5" rel="external nofollow" target="_blank" class="external"><img src="/browse.p
hp?u=7DIUES8Zt%2Fr1udcjR45SByEc7Qq6LD2eiK6MPZBNMb%2BeyPkswbJ7nTUlPd5Zs1kjnDIBFzF
9PUVq57qs3wVFaNE9JzPh115oTFY%3D&b=5" alt="Get Adobe Flash player" /></a></sp
an></p> <p style="text-align: center;"><strong><em>Video: </em></strong></p
> </div></div><div title="Core/Inorganic_Chemistry/Crystal_Field_Theory/Crystal_
Field_Theory" class="mt-section" id="section_7"><span id="References"></span><h3
class="editable">References</h3> <ol> <li>General Chemistry Principles and Mode
rn applications by Petrucci, Harwood, Herring, and Madura.</li> <li>General Chem
istry by McQuarrie and Rock.</li> <li> J. H. Van Vleck, "Theory of the
Variations in Paramagnetic Anisotropy Among Different Salts of the Iron Group&q
uot;, Phys. Rev. 41, 208 - 215 (1932)</li> <li><a href="/browse.php?u=
7DIUAzZAqf7%2Ft8I1DYZXRiwLpEaiKHmeyoyZIZAWI7ug3PUtgrJLnjMsPc1E&b=5" rel="ext
ernal nofollow" target="_blank" class="external">http://en.wikipedia.org/wiki/Cr
ystal_field_theory</a></li> </ol> </div><div title="Core/Inorganic_Chemistry/Cry
stal_Field_Theory/Crystal_Field_Theory" class="mt-section" id="section_8"><span
id="Problems"></span><h3 class="editable">Problems</h3> <p style="text-align: ju
stify;">For each of the following, sketch the d-orbital energy levels and the di
stribution of d electrons among them, state the geometry, list the number o
f d-electrons, list the number of lone electrons, and label whether they ar
e paramagnetic or dimagnetic:</p> <ol> <li>[Ti(H<sub>2</sub>O)<sub>6</sub>]<sup>
2+</sup></li> <li>[NiCl<sub>4</sub>]<sup>2-</sup></li> <li>[CoF<sub>6</sub>]<sup
>3- </sup>(also state whether this is low or high spin)</li> <li>[Co(NH<sub>3</s
ub>)<sub>6</sub>]<sup>3+ </sup>(also state whether this is low or high spin
)</li> <li>True or False: Square Planer complex compounds are usually low spin.&
nbsp;</li> </ol> </div><div title="Core/Inorganic_Chemistry/Crystal_Field_Theory
/Crystal_Field_Theory" class="mt-section" id="section_9"><span id="Answers"></sp
an><h3 class="editable">Answers</h3> <p>1. octahedral, 2, 2, paramagnetic</p> <p
style="text-align: center;"><img alt="" class="internal" height="183" width="25
6" src="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4
Y4sS0WpniWgECSVtKEVo0a%2Bp0RgQBg%3D%3D&b=5" /></p> <p>2. tetrahedral, 8, 2,
paramagnetic (see <span><a title="II.7 Octahedral vs. Tetrahedral Geo
metries" href="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj20ir2Od6oMLaWY2%2FIhj
YlXgj4kO8xJnkJ5qykBCyY7NEFq0bOu4TVFUsw4NT723F9ARkTU6JFsZmjJmAYT3Mm%2BQR5SdvEqZca
WFFr3LENaQrfzBRIj&b=5" rel="internal">Octahedral vs. Tetrahedral Geometries<
/a>)</span></p> <p style="text-align: center;"><img alt="" class="internal" heig
ht="180" width="242" src="/browse.php?u=7DIUBTALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4
cHKb7Q3PUki6U722J4Y4gS0WpkxiweHn0gP1Z3y7Wv0Esc&b=5" /></p> <p>3. octahedral,
6, 4, paramagnetic, high spin</p> <p style="text-align: center;"><img alt="" cl
ass="internal" height="187" width="262" src="/browse.php?u=7DIUBTALs7n4t9AiDJtTE
DcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4Y4oS0WplxiweHn0gP1Z3y7Wv0Esc&b=5" /></p
> <p>4. octahedral, 6, 0, diamagnetic, low spin</p> <p style="text-align: center
;"><img alt="" class="internal" height="215" width="255" src="/browse.php?u=7DIU
BTALs7n4t9AiDJtTEDcK7QanJj23hL%2BCd4cHKb7Q3PUki6U722J4Y4kS0WpixiweHn0gP1Z3y7Wv0E
sc&b=5" /></p> <p>5. True</p> </div><div title="Core/Inorganic_Chemistry/Cry
stal_Field_Theory/Crystal_Field_Theory" class="mt-section" id="section_10"><span
id="Contributors"></span><h3 class="editable">Contributors</h3> <ul> <li>Asadul
lah Awan (UCD), Hong Truong (UCD)</li> <li><p><span class="c3"><a class="externa
l" href="/browse.php?u=7DIUES8Zvf%2Fxs5wlHoZbBy0Y7QyxNDydiOCIMJEObL%2BL1%2FA%3D&
amp;b=5" rel="external nofollow" target="_blank" title="/chrl.html">Prof. Robert
J. Lancashire</a> (</span>The Department of Chemistry, University of the West I
ndies)</p></li> </ul></div>
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p style="text-align: justify;">Consequentially, \(\Delta_{t}\) is typically smal

4/9 that of the <em>octahedral </em>splitting (\(\Delta_o\)).</p> <p style="text

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