H colour the few

we
say any cysk spllmy
chey

A du then thin
inbnnyd
(
buyer
urges Cheng ocany

A huh bh thugs
-

chefs
are
.

angry


Light consists of delteoent 2

Emission
-

RELAXATION Lifetime of
wavelengths
exceed
f
max
four exited

state
RAYS microwaves
goes

-

fy
beach to
gnmd
stare

After absorbed
dlfffencl
is and
hard soft
light a
photon

between
has excited an election . lheeeeaon
'

to
Em ' ) ' ' ~
C
Xf will
go
back state
grand
= .

and
Essentially inhumation
can same
Ger

C Ch s in medium ; blue trails faster as fan absorption .

ATDWPHM
'
'
hv of exceed shoe = 10 seconds
Again Energy
.

of
ground
stare
Energy
-

of mother
dlyhv

3 interaction with
types
3
Scathing T WHAZISINKRESHNG
-

INELASTIC sintering
.

to
/
Excitation Relaxation
diffraction 0
1
Absorption absorbed
rest
speak wavelengths
.

travels of hVi this

colour sample T
through
ELASHI
scattering 8
colours that nor RAMAN Frouresccwce
remaining
=
are

and does nor

photon
his
sample f
absorbed CITATION
scattered
.

incident

lose No loss and no

energy every
,

Energy of excited state of state

hf Emission have to
ground *
-

energy
transferred to bean of
yhr
energy sample
.
.

cnn.mn

f is the of the
photon
where
frequency fend f
not to bother with this ,

Sample could get

2 step proof ! Goes in time then comes out Warner
-
,
delay -

Another Ray EKHKAIKR

.

HV ; = his name = (
incident Scathe -
 Matcwk an
'
he .
dearie
-

Wu

hbrahaal
-

's
INFRARED

#
rdahad microwave
-

tnaahual%
b
A

WN

RM
H Vlbi { lean
 (
R4HmHa
}W@\
In
"

/
6
arrow

eewnle "
species
Wythe
tend w

menu

:
, . ,

lewis
b
lyud base

au

'

'D

Inns

sphere
f
FED to

artier
sphere
%
eg
=
.

!
.

Cybil held splits degenerate energy

Wels hw hosen .

it lie then dz
'
and
dxy
*
ligands
wing

g
 CRYSTAL
+ AHN -
TELLER DISTORTION SQUARE PLANAR
Field SPLITTING

To -

realise that oct=} % of

remember just reverse at
=

?
22 -

y
-

See shoulder in shaped hell

pyramid just
wie field and
speemnu
=
new
gangster
a a remove
g
shoulder
-

dY levels i.

Energy
OCTAHEDRAL Gnwaster

ftp.aa.mn
incase Taea

-
de

Basic idea how two orbitals deft OCTAHEDRAL

= can
containing - -
oxzoyz TETRAHEDRAL

e- in ?
be
of equal
energy
no

eg tz

3/500

{
.

looking at octahedral case ELONGATION Compression /

.
. . .

oTo=a00
21500
o

going orbitals

Z orbitals are Z will be o

to be lower When f. 2/5

y y y yf y y y y uieuergy energy 00
/ ] , oo

" 2
- "
"

NO JAHN TELLER JAHN TCUCR JAHN TELLER /

t da =

Oxydyzdzx
- -

lacks fwmaedany go
to \ -
du
- kg @

remember
degeneracy

/ TIY
-

cnemmniucdais

-
any

- - -

fdxy th " "

Jahn Yeller distorts so as to restore

dyeeraay
ie 7-+
-

oI - -

Assume
ligands Assume
.
, , approach an the axis
ligands approach
RED i. JAHN X
TELLER

between the axis

The definition Geometrical of nonlinear
distortion
Yi
'
a

molecule that reduces and obxved

"
,# *
symmetry
in
energy
.
"
,

ablhlls In och
when the are
asymmetrically ocappied
.

hedral two axial bonds be

complexes can
kyerlsherher
.

3 PARAMETERS DETERMINE
haanb FIELD STABILISATION ENERGY
SPECTRO CHEMICAL SERIES
IGH / LOW SPIN

)
gook (oo)y
= -

007 >

1)
-

Use Spin only formula .

=
Gs
#TB ,z=e where
=

0o( }x
-

y )
=

@4x
.6y)0o -

METAL CATION : 2+
, 3+ ,
a +

Zme
s
Canuse this determine this
to whether
hollow spin can
I
.

density
-1 >
charge
2) Do
dependent
Lynd
on + achieved spin spiw LCSE

chcye
= 8 low
be
by caluiahg mp
metal ion
density on LFSE
favorable 4 Edarw
.
more
=
which ever
energetically
=
:
or
only

A acceptor

the is
one
that adopted .

- \
3)
|
Pairing energy
.

/
.

low spin
minimise s Tt them
pair

f- 1120
-

1- OH CO
,
NH }
, , , ,

444
high spin
maximise s
 t HE caourol complexes

IT darcv 0 IT ACQPW Need

only
to crew
ligand field theory explain mangoes
. .
.

Absorbs red
see blue

This is what we expect to Occur ' .

And
tye
Absorbs blue
see red
indeed for Oarly ligands this is what

#
f#
g
it
of
assure or

inept on,}i
we oaus being white
.

Absorbs visible
spectrum
see
non
pan
. ,

,
.

#
"
" "
"

-1
"

Ittff
=eg #
"
LIAANDFIELDTHEORY
as

tFf?y=g
"

CFT metal covalent interactions assumed

ignored ligand purely
- -

ionic t
predict speemochemical series + o in corner . .
.

LFT
diagrams
+ of CFT (
combining principles splithy
= mo

A of d orbitals electrostatic
anus
they occurs when the
Lynd
has it
degenerate ; not me
purely
nature ) .

[ I '

( 0 # of
abides The onsides iweraev with the same as
MO
they
MO
applicant theory
.

it can , an
.

20 dobras 4ham Dewar -

Duncanson
. chan

Basically what we are

doing
here is seems how 00

ft model . Get A
baurbondng
. . .

www.ebechcly
changes
with different
ligands ( experimentally
HZO creates a
tzg type abivw which can
colour denned
dsseved
twoyh changes
.
so is
always

be
interact with of 3d a A donor would
tzg
.

the LUMO and HOMO

as the difference between

elector non : donate e- to the

very and .

A would not donate let orbital

metal centre . T
acceptor Now us constrict the MO
diagram

E .

any

absorbed
Larger smithy Her frequency
means is
hpv
: .
CHANGING COLOUR COMPLEXES QUESTIONS
 GOING TO EXPLAIN IT IN TERMS of a
d2 SYSTEM

RACAH PARAMETERS
waw to determine ale the
possible cabanas
of now

'

2 d orbitals then
elections can and
arrange
in
jmp

Depend an calawbic repulsion

the different cahjwahias according to
energy
.

between E in
complexes
.

Using n!_ we can know now

many
microstates

e ! ( n
-

e) !

we expect
.

A= total eleuonic
average repulsion
.

ken we
know "l"ll#_
for metal
app equal each

So Mc ( both +2
)
+4 ki state
possible values =

centre .

+3 ( 1 in +2 and 1 in Hskue
)

B band between
+2 ( 1. in +2 state s In + ishue )
Appnx strength
=

ti ( l in +1 store 8 I in a state ) er

and moral
legend
An for -1 -2
help 0 , , -3 er . we know their

going
,

there two
for to state are e- in same orbital = .
5=0

C
B-
~

Mwhphy
uhk +3 state
ca hue s= o ,
i
,
-
i .

spin mwhpl.ly

and )
WHY C 2s+D(
2 241 # miowonies
mummy an
=

FORBIDDEN TRANSITIONS SEEN ?

thr for d2
given Usiy get
energy
.

when form band between

-

a the
1C 3f '
D 3P Is
-

, , , ,

metal and
hyud hybridisation Expander
-

(25+1)
get hephelcwxetic
that

parameter
.
so max then Lmae
.

3f
1

3P
'

G D IS
Hybridisation would
, ,

the
,
cause
,

B ( )
P complex
character to
=
Actual order 3f '
-

D 3p 26,15
change slightly
. . . .

:
, , ,

B ( fneeiar
allow the Hansman to occur
.
Vlbnhic In this example
determined the and excited
grind
we

character smaller states In determine the

P store
to
Caphy cheyes gmd
.

= .

order
jusv
use
. . . .

move covalent the character of the EL and

bonding between
hgard and metal .
|
YE
|
- | |
T 25 + '

L =
Grab
- SHE
-
 '

Given Tag ( f ) 372g Great the

finally
1
now that

here
'
wwenwubers azoocm
'

you

=
3
'

3Tig ( F ) Tag C P ) read

D=
Vz=
ratio all the
.

25700cm
vows
.

B
Vs =
xari
'

3Tzg ( f )

3Azg
-

39.5 29
0g
= =
,

by

3-7
2 the Ts
Identify
this an
diagram

26 5 = 29
0
.

=
,

3 Take ratio of 1.49
257-00
=

Vy
=
'
'
, 17200 =) B = I = Vz t
650cm
.

39.5 26.5

' '

@ Warr to kind there rano 's Oo = 29 ( 650 ) = 18822 cm

an Want two
diagram
.

J
o

7 Now We Want to determine

=
numbers where rano gives } .

1.49
A2g
us
}
.

= . . .

55
5
These two hare a
pretty
nveeh constant dsknce
VI. =

does let's 1.43
iv
equal
1.49 .
see 41 =

30

)
'
(
'

Vs Ss
Socio
a
680cm = 357
-

try
6 It Seem to another
does
vary slightly

value
CURVATURE
States their come from different free iou states

and which hare same =L :

symmetry
cross .

= 1.54

24
'
awe
from eaee other
Aig from
away Eg
.

sa
= 1.49 YAY

3zg
"
15 and 16
 CHARGE TRANSFER BANDS STED MICROSCOPY VS CONFOCAL LIGHT MICROSCOPY

100 at
" photons sample
already faked

~
absorbed then neenuhed

about there can to in

expels back what
gen you get

ii that
be deduced from eg put green
X
left expo to
get
back

Some occur
processes
.

TANABE SUNAGO DIAGRAM

-

( nor radiative transfer )
change
in the red
pnosphcrence
occurs will emir
.

These are the transfer bands

phosphorescence
has
long
Hennes so car
distinguish
.

charge

Charge

transfer bands occur when no dei .

Improves resolution

shine
light sample
on

Electronic transitions our between metal

excite sample

event
gevanswpwar
and
legend
.

then for to and

typically
wow sample decay even
light
.

As transition is not forbidden here

instead of second and iv
warning , cnpilr pulse Maine Care back

tune
have intense transitions and if in down -

more N Ameren and can this process

.

Very

visible
par of then
spectrum vary

slung colours .

Two
types :

Selection
Opto
rules
electronegative Ey
.

1 " GAND To maaicnarae Transfer

It orbitals filled and metal orbitals 05 fw Allowed transmit

ligand
=
then e

empty j= of
buyer
are
waenunber query ouege band
energy

IT forbidden transition
MHALI ox State then
hyh
from to metal . mic ,
occurs will be weak
Goes beyond
. .
.

j = /
Xugwg
-

Xmekd / yo
'

for allowed

|[
a 1
transition
/
=
'
J= 3000 ( chi
metal
)

#
Xcymd
X
-

ma

METAL TO LIGAND 2 CHARGE TRANSFER lw

Lower
euey
amir bad
Energy aid due to
; and Change panty g U =
allowed

Fnyhs
I knew

metal
/
Br MC " lower different ions / -

be
coupling

If and metal
filled Can relaxed structural distortion vibronic
by
arsenals arsenals
ligand empty
are her
a
ligand X
mat ) hghw

then e- from moral to ! METAL = low A state structural

go / distortion
.

Yao
 -

Ryutaro} lraanerf out electric

dipole moment
FK
Wave ) Pk =P

f-
( complementary to
W vis V Hz
I J
-

for -1
-

number in
strong bonding
=

=
=

wavelength
x

UV vis
for
-

to look TM metals J
vis
good
-

heavy f
uv or
mass
-

f
for T
-

@ ligands
112
NEAR |R transition metals '

2.5m spectroscopy
z.ly

# = cmi
why see
.

too
'

J
mass =

heay =/ too
. .

two techniques Infrared

-

MID ) R low
25m

Raman

Mmx
IR
FAR 100
m

=

Mz
-

Number of :
nonlinear

3N -6
Eubv 2,3
( Yz
nbrabianal modes
= nt
) hv
;
n = 0 , 1 , ,
One 1 1
Based harmonic mode But do
anhavmarichy
an
gen
Can tell anharmonic because 4mV
:
3N
-
OE
wear 5

told
between
! i
~ " l A "wht " " "
9 & '
HWMMKNY
spacing energy levels no
Strang
=

men on =1

intensity
Number of of
stretching modes =
number bonds
overtones
constant Another On 2,3
is that get
.
OE =
on with V constant even
.

Consequence
( Weak
intensity On 2,3
=
of when
bend b twin as
nod wins
)

ie caur
double band
same as
band )
single
weak
if typically
-

increases will she

very
.

same
energy get
of
Number bending modes =

Ubralioual
frequency
# vibraliaral modes # modes
stretching
-

mm

Gasping @lDPHAsn)
handmaiden
IR has nor
spectrum only

WI
Need to take into avant the lattice
crystal
fundamental vibration ie On =1 In liquid bunted what
get
but also
get done tensions aware
geedam ... no waning
que punched
same Vibration Modes Not Visible because

are nw one ' but also nor 0n=2B

Bae we see nbrahcnae ( an ) some movements united .
Get band
sphthy
ie

2 bands
mulu too small .

crystal held
spumy
.

olid Sdn
These :c

occur due to rorahcual

( Think Ctt
energy changes
.

Mclean Pans )
nvibvahonalspeerh Characteristic frequencies for =)

n
rotational fine structure
/ \

P



m H CIO M CN M N 02 m

.
a - - -
m

m
, , , ,

yMfhhphu
p

roahinal rraninal CO metal donates E to Iaabitals

The duration =
f

On =
1 vibrahural
purely
bond
'

stnyn of CIO an
fury f frequency
as . . .
 WATER

TETRAHEDRAL
3N 6=3
@ yznawe
-

Iot8gtg
y
,

W. %g
zsneuanng

1 P
Symmetric antisymmetric bending

f
to

6%

{ {

Sheathe LINEAR DIATOMIC 1

}nn ,
.
6
}nn

of=
,
.

o}%
Gamma 34 )
-
5=1 to
f

02 OCTAHEDRAL
36 ) 5 4 # 2 =#
stretchy
-

bending
=
,

symmetric mmOmn8 among antisymmetric

,
air of plane toy
nk

I##=%n
degenerate

=I=#m/
hare
f
-

the same vibration

frequency
in
pane

to
Supposed be 4 .

observe 2 ?
only
.
. -

why

2 are
degrate

symmetric in dipole manner i. nw Raceme

Charge
 RAMAN
JE
sane t= men

=mI: -

MZ

2
sleep process :

photon absorption
SELECTION RULE

followed by
emission

Require morewhe
change
puarisaesihhyol
in
Roman
) for

( vibration
hvi
activity
his inelastic
during
.

Roman how Can we move E aenss a band
spectroscopy
.

any

1/100000 whll do Ramon

'

inefficient
.

very
. .

Absorb exceed
prawn , gen

to virtual excited level

Then decays back down

Ashes )

Ei Es owkveskdui
If > then ( mon

If Ei < Es then autisms .