AtomicandMolecular

Spectroscopy
Spectroscopy
Dr Stuart Mackenzie
DrStuartMackenzie

thermodynamics
AtomicStructure
kinetics

Rate
Rate
processes

Statistical
Statistical
mechanics

Quantumtheory
atoms/molecules

Atomic&Molecular
Atomic
& Molecular
Spectroscopy

Quantum
Mechanics
Valence

NMR

Photochemistry

Reaction
ynamics
Dynamics

Lasers

Solids&
surfaces

Resources
Handouts(colouronline)
Tutorials
uto a s
Books:

ModernSpectroscopy (4th ed.2004)JMHollas

HighResolutionSpectroscopy(2nd ed.,1998)JMHollas
MolecularSpectroscopy(OUPPrimer)JMBrown
Spectra of Atoms and Molecules (2nd ed.2005)Bernath
SpectraofAtomsandMolecules
ed 2005) Bernath
FundamentalsofMolecularSpectroscopy(4th ed.1994)Banwell &McCash
AtomicSpectra (OUPPrimer)TPSoftley
MolecularQuantumMechanics (4th ed.)AtkinsandFriedman
ElectronicandPhotoelectronSpectroscopy,Ellis,Feher andWright

Practicals:
P
i l

II03HCl,DCl spectra
II04Fluorescenceandquenching
p
II08Flameatomicabsorption
p
II05I2 visiblespectrum
II10Na/Na+ atomicspec II17ComputationalRaman
II18N2+ spectrum

Lecture1:GeneralAspectsofSpectroscopy
1.1Electromagneticradiation
Transverse
Transversewaveofperpendicular,sinusoidally
wave of perpendicular sinusoidally
oscillatingelectricandmagneticfields

E = E 0 sin
i ( kkx t + )

withwavevector,k =2/
and angular frequency =2
andangularfrequency,
2
Characterisedby:
wavelength, (inm)or
frequency, (inHz)
Speedinvacuo defined ascvac =299792458ms1
c =
= = /k
cvac isrelatedtothepermittivity(electricconstant)
andpermeability(magneticconstant)offreespace:
(proofcomesfromMaxwellsEquations)

Aplaneelectromagnetic
wavepropagatinginthe
zdirection

c2 =

0 0

1.2QuantisedLight:Photons
Itwillusuallybeconvenienttoconsiderlightasastreamofzerorestmass
It
ill
ll b
i tt
id li ht
t
f
t
particlesorpackagesofradiationcalledphotonswiththefollowingproperties:
MaxPlanck
(18551947)

Energy,E=h
inwhichh isPlancksconstant,h =6.626x1034 Js

Linearmomentum,
Linear momentum p=
p = E/c=h
E/c = h/c=h/
/c = h/ (deBroglie)
(de Broglie)
LouisdeBroglie
(18921987)
(1892
1987)

(spin)Angular momentum equivalenttoaquantumnumberof1:

jph = 1i .e.,, jph

= 2=
ph
n.b., 1)photonsareBosons(i.e.,obeyBoseEinsteinstatistics)
2)photonshavehelicity
2)
photons have helicity (projectionofangularmomentumonthe
(projection of angular momentum on the
directionoftravel)of1only(i.e.,not0)

1.3QuantitiesandUnits
10 m]
Wavelength,:SIunit=m
[orm,nmorAngstrm,1=10

isdependent onthe(refractiveindexofthe)mediuminwhichthewavetravels

Frequency,: SIunit=Hz(i.e.,cycless1) [orMHz=106 Hz,GHz=109 Hz]

frequencyisindependentofthemedium
Energy,E: SIunit=J,
BUT:Itishardtomeasureenergydirectly.Spectraarerecordedaslineintensities
asafunctionoffrequency
f ti
ff
orwavelength.
l th
Theconversiontoenergyappears simple:E=h =hc/
Buthisonlyknownto8significantfigures.Hence,itisconvenienttointroduce
Wavenumber,aproperty definedasreciprocalofthevacuumwavelength:
andwhoseunitsareuniversallyquotedascm1 (n.b.notm1)

vac

Wavenumber isdirectlyproportionaltoenergy,E = hc andthuswecommonly

quoteenergiesinunitsofcm1.

1.4Energylevels:TheBornOppenheimerApproximation

tot

ee

ne

as trivial)

nn

SeeValencee
notesHTyear2

Thetotalenergyofamolecularsystemcomprises:
Thetranslationofthewholemolecule,Ttrans (n.b. well neglect this
Kineticenergy,Te and Tn ofelectronsandnuclei,respectively
Potentialenergy,Vee andVnn ofelectronsandnuclei,respectively
Potentialenergybetweennucleiandelectrons,Vne

TheBornOppenheimerApproximation(Annal.Phys.,84,457(1927))
The
orn Oppenheimer Approximation (Annal. Phys., 84, 457 ( 9 7))
Duetothedifferenceinmassbetweentheelectronandnuclei,themotionofthe
twomaybeseparatedandthetotalmolecularwavefunction, tot, may,toagood
approximation be written
approximation,bewritten
tot = el q ,Q n Q

electron coordinates

) ( )

nuclear coordinates

andtheresultingtotalenergyisasimplesum Etot =Eel +Enuc

Itwillbeconvenient,thoughlessrigorous,tofurtherfactorisen furtherinto
vibrational androtationalpartssotot = elvibrot and Etot=Eel+Evib+Erot

Molecular
EnergyLevels
l

i.e.,typically Eel >> Evib >> Erot

Differentelectronicstates
(electronic arrangements
(electronicarrangements,
configurationsorterms)

E 2x104 105 cm1 102 5x103 cm1

Transitionsat
500 100nm
100m
00
2m

Vis UV
infrared

3 300GHz
(0.1 10cm1)
10cm 1mm
microwave

1.5ThePopulationofEnergylevels
ni

Ei
E

n0

E=0

The Boltzmann Law

TheBoltzmannLaw
Atthermalequilibrium,thepopulationofthei th
energylevel isgivenby:
Ei
N
ni = g i exp

q
kT
Ei
q=
g i exp
levels ,i
kT

Where:
q isthemolecularpartitionfunction(seeHTStat.Mech.notes)
gi isthedegeneracy ofthei th level(theno.stateswithsameenergy)
Ei istheenergy
is the energy ofthei
of the i th level
k istheBoltzmannconstant (=R/NA=1.381x1023JK1)
T istheKelvintemperature

Hence relative to n0:

Hence,relativeton

ni g i
E
= exp

n0 g 0
kT

LudwigBoltzmann18441906

1.6TheInteractionofLightandMatterI:Asimpleclassicalpicture
Considerthewaysinwhichasinglephotonmightinteractwithasystemoftwo
Consider
the ways in which a single photon might interact with a system of two
energylevelsE1 andE2,withpopulationsn1 andn2,respectively:
A.Stimulatedabsorption,M+h
i l d b
i
h
M**
Thephotonislost
ThesystemabsorbsenergyE =h =E2E1

E2

n2

E1

dn1
dn1
n1 rateofabsorption
rate of absorption =
E 21 n1
= B 12 E 21 n1
dt
dt

InwhichB12 istheEinsteinCoefficientofAbsorptionand (E21)isthe

radiationenergydensity(energyofradiationfieldm3)atenergyE21, which,for
ablackbodyattemperatureT,isgivenbyPlancksLaw
y
p
, g
y

( )

radiationdensity, E =

8 h 3

c3

1
E
1
kT

exp

B.Stimulatedemission M*+h M+2h

E2

n2

E1

n1

Additional
Additionalphotoncreatedwithsamefrequency,
photon created with same frequency
polarization,directionandphaseastheoriginal
Thesystemrelaxes,i.e., emitsenergy

rateofstimulatedemission =

dn2
dn
E 21 n2 2 = B 21 E 21 n2
d
dt
dt
d

inwhichB21 istheEinsteincoefficientofstimulatedemission.
Einsteinshowedthatforasystemtoreachequilibriuma3rd processmustoccur:
C.Spontaneousemission M* M+h
E2

n2

E1

n1

AphotoniscreatedwithE =E2 E1 =h
Thesystemrelaxes,i.e.,
Th
t
l
i emitsenergy
it
dn2
dn2
rate of spontaneous emission =
rateofspontaneousemission
n2
= An2
dt
dt

andA istheEinsteincoefficientofspontaneousemission(orEinsteinAcoefficient)

1.7TheEinsteinCoefficients[A.Einstein,Z.Phys.,18,121(1917)]
spont.
emission

absn

stim.
stim
emission

dn1
Atequilibrium:
= 0,i .e., B 12 ( E 21 ) n1 = A21n2 + B 21 ( E 21 ) n2
dt
A21n2
=
Rearranging, ( E 21 ) =
B 12n1 B 21n2 B
12
c.f.PlancksLaw
f

Yielding:

( )

E 21 =

8 h 3

c3

A21
g1
g2

exp

( )} B
E 21
kT

21

1
E 21
1
kT

exp

g 1B 12 = g 2B 21 andA 21 =

8 h 3

B 21

ThereisonlyoneindependentEinsteincoefficient
WhataretheimplicationsofthefactthattheAcoefficient,A 3?

1.8InteractionsofLightandMatterII:Atimedependenttreatment
E2

n2

Wewilloftenusepictureslike

toconsidertransitions.
E1

n1

Indeedourapproachwillbe
i)todeterminetheeigenstates (stationarystates)ofasystem
andthen ii)considerallowedtransitionsbetweenthesestates
i.e.,thephotondoesntexpicitly figure

Thetotalwavefunction,tot ,satisfiesthetimedependent Schrdingerequation:

whereH = H 0 +V t andV t = E 0 cos t

H = i =
t
Eigenstates arethesolutionsofthetindependentSchrdingereqn:H 0n = E n0n
andthefull(tdep)wavefunction is

n exp {iE not / =}

 tot isalinearcombinationofstationarystates =

c
n

t n exp {iE not / =}

Time-dependent coefficients
Aftersomemanipulation(seeMQM,Ch6),wearriveattherateoftransitiontostate
Aft
i l ti (
MQM Ch 6)
i
t th
t ft
iti t t t
m fromawelldefined,i.e.,pure,initialstate,j,tobe:

0
0
0
0

i
E

E
+
=

t
i
E

E
= t
E0
dc m t
m
j
m
j
j d
=
+ exp
exp
m
2i =
=
=
dt

Thus,fornonzerotransitionprobability(i.e.,allowedtransitions):
1 E 0 0theremustbenonzeroradiationintensity,
1.
0 there must be non zero radiation intensity aand
nd
2.E m0 E j0 = = i .e. ,energymustbeconserved, and

j d 0The
3
3.
m
0 The "transitiondip
transition dipolemo
ole moment"mustbenonz
must be nonzero
o

1.9TheTransitionDipoleMoment,R21

Thetransitiondipolemoment, TDM,isdefinedas R 21 = 2*
1d = 2 1

=
wherethedipolemomentoperator,

qi r i

P
Position
vector off ithh particle
l

Charge on i th particle

operatesuponourinitialwavefunction 1 producinganewstate = 1
TDM,R21, thusrepresentsthetransitionamplitude ofendingupinourparticular
state,, 2 ,,determinedbytheoverlapintegralof
y
p
g
2 with :

1
2 = 2

Therateoftransition(orintensity)isthesquareofthisamplitude:

i .e., transitionintensity
t
iti i t it R =
21
2

1d
2
*

1 2
= 2

TheTDMis,unsurprisingly,closelyrelatedtotheEinsteinBcoefficient(afterall
theybothdescribethesamething):
3

B 21 =

( 4 )3h

2
R
=
21
2

1
2
R
6 0 =2 21

1.10TheTransitionDipoleMomentandspectroscopicselectionrules

2
21

2* 1

= 2 1 2

The TDM is thus the ultimate source of spectroscopic selection rules for dipole
allowed transitions
transitions.
i.e., of all the conceivable energetically allowed transitions it determines which
actually occur and encompasses symmetry and angular momentum constraints.
Forbidden transitionshaveR21 =0
Allowed transitionshaveR
transitions have R21 0
0