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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:

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)

= 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

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

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

Itwillbeconvenient,thoughlessrigorous,tofurtherfactorisen furtherinto

vibrational androtationalpartssotot = elvibrot and Etot=Eel+Evib+Erot

Molecular

EnergyLevels

l

Differentelectronicstates

(electronic arrangements

(electronicarrangements,

configurationsorterms)

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

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,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

radiationenergydensity(energyofradiationfieldm3)atenergyE21, which,for

ablackbodyattemperatureT,isgivenbyPlancksLaw

y

p

, g

y

( )

radiationdensity, E =

8 h 3

c3

1

E

1

kT

exp

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

H = i =

t

Eigenstates arethesolutionsofthetindependentSchrdingereqn:H 0n = E n0n

andthefull(tdep)wavefunction is

tot isalinearcombinationofstationarystates =

c

n

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

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