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LecturesLectures 1-2:1-2: IntroductionIntroduction toto AtomicAtomic SpectroscopySpectroscopy

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Line spectra

 

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Emission spectra

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Absorption spectra

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Hydrogen spectrum

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Balmer formula

Bohr’s model

Atomic emission

spectra

Bulb

Sun

Na

H

Hg

Cs

Molecular absorption

spectra

Chlorophyll

Diethylthiacarbocyaniodid

Diethylthiadicarbocyaniodid

Diethylthiacarbocyaniodid Diethylthiadicarbocyaniodid PY3004 EmissionEmission andand AbsorptionAbsorption
PY3004 EmissionEmission andand AbsorptionAbsorption SpectroscopySpectroscopy Gas cloud 3 1 2 PY3004
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EmissionEmission andand AbsorptionAbsorption SpectroscopySpectroscopy
Gas cloud
3
1
2
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TypesTypes ofof SpectraSpectra

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Continuous spectrum: Produced by solids, liquids & dense gases produce - no “gaps” in wavelength of light produced:

produce - no “gaps” in wavelength of light produced: o Emission spectrum: Produced by rarefied gases

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Emission spectrum: Produced by rarefied gases – emission only in narrow wavelength regions:

gases – emission only in narrow wavelength regions: o Absorption spectrum: Gas atoms absorb the same

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Absorption spectrum: Gas atoms absorb the same wavelengths as they usually emit and results in an absorption line spectrum:

usually emit and results in an absorption line spectrum : Line Line Spectra Spectra PY3004 o

LineLine SpectraSpectra

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Electron transitions between energy levels result in emission or absorption lines.

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Different elements produce different spectra due to differing atomic structure (discovered by Kirchhoff and Bunsen).

H

produce different spectra due to differing atomic structure (discovered by Kirchhoff and Bunsen). H He C

He

produce different spectra due to differing atomic structure (discovered by Kirchhoff and Bunsen). H He C

C

produce different spectra due to differing atomic structure (discovered by Kirchhoff and Bunsen). H He C

! "

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Emission/AbsorptionEmission/Absorption ofof RadiationRadiation byby AtomsAtoms

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Emission/absorption lines are due to radiative transitions:

1. Radiative (or Stimulated) absorption:

Photon with energy (E # = h $ = E 2 - E 1 ) excites electron from lower energy level.

E # =h $

excites electron from lower energy level . E # = h $ E 2 E 1

E 2

E 1

from lower energy level . E # = h $ E 2 E 1 E 2

E 2

E 1

Can only occur if E # = h $ = E 2 - E 1

2. Radiative recombination/emission:

Electron emits photon with energy (h $ = E 2 - E 1 ) and makes transition to lower energy level.

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SimplestSimplest AtomicAtomic Spectrum:Spectrum: HydrogenHydrogen

In 1850s, the visible spectrum of hydrogen was found to contain strong lines at 6563, 4861 and 4340 Å.

H %

H &

H #

6563 4861 4340 !" (Å)
6563
4861
4340
!" (Å)
4340 Å. H % H & H # 6563 4861 4340 !" (Å) Lines found to

Lines found to fall more closely as wavelength decreases.

Line separation converges at a particular wavelength, called the series limit.

In 1885, Balmer found that the wavelength of lines could be written

where n is an integer >2, and R H is the Rydberg constant.

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Emission/AbsorptionEmission/Absorption ofof RadiationRadiation byby AtomsAtoms

o Radiative recombination can be either:

a) Spontaneous emission: Electron minimizes its total energy by emitting photon and making transition from E 2 to E 1 .

E 2 E 1
E 2
E 1
E 2 E 1
E 2
E 1

E # =h $

Emitted photon has energy E # = h$ = E 2 - E 1

b) Stimulated emission: If photon is strongly coupled with electron, cause electron to decay to lower energy level, releasing a photon of the same energy.

E # =h $

level, releasing a photon of the same energy. E # = h $ E 2 E

E 2

E 1

E 2 E 1
E 2
E 1

Can only occur if E # = h $ = E 2 - E 1 Also, h $ = h $

E # =h $

E # =h $

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SimplestSimplest AtomicAtomic Spectrum:Spectrum: HydrogenHydrogen

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If n =3, =>

 

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Called H % - first line of Balmer series.

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Other lines in Balmer series:

 
 

Name

Transitions

Wavelength (Å)

H

%

3 - 2

6562.8

H

&

4 - 2

4861.3

H

#

5 - 2

4340.5

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Balmer series limit occurs when n '(.

4340.5 o Balmer series limit occurs when n '( . Road to National Solar Observatory in

Road to National Solar Observatory in New

Mexico: “Highway 6563”

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SimplestSimplest AtomicAtomic Spectrum:Spectrum: HydrogenHydrogen

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Rydberg showed that all series above could be reproduced using

where n are principal quantum numbers.

Series limit occurs when n i = !, n f = 1, 2, …

Other series of hydrogen:

Lyman

UV

f = 1, n i )2

n

Balmer

Visible/UV

f = 2, n i )3

n

Paschen

IR

f = 3, n i )4

n

Brackett

IR

f = 4, n i )5

n

Pfund

IR

f = 5, n i )6

n

n i ) 5 n Pfund IR f = 5, n i ) 6 n Series
n i ) 5 n Pfund IR f = 5, n i ) 6 n Series

Series limits

BohrBohr ModelModel forfor HydrogenHydrogen

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Simplest atomic system, consisting of single electron-proton pair.

First model put forward by Bohr in 1913. He postulated that:

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1.

Electron moves in circular orbit about proton under Coulomb attraction.

2.

Only possible for electron to orbits for which angular momentum is quantised,

ie.,

L = mvr = nh

where n = 1, 2, 3, …

3.

Total energy (K + V) of electron in orbit remains constant.

4.

Quantized radiation is emitted/absorbed if an electron changes orbit. The frequency emitted is $ = (E i - E f ) / h.

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SimplestSimplest AtomicAtomic Spectrum:Spectrum: HydrogenHydrogen

o Ritz Combination Principle: Transitions occur between terms: where T f = R H /n
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Ritz Combination Principle: Transitions
occur between terms:
where T f = R H /n f 2 etc.
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Transitions can occur between certain terms
=> selection rule. Selection rule for
hydrogen: *n = 1, 2, 3, …
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Transitions between ground state and first
excited state produce a resonance line.
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Grotrian diagram shows terms and the
transitions.
Energy level or term diagram for hydrogen
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BohrBohr ModelModel forfor HydrogenHydrogen
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Consider atom consisting of a nucleus of charge +Ze and mass M, and an electron
on charge -e and mass m. Assume M>>m so nucleus remains at fixed position in
space.
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As Coulomb force is a centripetal:
(1)
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And assuming angular momentum is quantised:
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Solving for v and substituting into Eqn. 1 =>
(2)
and
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Quantized AM has restricted the possible circular orbits of the electron.

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BohrBohr ModelModel forfor HydrogenHydrogen

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The total mechanical energy is:

Using Eqn. 1,

The potential energy (V) can be calculated from

Total mechanical energy is therefore

Using Eqn. 2 for r,

Total mechanical energy is therefore Using Eqn. 2 for r, Therefore, quantization of AM leads to

Therefore, quantization of AM leads to quantisation of total energy.

(3)

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o

o

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BohrBohr ModelModel forfor HydrogenHydrogen

The wavelength of radiation emitted when an electron makes a transition, is (from 4th postulate):

or

an electron makes a transition, is (from 4th postulate): or where (4) Theoretical derivation of Rydberg

where

(4)

Theoretical derivation of Rydberg formula.

Essential predictions of Bohr model are contained in Eqns. 3 and 4.

predictions of Bohr model are contained in Eqns. 3 and 4. PY3004 o o Bohr Bohr

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BohrBohr ModelModel forfor HydrogenHydrogen

Substituting in for constants, Eqn. 3 can be written

and Eqn. 2 can be written

where a 0 = 0.529 Å = “Bohr radius”.

Eqn. 3 gives a theoretical energy level structure for hydrogen (Z=1):

a theoretical energy level structure for hydrogen (Z =1 ): o For Z = 1 and

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For Z = 1 and n = 1, the ground state of hydrogen is: E 1 = -13.6 eV

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CorrectionCorrection forfor MotionMotion ofof thethe NucleusNucleus

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Spectroscopically measured R H does not agree exactly with theoretically derived R ! .

But, we assumed that M>>m => nucleus fixed. In reality, electron and proton move about common centre of mass. Must use electron’s reduced mass (µ):

As m only appears in R ! , must replace by:

It is found spectroscopically that R M = R H to within three parts in 100,000.

Therefore, different isotopes of same element have slightly different spectral lines.

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CorrectionCorrection forfor MotionMotion ofof thethe NucleusNucleus

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Consider 1 H (hydrogen) and 2 H (deuterium):

Using Eqn. 4, the wavelength difference is therefore:

Called an isotope shift.

H & and D & are separated by about 1Å.

Intensity of D line is proportional to fraction of D in the sample.

cm -1

is proportional to fraction of D in the sample. cm - 1 Balmer line of H

Balmer line of H and D

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SpectraSpectra ofof Hydrogen-likeHydrogen-like AtomsAtoms

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Hydrogenic or hydrogen-like ions:

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He + (Z=2)

Li 2+ (Z=3)

Be 3+ (Z=4)

Hydrogenic

isoelectronic

sequences

Energy

(eV)

0

20

40

60

80

From Bohr model, the ionization energy is:

E 1 = -13.59 Z 2 eV

100

120

Z=1 Z=2 Z=3 H He + Li 2+ n n n 2 3 4 1
Z=1
Z=2
Z=3
H
He +
Li 2+
n
n
n
2
3
4
1
2 3
13.6 eV
2
1
54.4 eV
1

122.5 eV

Ionization potential therefore increases rapidly with Z.

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SpectraSpectra ofof Hydrogen-likeHydrogen-like AtomsAtoms

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Bohr model works well for H and H-like atoms (e.g., 4 He + , 7 Li 2+ , 7 Be 3+ , etc).

Spectrum of 4 He + is almost identical to H, but just offset by a factor of four (Z 2 ).

For He + , Fowler found the following in stellar spectra:

1 / " = 4 R He & $ 1 2 #

% 3

'

)

n 2 (

1

Energy

(eV)

See Fig. 8.7 in Haken & Wolf.

0

20

40

60

80

100

120

Z=1 Z=2 Z=3 H He + Li 2+ n n n 2 3 4 1
Z=1
Z=2
Z=3
H
He +
Li 2+
n
n
n
2
3
4
1
2 3

13.6 eV

1

54.4 eV

2

1

122.5 eV

 

ImplicationsImplications ofof BohrBohr ModelModel

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We also find that the orbital radius and velocity are quantised:

 

and

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Bohr radius (a 0 ) and fine structure constant (%) are fundamental constants:

 
 

and

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Constants are related by

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With Rydberg constant, define gross atomic characteristics of the atom.

 
 

Rydberg energy

R

H

13.6 eV

Bohr radius

a

0

5.26x10 -11 m

Fine structure constant

!

1/137.04

 

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ExoticExotic AtomsAtoms

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Positronium

 

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electron (e - ) and positron (e + ) enter a short-lived bound state, before they annihilate each other with the emission of two #-rays (discovered in 1949).

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Parapositronium (S=0) has a lifetime of ~1.25 x 10 -10 s. Orthopositronium (S=1) has lifetime of ~1.4 x 10 -7 s.

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Energy levels proportional to reduced mass => energy levels half of hydrogen.

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Muonium :

 

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Replace proton in H atom with a µ meson (a “muon”).

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Bound state has a lifetime of ~2.2 x 10 -6 s.

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According to Bohr’s theory (Eqn. 3), the binding energy is 13.5 eV.

o

From Eqn. 4, n = 1 to n = 2 transition produces a photon of 10.15 eV.

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Antihydrogen:

 

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Consists of a positron bound to an antiproton - first observed in 1996 at CERN!

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Antimatter should behave like ordinary matter according to QM.

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Have not been investigated spectroscopically … yet.

 

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FailuresFailures ofof BohrBohr ModelModel

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From the Bohr model, the linear momentum of the electron is

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However, know from Hiesenberg Uncertainty Principle, that

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Comparing the two Eqns. above => p ~ n*p

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This shows that the magnitude of p is undefined except when n is large.

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Bohr model only valid when we approach the classical limit at large n.

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Must therefore use full quantum mechanical treatment to model electron in H atom.

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FailuresFailures ofof BohrBohr ModelModel

Bohr model was a major step toward understanding the quantum theory of the atom

- not in fact a correct description of the nature of electron orbits.

Some of the shortcomings of the model are:

1. Fails describe why certain spectral lines are brighter than others => no mechanism for calculating transition probabilities.

2. Violates the uncertainty principal which dictates that position and momentum cannot be simultaneously determined.

o

Bohr model gives a basic conceptual model of electrons orbits and energies. The precise details can only be solved using the Schrödinger equation.

o

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HydrogenHydrogen SpectrumSpectrum

Transitions actually depend on more than a single quantum number (i.e., more than n).

Quantum mechanics leads to introduction on four quntum numbers.

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Principal quantum number: n

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Azimuthal quantum number: l

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Magnetic quantum number: m l

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Spin quantum number: s

Selection rules must also be modified.

l o Magnetic quantum number: m l o Spin quantum number: s Selection rules must also

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AtomicAtomic EnergyEnergy ScalesScales

Atomic Atomic Energy Energy Scales Scales Energy scale Energy (eV) Effects Gross structure   1-10

Energy scale

Energy (eV)

Effects

Gross structure

 

1-10

electron-nuclear attraction Electron-electron repulsion Electron kinetic energy

Fine structure

0.001 - 0.01

Spin-orbit interaction

Relativistic corrections

Hyperfine structure

10

-6 - 10 -5

Nuclear interactions

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