1

CHEM 1004 | Physical Chemistry

ATOMIC SPECTROSCOPY
Introduction

• Spectroscopy involves the investigation of the interaction of light with matter

• A spectrum shows how this interaction varies with the frequency of light

• Atomic spectroscopy involves the study of absorption and emission

• Quantum theory showed that electrons in atoms and molecules could not exist
with any arbitrary energy, but only in a set of quantized discrete energy states (or
ʻlevelsʼ) that were characteristic of the species in question

Principles of spectroscopy

• Based on the fact that atoms and molecules can only possess energy (electronic,
rotational, vibrational) in quantized amounts

hcRH
E =− J

n2
• Where h = Planckʼs constant c = speed of light in vacuum
n = principal quantum no RH = Rydbergʼs constant for H atom

• When a H atom€ re-arranges its electrons to move between 2 levels, it emits or

absorbs a photon with an energy equal to the separation of the levels

• Photon energy = E2 – E1 = hf = hv

• By measuring the energies of the photons that atoms emit or absorb, the
electronic energy levels and electronic structure can be determined

 2

Experimental Set-up

• 2 types of spectroscopy: absorption and emission

• Absorption spectra involves measuring the wavelength of light that are absorbed
by a sample where atoms are taking up energy and moving to higher energy
levels

• Emission spectra involves putting energy into the sample of atoms (heat /
electrical discharge) and exciting the atoms to higher levels. The wavelengths of
light emitted is measured as atoms return to the lower levels (give up energy)

• A typical absorption spectroscopic experiment will consist of:

• Light source to produce a broad range of wavelengths of light for the atoms to
absorb

• Sample usually in gaseous state, thereby requiring heating of the sample

• Wavelength-selecting element to ʻdisperseʼ the light after passing through the

sample to see which wavelengths (energies) of light are absorbed (e.g. prism or
diffraction grating)

• Detector which detects the position of light and hence the wavelength (e.g.
photographic plate / highly sensitive cameras)

• For an emission spectroscopic experiment, the light source is not needed but the
atomic sample has to be excited and the wavelengths of light emitted is
monitored

Atomic Spectra

• Consists of lines, showing that the electronic energy of atoms is quantized

(that atoms have energy levels)

• Different atoms have different patterns of lines and atomic spectra can be
used to identify different atoms

 3

E = hf
c = fλ
hc
E=
λ
• Energy ∝ 1/λ

• Wavenumber ( v˜ ) = 1/λ Hence, E = hc v˜

€
• Wavenumber is proportional to the photon energy (energy equivalent unit)

• Units:€length-1 (usually cm-1) €

Hydrogen Atomic Spectrum

• The emission spectrum of H shows many lines which are clearly in groups
(series), with each series converging with decreasing λ

• Four of the lines in the Balmer series in the visible are at approximately 410 nm,
434 nm, 486 nm and 656 nm

1 1
v˜ = −R H  2 − 2 cm −1
 n 2 n1 
• Where n1 = 1,2,3,4 for the Lyman, Balmer, Paschen and Brackett series and n2 is
an integer greater than n1; n2 is the quantum no of the upper level of the
transition and n1 is that of the lower level
€

• RH is the Rydberg constant for H atom, experimentally RH = 109677.8 cm-1

 hcR   hcR 
E = hcv˜ =  − 2 H  − − 2 H  = E 2 − E1
 n 2   n1 

€

 4

• The energy of the photon emitted must be equal to the energy difference of the 2
energy levels involved

• This is the energy level expression for the H atom (where n = principal quantum
no)

• The zero of energy (ionisation limit, n = ∞) is defined as a separated nucleus and

electron

• Orbital energies are negative (lowest energy orbital: most negative no)

• To determine R, we look at the wavenumbers of lines from an individual series

(i.e. where n1 is the same for all lines)

• Since n1 is a constant,
 
















































 v˜ = C −  R2 
 n2 
2
• Thus, by plotting (1/n2 ) as x against v˜ as y, a straight line with gradient –RH is
obtained
€
• Note: RX refers to the Rydberg constant derived from experiment for atom X
€
(since it differs slightly for different atoms)

Bohrʼs Postulates

1. Electrons move in circular orbits around the positively charged nucleus

2. Only certain orbits are allowed with integer values of n. The electron does not
emit energy when it is in one orbital

3. A single photon is emitted or absorbed when an electron moves from one orbit to
another

Angular Momentum

• If a particle has mass m and velocity v, the force F required to maintain it in a

circular orbit of radius r is

 5

mv 2




















































 F = −
r
• The negative sign shows the force is in the opposite direction to r

• Recap: Linear momentum

€ p = mv

• Where p is a vector quantity (direction being that of v)

• Similarly, for rotational motion, angular momentum L = Iw = mrv

• Where I = moment of inertia (angular equivalent of mass)

w = angular velocity (how fast we are rotating)

2
• Note: I = ∑m r i i where m = mass, r = radius (distance from rotational axis)
i
• The greater the angular momentum, the harder to stop it from spinning

• Heavy objects with large mass far from the axis of rotation have large I
€
• Angular momentum is also a vector quantity (direction being that of the rotation
axis)

• Important as electrons and photons have angular momentum which is usually

conserved in chemical processes

Energy in the Bohr atom

• Kinetic energy is energy due to movement; ½ mv2

e2
• Potential energy is energy due to position in a field; V = −
4 πε0 r
where e = fundamental charge, 1.602 x 10-19 C
ε0 = permittivity of free space, 8.854 x 10-12 F m-1

• Potential energy is a relative quantity €

• For a H atom, the zero of energy is defined as the electron and nucleus infinitely
separated

• As the electron gets closer to the positive nucleus, it becomes more stable and
its PE becomes negative

• Work W needed to move an electron from a distance r from the nucleus to infinite
separation
e2
























































 W = −V =
4 πε0 r

€

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q1q2e 2
• Force between 2 charged species F =
4 πε0 r 2
q1 = +1 for a proton and q2 = -1 for an electron

e2
• For the H atom, F = − € 2
4 πε0 r

Quantifying the Bohr Model

• €
Bohr assumed the angular momentum (mevr) was quantized in units of h/2π (ħ)

nh







 L = me vr = where n = 1,2,3,4... me = mass of e- r = orbit radius
2π
nh
• Rearranging the above equation, velocity of the orbiting electron is v =
2πm e r
€
• If the electron is moving in a circular orbit, the force required to maintain the
electron in that orbit must come from the electrostatic interaction of the proton
and the electron €
nh
Sub v =
2πm e r



 nh  2 e2
me   =
me v€2
e2  2πm e r  4 πε0 r
− =−



















 r 4 πε0 r 2 
















 n 2 h 2ε e2 

0
2 =
e rπme ε0
mev 2 =
4 πε0 r 2 2
n hε
r= 2 0
e πm e

• € orbit of the electron as a function of the principal quantum no

The radius of the
(n) can be calculated €

• To derive the energy level expression for the H atom,

E = E kin + V
1 e2
E = mev 2 −















































 2 4 πε0 r 


1 e 2  e2
E=  −
2  4 πε0 r  4 πε0 r
e2
E =−
8πε0 r
e 2 e 2πm e e 4 me  1 
E =− =  
8πε0 r n 2 h 2ε0 8ε02 h 2  n 2 

€

 7

e 4 me
• The final form is equivalent to E = –hcR(1/n ), where –hcR = 2


8ε02 h 2
e 4 me
= −hcR
8ε02 h 2






















































 

e 4 me €
Rcalc = 2 3
8ε0 h c

Extensions to the Bohr Model

Reduced Mass €

• To get better agreement between experiment and theory, the reduced mass of
the system µ is used instead of the mass of the electron

me mn























 µ = 




where mn = mass of the nucleus (molar mass)
me + mn
e 4µ
• Thus, R =
8ε02 h 3c
€
me mn mm
• However, if the nucleus is infinitely heavy (me << mn), µ = ≈ e n = me 

me + mn mn
€
• The value of R calculated with me is labelled as R∞ = Rcalc = 109737 cm-1

• To use the correct reduced mass for H atom,€1800me = mn

• µ = 1800me2 / 1801me = (1800/1801)me = 0.99944 me

RH(calc) = 0.99944 R∞ = 109676 cm-1

One-electron atoms

• For other one-electron atoms (e.g. He+, Li2+ etc), the charge on the nucleus Z
(proton no) has to be accounted for
hcZ 2 R
























































 E = −
n2

Ionisation Energies

• Refers to the energy € required to remove an electron from the ground state of the
atom to an infinite distance

• The IE of a given orbital corresponds to exciting the electron from that orbital to
an orbital with n = ∞

 8

• IE of H atom = 13.61 eV

• The value of 13.6 eV is vital in astrophysics; most of the atoms in the interstellar
medium are H. Hence, if UV photons of greater than 13.6 eV are emitted by a
star, they will be absorbed by ionising H atoms. Thus, UV photons greater than
13.6 eV do not propagate far through the UV medium

• IE can be determined experimentally using a graph of v˜ 
against 1/n2

Note: IE = R/n12 v˜ = IE – R/n22

• Gradient = –R and intercept = IE

• For a series where n1 > 1, IE will be the energy€needed to remove an electron

from the given orbital

Breakdown of the Bohr Model

• However, Bohr theory could not explain the doublets in the atomic spectra of the
alkali metals and hence was not a completely correct description of atomic
structure

• Wave mechanics (Schrodinger equation, Heisenberg uncertainty principle) gives

a satisfactory explanation of all atomic spectra

Quantum Theory

• The Schrodinger equation for the H atom shows that electrons occupy orbitals (s,
p, d, f etc.) with quantised energies

• Solving the SE for the H atom reveals that the electron can occupy various
orbitals, the orbitals (state) are characterised by quantum no.

• Principal quantum no (n) can take values from 1 to ∞ and is important in

determining the energy of the H atom

 9

• Orbital angular momentum quantum no (l) can take values from 0 to n–1 and
represents the angular momentum of the electron (or how fast the electron orbits
the atom)

• Note: In the H atom, for a given value of n, all the values of l have almost exactly
the same energy (degenerate), which is not true for more complex atoms

• Magnetic quantum no (ml) can take values from –l to +l for a given value of l
there are 2l + 1 independent wave functions (orbitals)

• For a given value of l all the different ml states have the same energy if there is
no applied electrical magnetic field (degenerate)

• In fact, ml represents the component of the orbital angular momentum along the
z-axis and that this orientation is quantized

Absorption Spectrum

• The energies of the orbitals, to a very good approximation depend only on n

• Levels with different l and ml values and the same value of n have effectively the
same energy

• In absorption, only transitions from the 1s level are observed as it takes a huge
amount of energy to get atoms to the 2s level (i.e. Lyman series where n1 = 1)

 10

• Note: Transitions in absorption involve 1s → np due to angular momentum and

symmetry conservation (i.e. can only excite from 1s to p orbital), thereby resulting
in the selection rule (Δl = +1)

• Similarly, upon absorbing or emitting a photon, l must change by 1 as the photon

has 1 unit of angular momentum (which needs to be preserved)

• There is no restriction on the change in n

• Note: Δml = 0, +1

Emission Spectrum

• It is more complicated as atoms can be excited to many different levels and many
transitions are possible

• All of the transitions must still conform to the selection rules of Δl = +1 and Δml =
0, +1

• The energies of these transitions can be calculated using the Bohr formula

Electron Spin

• Lines in the sodium spectrum are doublets due to ʻelectron spinʼ and its
interaction with the orbital angular momentum of the electron

• Experimental evidence for electron spin came from the Stern-Gerlach experiment where a beam of
Ag atoms was passed through an inhomogeneous magnetic field. The Ag beam was observed to
split into 2 parts and hence was assigned to the outer electron having a spin angular momentum, s
=½

 11

• Just like l has 2l + 1 possible orientations given by ml, s has 2 orientations (+½,
up and down)

• In the inhomogeneous magnetic field, these 2 spin orientations have different

energies and separate

• Note: ʻspinʼ is a convenient name for the intrinsic angular momentum of the
electron and there is no evidence that the electron ʻspinsʼ in a real sense.

Spin-orbit Interaction / Coupling

• Refers to the interaction between the spin angular momentum s of the electron
and its orbital angular momentum l

• Qualitatively, electrons in atoms have orbital angular momentum (l) but the
electrons also have its spin angular momentum (s = ½)

• The presence of the electron spin splits all energy levels (except ns, where l = 0)
of the H (and Na) atom into 2

• Reason for splitting: The electron has a magnetic moment and behaves like a
small bar magnet, this magnetic moment can be considered to arise from the
charged electron spinning on its axis

• However, if l > 0, the electron has angular momentum and the charge circles the
nucleus, which generate magnetic fields so the circulating electron also
generates a magnetic field at the nucleus. Thus, this gives rise to 2 magnetic
moments in the system

 12

• For 1 electron in the orbital, there are 2 different energies

• These magnets can be aligned (N–N) or opposed (N–S), where the opposed
arrangement has a lower energy than the aligned

• Spin-orbit coupling is the interaction between the electron spin and its orbital
motion via these magnetic effects

• Hence, a level with l > 0 is split into 2 by spin-orbit interaction

• Note: these splittings explain the doublets in the sodium spectrum and are also
present in the H atom but are small (0.1 cm-1 that we can often ignore them) and
have only been observed recently

• Such spin-orbit effects are not included in the Bohr equation

• The strength of the spin interaction (or how much they split apart) increases with
4
Z so it is larger for heavy atoms

• Quantitatively, in order to characterise the different states that come from the
different levels when considering spin-orbit coupling, the total angular
momentum, j, needs to be accounted for

• If an electron has orbital angular momentum l and spin angular momentum s then
the possible values of j are given by

j = l + s, l + s – 1, ... , | l – s |

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• Example: If an electron (s = ½) is in a p orbital (l = 1), j = 3/2, ½. In the same

manner, this proves that an electron in the p orbital results in 2 states (j = 3/2 and
½)

• In a H atom, the j with the lower value is lower in energy

• The Clebsh-Gordon series are used often in quantum mechanics to couple

together angular momentum (proton spins in NMR, rotational angular momenta)
to find a resultant angular momentum

Term Symbols

• Specifies the angular momentum states of an atom and shows the values of l, s
and j for a given state, e.g. 2P½

• The letter (e.g. S, P, D) represents the value of l (0, 1, 2, 3)

• The superscript represents the multiplicity (2s + 1)

• The subscript is the value of j

• Note: For a one-electron atom, 2s+1 is always 2 but for multi-electron atoms,
there is a need to combine the spins and l values of all the electrons in the atom

Fine Structure

• If we look with very high resolution at the H atom transitions, there is evidence of
these split states

• These multiple lines are termed the fine structure of the transition and is due to
spin-orbit coupling

Example

• The n=3 to n=2 transition has ʻfine structureʼ due to splitting of orbitals by spin-
orbit coupling (in fact it is made up of 7 lines). This splitting is very small and is
not accounted for in the Bohr formula

• When the electron is in the n=2 shell, s and p orbitals are present. When the
electron s in the n=3 shell, s, p and d orbitals are present

• Each of the orbitals where l > 0 will be split into a doublet

• In general, for H atom, ns: 2S½ , np: 2P3/2 2P½ , nd: 2D5/2 2D3/2
(this indicates that transition is independent of n)

• Note: In the H atom, the level with the lowest value of j has the lowest energy

 14

• Selection rules: Δl = +1, Δml = 0, +1, Δs = 0, Δj = 0, +1

• Proceed to mark the ʻallowedʼ transitions on the diagram (indeed there are 7
predicted transitions, just as observed experimentally)

• Total angular momentum has a quantised orientation, given by mj, where mj can
take values from j down in steps of 1 to –mj

mj = j, j – 1, ..., –j

• In the absence of an external field, all the mj sublevels of a given j state are
degenerate (same energy)

• Example: the 4p 3P3/2 state with j = 3/2 has mj = 3/2, ½, -½, -3/2 is composed of 4
degenerate sub-levels if there is no field whereas the 4p 3P1/2 state with j = ½ has
mj = ½, -½ and is composed of 2 sublevels

• However, in an external field (magnetic, electric) the degeneracy of the mj levels

is removed and our atomic spectra exhibit more lines

• This removal of degeneracy of the mj levels in a magnetic field and the

consequent increasing complexity of the atomic spectrum is called the Zeeman
effect

Zeeman and Stark effects

• The Starck effect refers to the separation of the mj levels due to an electric field

• The Zeeman effect is the separation of mj levels due to a magnetic field

• If the atom under consideration has non-zero spin angular momentum (s > 0) as
in the H atom, the splitting in a magnetic field is described as the anomalous
Zeeman effect

Anomalous Zeeman Effect

• In a magnetic field, the energies of the mj sublevels of a given j state vary as

EZeeman = k gj mj

• Where k is a constant depending on the size of the magnetic field (B)

• The splitting is proportional to mj, so mj sublevels with large positive or negative

values of mj are shifted most in energy

 15

• mj sublevels with negative values are shifted to lower energy, mj sublevels with
positive values to higher energy

• The splittings between mj levels are the same for the given j state

• The splittings between mj levels from different j states are not necessarily the
same, probably different

• The splitting between the different mj levels of a given state at a given field is
given by gj (the Lande g factor)

• Levels with different combinations of l, s and j split to different extents depending

on their values of gj

• Need to calculate gj to know the relative splitting of the levels (whether they split
differently or by the same amount) and hence work out the pattern of lines that
will be observed

Example

• The 2 lines occur at the same energy if j=1/2 and j=3/2 levels split the same
amount

• If the j=1/2 and j=3/2 levels have different values of gj, and split different
amounts, the 2 transitions will have different energies

 16

3 j( j + 1) + s(s + 1) − l(l + 1)
gj =
2 j( j + 1)
• Value of gj determines how much the levels split for a given value of the
magnetic field (B)

•
€
If gj is large for a given (l, s, j) state then the different mj levels split a large
amount

• Note: In the absence of a magnetic field, due to selection rules, the transition will
be a doublet

Zeeman effect for 3p → 2s

• Need to consider the individual j levels (or terms / fine structure levels) and then
work out which transitions are possible between the different mj levels

• 3p 2P3/2 : l = 1, s=1/2, j=3/2, mj=3/2, ½, - ½, -3/2 (this level will split into 4 in a
magnetic field)

And so on for 3p 2P1/2 (split into 2), 2s 2P1/2 (split into 2)

• Work out how much the states split to determine if different transitions will occur
at the same energy and overlap in the spectrum

• To work out how much the levels split, calculate gj for the 3 different spin orbit
levels invoved (2P3/2, 2P1/2, 2S1/2)

• If gj is the same for 2 j levels then the mj components of the 2 levels will split the
same amount

• The greater the value of gj, the greater the splitting

• Sketch out the energy level diagram of the split levels

• In the absence of a field, selection rules (Δl = +1, Δs = 0, Δj = 0, +1) show the
transition is a doublet

• To see which transitions are possible in the field, selection rule for mj:
Δmj = 0, +1

• Note: Consider the possible transitions in the zero field first before considering
those in the magnetic field

• No magnetic field: Δmj does not matter as all the given mj sublevels of a given (l,
s, j) state have the same energy

• In a magnetic field, individual mj components of l, s and j split


 17

Working

• Without a magnetic field, 2P3/2 and

2
P1/2 states are allowed to move
to the 2S1/2 state by emission of a
photon

• Indeed, 2P3/2 → 2S1/2 transition

splits into 6 lines and 2P1/2 → 2S1/2
transition splits into 4 lines

• Note: If it is split equal amounts,

then there will be overlap and
lead to less no of lines than
expected

Answering Technique

1. Begin with the orbital of interest and work out the spin-orbit states possible (fine
structure)

2. Consider the orbital at which the orbital can ʻfallʼ to and account for spin-orbit
states

3. Sketch out the transition lines possible

4. Calculate gj for the corresponding states to determine which of these states will
split the most
3 j( j + 1) + s(s + 1) − l(l + 1)

 
 
 gj = 

2 j( j + 1)

5. With the calculated gj, see if there are any transitions overlapping (same gj for
different states)
€
6. Construct the energy level diagram and indicate the allowed transitions / lines

 18

Applications of Atomic Spectroscopy

Beer-Lambert Law

• Converts the intensity of light absorbed or emitted into a number density /

concentration so as to determine the abundances of atoms, molecules or ions
etc.

I = I0e−κcl

• Where I0 = incident light intensity, I = transmitted light intensity, l = length of

absorbing medium, c = concentration, κ = wavelength-dependent absorption
coefficient (molar absorptivity), units: dm3 mol-1 cm-1
€
• The larger the value of κ, the more strongly light is absorbed by individual target
molecules at a given wavelength

• Note: the exponent in Beer-Lambert Law, κcl, is dimensionless

• In Beer-Lambert Law, the ratio of I/I0 is always measured hence they must be in
the same units
I I
= e−κcl 



 A = −ln  = κcl 

I0  I0 

• Measuring the absorbance provides a means to find the concentration of an

absorber
€ €
• Construct a calibration graph for absorbance of standard samples of known
concentration in a standard cell (cuvette) with fixed length and read off the
absorbance for the unknown sample to find concentration

• In the gas-phase, Beer-Lambert law is written using number density instead of

concentration, i.e.

 
 
 
 I = I0e−σnl

• Where n = no of absorbing species per unit vol (units: cm-3) and σ = absorption
cross section (units: cm2) (does not necessarily depend on physical size)
€
• The larger σ, the more strongly an individual molecule absorbs the wavelength of
light

• σ is an effective area of the absorbing atom / molecule and σ can be larger or

smaller than the geometric cross section of the molecule

 19

Metals in the upper atmosphere

• Experiments based on atomic spectroscopy have been used to probe the

presence of metal atoms in the atmosphere (specifically in the mesosphere at
altitudes of 70 – 100 km)

• Na, K, Fe and Ca+ were detected

• Tunable lasers, based on the same principle as RADAR (Radio detection and
ranging), were used, which involved sending out a pulse of radio waves and
measuring the time taken by the pulse when it is reflected from a target

• By knowing the speed of light, the delay of the echo gives its distance

• Similarly, a laser was used to send a pulse of light into the atmosphere at
precisely the wavelength of one of the transitions of the atom of interest

• A spectrometer is used to detect the time taken for the reflected light to return. It
shows the no of photos returning to the detector (LIDAR – Light detection and
ranging)

• If there are many atoms of interest present at a given altitude, there will be a big
increase in the light reflected back at the relevant time, as the atoms absorb and
then re-emit the light

• Using LIDAR, the concentration of atoms with altitude can be mapped out,
allowing the modelling of the chemistry of these layers in the atmosphere

• The layers have seasonal variations

• The metals arise from the ablation (burning up) of meteors which hit the upper
atmosphere

• LIDAR shows strong, very localised metal layers which rapidly form and quickly
disappear, which are thought to be associated with meteor showers depositing
large quantities of metals into the upper atmosphere

• There are chemical reactions which then remove the metal atoms (e.g. Na →→
NaOH)

Solar Magnetic Field

• The Sun has a complex magnetic field and sunspots are related to regions of
high solar magnetic field

• Magnetic fields on the sun can be measured by measuring the Zeeman splitting
of atomic emission lines as a function of the position on the sunʼs surface

 20

• These measurements show the magnetic field in sunspots is about 1000 times
bigger than the average solar magnetic field

• The ʻloopsʼ of hot gases are trapped in the high magnetic fields (these gases /
ions have rich chemistry)

Auroras

• Auroras are emissions from atoms – natural atomic spectra

• The atoms are excited by collisions with energetic particles emitted from the sun
(solar wind)

• Auroras are dominated by emission from atomic oxygen

• The charged particles, the solar wind, reach the earthʼs atmosphere near the
poles due to the earthʼs magnetic field

• Spectroscopy of aurora allows atmospheric modellers to probe the chemistry and

composition of the upper atmosphere