Optical Electronic Spectroscopy 1

Lecture Date: January 23rd, 2008

The Electromagnetic Spectrum

UV-Visible
X-ray

What is Electronic Spectroscopy?

Spectroscopy of the electrons surrounding an atom or a

molecule: electron energy-level transitions
Atoms: electrons are in
hydrogen-like orbitals
(s, p, d, f)

Molecules: electrons are in

molecular orbitals (HOMO,
LUMO, )

From
http://education.jlab.org

(The Bohr model for nitrogen)

(The LUMO of benzene)

Optical Electronic Spectroscopy

Definition:

Spectroscopy in the optical (UV-Visible) range

involving electronic energy levels excited by
electromagnetic radiation (often valence electrons).

This lecture is related to the high-energy (non-optical)

electron spectroscopy covered in the X-ray lecture

Methods:
Atomic absorption
Atomic emission (e.g ICP-OES)
Molecular UV-Visible absorption
Luminescence, Fluorescence, Phosphorescence

Definitions of Electronic Processes

Emission:

radiation produced by excited molecules, ions,

or atoms as they relax to lower energy levels.

Absorption:

radiation selectively absorbed by molecules,

ions, or atoms, accompanied by their excitation (or
promotion) to a more energetic state.

Luminescence:

radiation produced by a chemical reaction

or internal electronic process, possibly following
absorption.

More Electronic Processes

Fluorescence:

absorption of radiation to an excited state,

followed by emission of radiation to a lower state of the
same multiplicity
Occurs about 10-5 to 10-8 seconds after photon absorption

Phosphorescence:

absorption of radiation to an excited

state, followed by emission of radiation to a lower state of
different multiplicity
Occurs about 10 to 10-5 seconds after photon absorption

What is Emission?

Atoms/molecules are driven to excited states (in this case

electronic states), which can relax by emission of
radiation.
M + heat M*
Higher energy

E = h
Lower energy

Other process can be active, such as non-radiative

relaxation (e.g. transfer of energy by random collisions).

M* M + heat

OES = Optical Emission Spectroscopy

What is Absorption?

Electromagnetic radiation travels fastest in a vacuum.

When EM radiation travels through a substance, it can be slowed
by propagation interactions that do not cause frequency
(energy) changes:

c
ni
i

c = the speed of light (~3.00 x 108 m/s)

i = the velocity of the radiation in the medium in m/s
ni = the refractive index at the frequency i

Absorption does involve frequency/energy changes, since

the energy of EM radiation is transferred to a substance,
usually at specific frequencies corresponding to natural
atomic or molecular energies
Absorption occurring at optical frequencies involves low to midenergy electronic transitions.

Absorption and Transmission

Transmittance:
T = P/P0

P0

Absorbance:
A = -log10 T = log10 P0/P

A is linear vs. b!
(A preferred over T)

Graphs from http://teaching.shu.ac.uk/hwb/chemistry/tutorials/molspec/beers1.htm

The Beer-Lambert Law

The Beer-Lambert Law (a.k.a. Beers Law):

A = bc
Where the absorbance A has no units, since A = log10 P0 / P
is the molar absorbtivity with units of L mol-1 cm-1
b is the path length of the sample in cm
c is the concentration of the compound in solution, expressed in mol L-1 (or M,
molarity)

Beers law can be derived from a model that considers

infinitesimal portions of a block absorbing photons in

their cross-sections, and integration over the entire block
Beers law is derived under the assumption that the fraction of the
light absorbed by each thin cross-section of solution is the same
See pp. 302-303 of Skoog, et al. for details

Deviations From the Beer-Lambert Law

Deviations from Beers law (i.e. deviations from the

linearity of absorbance vs. concentration):

Intermolecular interactions at higher concentrations

Chemical reactions (species having different spectra)
Peak width/polychromatic radiation
Beers law is only strictly valid with single-frequency radiation
Not significant if the bandwidth of the monochromator is less
than 1/10 of the half-width of the absorption peak at halfheight.

For an alternative view, see: Bare, William D. A More Pedagogically Sound Treatment of Beer's Law:
A Derivation Based on a Corpuscular-Probability Model, J. Chem. Educ. 2000, 77, 929.

Deviations from the Beer-Lambert Law

Intermolecular interactions at higher concentrations:

Dimers,
oligomers

Figure from Chapter 5 of Cazes, Analytical Instrumentation Handbook 3rd Ed. Marcel-Dekker 2005.

Deviations from the Beer-Lambert Law

Deviations caused by use of polychromatic light on a

spectrum in which changes a lot over the bandwidth of

the light.

Consider two wavelengths a and b with a and b

1

Aa b log

= 1500, 500

P a 10 abc P b 10 bbc
0
0

0.8

Absorbance (A)

P0a P0b

= 1000, 1000

= 1750, 250

0.6

0.4

0.2

0.2

0.4

0.6

Concentration (M)

0.8

Basic Instrument Layout for

Optical Spectroscopy

Absorption:
Radiation
Source

Wavelength
Selector

Sample

Detector
(photoelectric transducer)

Fluorescence, Phosphorescence and Scattering:

Wavelength
Selector

Sample

Detector
(photoelectric transducer)

(90 angle)
Radiation
source

Emission and chemi-luminescence

Sample
(source)

Wavelength
Selector

Detector
(photoelectric transducer)

Atomization: The Dividing Line for Atomic/Molecular

Samples used in optical

atomic (elemental)
spectroscopy are usually
atomized

This destroys molecules (if

present) and leaves the
atoms

The UV-visible spectrum of

the atoms is of interest, not

the molecular spectrum.

Elemental Analysis

Elemental analysis qualitative or quantitative

determination of the elemental composition of a sample

Optical electronic methods are heavily used in elemental

analysis

Other elemental analysis methods not discussed here:

Mass spectrometry (MS), e.g. ICP-MS
X-ray methods
Other methods (radiochemical)
Classical

Atomic Electronic Energy Levels

Electronic energy level

transitions in hydrogen
the simplest of all!

Balmer series (visible)

Transitions start
(absorption) or end
(emission) with the first
excited state of
hydrogen

Lyman series (UV)

Transitions start
(absorption) or end
(emission) with the
ground state of
hydrogen
Diagrams from http://csep10.phys.utk.edu/astr162/lect/light/absorption.html

Atomic Electronic Energy Levels

Term symbols and electronic

states: used to precisely define

the state of electrons

2 s 1 m j
spin
lj
multiplicity
s = total spin quantum number
j = total angular momentum quantum number
l = orbital quantum number (s,p,d,f)
mj = state

Term:

Level:

P3/2

State:

P3/2-1/2

Used to denote

s,p,d,f,g
(l value)
2j+1

energy levels, and

label term (Grotrian)
diagrams for the
hydrogen atom

Figure from the Sapphire Electronic Spectroscopy Software Package, Cavendish Instruments Limited.

Atomic Electronic Energy Levels

Term symbol (Grotrian)

diagram for the sodium atom

Each transition on the

diagram can be linked to a

peak in the spectrum

The number of lines can

approach 5000 for transitionmetal elements.

Line broadening can be

caused by:

Doppler effects
pressure broadening
(collisions)
Lifetime of state (uncertainty)
Figure from H. A. Strobel and W. R Heineman, Chemical
Instrumentation: A Systematic Approach, Wiley, 1989.

Atomic Electronic Energy Levels

The population of energy levels partly determines the

intensity of an emission peak

The Boltzmann distribution relates the energy difference

between the levels, temperature, and population:
Eexcited E ground
N excited
Pexcited

exp
N ground
Pground
kT

E = energy of state
P = number of states having equal energy at each level
N = number of atoms in state

Key point: to get more atoms into excited states, you need
higher temperatures. (See example 8-2, problem 8-9)
Element/Line (nm)

Ne/Ng at 2000 K

Ne/Ng at 3000 K

Ne/Ng at 10000 K

Na 589.0

9.9 x 10-6

5.9 x 10-4

2.6 x 10-1

Ca 422.7

1.2 x 10-7

3.7 x 10-5

1.0 x 10-2

Zn 213.8

7.3 x 10-15

5.4 x 10-10

3.6 x 10-3

(Values from Cazes pg 79, Table 1)

Atomic Electronic Energy Levels

The simulated spectrum for the sodium atom

Intensity / Arbitrary Units

100000

80000

60000

40000

20000

0
0

5000

10000

Wavelength / nm

15000

20000

Atomic Emission

Two types of emission spectra:

Continuum
Line spectra

Examples:
ICP-OES (inductively-coupled
plasma optical emission
spectroscopy), also known as ICPAES
LIBS (laser-induced breakdown
spectroscopy)

Torches and Atomic Emission

History: Emission came first (study of sunlight by Fraunhofer in

1817, identification of spectral lines), studied throughout the
1800s and early 1900s

Before the use of the plasma for

OES in 1964, the flame/gas torch (or
arc/spark, etc) had the following
problems:
Temperature instability
Not hot enough to excite/decompose
all materials

Atomizer/
Emission Source

Temperature
(C)

Flame

1700-3150

Plasma (e.g.
ICP)

4000-8000

Electric arc

4000-5000

Electric spark

>10000

Today: The plasma has become the almost universallypreferred method

History: atomic emission placed demands on monochromators

Today: Technology has led to polychromators/detectors with
sufficient resolution

Plasma Torches

Plasma:

a low-density gas
containing ions and electrons,
controlled by EM forces

Plasma Torches
In the inductively-coupled
plasma (ICP) torch, the
sample will reside for
several milliseconds at
4000-8000K.

Other torches direct

current plasma

Microwave induced plasma

An argon ICP torch in action:

Photo by Steve Kvech, http://www.cee.vt.edu/program_areas/environmental/teach/smprimer/icpms/icpms.htm#Argon%20Plasma/Sample%20Ionization

More on Plasma Torches

Another view of an argon ICP torch:

Diagram from Lagalante, Appl. Spect. Reviews. 34, 191 (1999)

Arc and Spark Sources for Atomic Emission

Arc and spark sources used for qualitative analysis of

organic and geological samples

Only semi-quantitative because of source instability

Spark sources achieve higher energies

Several mg of solid sample is packed between

electrodes, 1-30 A of current is passed achieving

several hundred volts potential.

Applications include metals analysis or cases where

solids must be analyzed.

Atomic Emission: Mono- and Polychromators

Diffraction gratings are used

to select wavelengths (in
combination with collimating
lens, and slits)

Echelle (ladder) gratings:

high dispersion and high
resolution

~1000-1500 grooves/mm
typical for UV-Vis work
Require filters to isolate
orders (i.e. n=1)

m = d(sin i + sin r)

Atomic Emission: Detectors

At the end of the spectrometer, photons are detected.

Commonly used detectors:
Photomultiplier tubes (PMT) dynamic range 109
Solid-state detectors:
Charge-coupled devices (CCD) 1D or 2D arrays
(charge readout or transfer devices)
Silicon photodiodes with thousands of individual
elements
Very sensitive, very well-suited to echelle grating
polychromators, very fast

Modern ICP-OES Spectrometers

Example system:
Varian Vista PRO

Features:
1. Axial flame view
2. Echelle grating
polychromator
3. CCD detector

CCD chips are

often made of subarrays matched to

emission lines.

Figure from Varian Vista PRO sales literature.

Detection Limits of ICP-OES

Typical detection limits

(Varian Vista MPX):

Considerations include

the number of emission

lines, spectral overlap

Linearity can span

several orders of
magnitude.

See also Figure 10-13 in

Skoog, et al.

Element Wavelength (nm)

Ag
328.068
Al
396.152
As
188.98
As
193.696
Ba
233.527
Ba
455.403
Ba
455.403
Be
313.107
Ca
396.847
Ca
317.933
Cd
214.439
Co
238.892
Cr
267.716
Cu
327.395
Fe
238.204
K
766.491
Li
670.783
Mg
279.55
Mg
279.8
Mn
257.61
Mo
202.03
Na
589.59
Ni
231.6
P
177.43
Pb
220.35
Rb
780.03
S
181.972
Sb
206.83
Se
196.03
Sr
407.77
Sn
189.93
Ti
336.12
Tl
190.79
V
292.4
Zn
213.86

Detection Limit
axial (ug/L)
0.5
0.9
3
4
0.1
0.03
0.03
0.05
0.01
0.8
0.2
0.4
0.5
0.9
0.3
0.3
0.06
0.05
1.5
0.1
0.5
0.2
0.7
4
1.5
1
4
3
4
0.02
2
0.5
2
0.7
0.2

Detection limit
radial (ug/L)
1
4
12
11
0.7
0.15
0.15
0.15
0.3
6.5
0.5
1.2
1
1.5
0.9
4
1
0.1
10
0.133
2
1.5
2.1
25
8
5
13
16
16
0.1
8
1
13
2
0.8

Atomic Absorption Early History

In the beginning atomic emission was the only way to
do elemental analysis via optical spectroscopy

Bunsen and Kirchhoff (1861) invented a non-luminous

flame to study emission. Showed that alkali elements in

the flame removed lines from a continuous source.

Walsh (1955) notices that molecular spectra are often

obtained in absorption (e.g. UV-Vis and IR), but atomic

spectra are always obtained in emission. Proposes to
use atomic absorption (AA or AAS) for elemental analysis
Advantages over emission far less interference, avoids
problems with flame temperature

Atomic Absorption (AA) and Elemental Analysis

Atomic absorption spectrometry

is one of the most widely used
methods for elemental analysis.

Source

Basic principles of AA:

P0

The sample is atomized via:

A flame (methane/H2/acetylene
and air/oxygen)
An electrothermal atomizer (an
electrically-heated graphite tube
or cup)

UV-Visible light is projected

through the flame
The atoms absorb light (electronic
excitation), reducing the beam
The difference in intensity is
measured by the spectrometer

Sample/Flame

P
Monochromator

Detector

Images are of Aurora AI1200, http://www.spectronic.co.uk

Atomic Absorption: Sources

Hollow cathode lamps sputtering of an element of

interest, generating a line emission spectrum:

Typical linewidths of 0.002 nm (0.02)

Other AA Sources: electrode-less discharge lamp (EDL)
see Skoog Ch 9B-1

Atomic Absorption: Monochromators

The monochromator filters out undesired light in AA

(typical bandwidths are 1 angstrom/0.1 nm)

Unlike ICP-OES, where the mono- or polychromator

actually analyzes the frequency.

In other words there is no need to scan the grating, just set

(aimed through a slit) and run

Echelle (ladder) gratings are popular:

Figure from T. Wang, in J. Cazes, ed, Ewings Analytical Instrumentation Handbook

Other Features of Atomic Absorption Systems

Sample nebulizers:

Produces aerosols of samples to

introduce into the flame (oxyacetylene is the hottest)

Detectors:

Common examples are photomultiplier tubes,

CCD (charge-coupled devices), and many more.

Monochromator:

removes emissions from the flame

(flame is often kept cool just to avoid emission)

Modulated source (chopper):

also removes the remaining

emissions from the flame. The signal of interest is given
an AC modulation and passed through a high-pass filter.

Spectral interferences:
Absorption from other things (besides the element of interest)
other flame components, particulates, etc Scattering can
cause similar problems
Background correction can help

Detection Limits of Atomic Absorption Systems

How Are Elements Actually Analyzed?

For AA and ICP-OES, samples are dissolved or digested

into solution.

Samples are flowed into the flame/plasma and analyzed.

Two methods for quantitative analysis:
Standard calibration: the unknown samples
absorbance/emission is compared with several references which
bracket the expected concentration. (Linear relationship)
Standard addition: the unknown sample is divided into several
portions. One portion is directly analyzed, the others have the
reference material added in varying amounts. The linear
relationship is determined, and the intercept is used to calculate
the real concentration of the unknown

At the end: the results yield elements in ppm, ppb,

mg/mL, etc

Atomic Fluorescence

Developed as an alternative to AA and ICP-OES, with

potentially greater sensitivity.

Has not yet achieved widespread use but cheaper tunable lasers
may change this.

Laser stimulated emission (coherent emission from an

excited state induced by a second photon)

Processes:
hv

Non-radiative
Thermal

hv

Resonance

Non-radiative

Direct Line

hv

Stepwise

hv

Thermally-assisted

Atomic Fluorescence

Instrumentation
Sample

Wavelength
Selector

(90 angle)
Radiation
source

Sources include hollow-

cathode lamps,
electrodeless discharge
tubes (brighter), and lasers
(brightest)

Picture from Perkin-Elmer

Detector
(photoelectric transducer)

Laser-Induced Breakdown Spectroscopy (LIBS)

Just like ICP-OES, except a focussed laser creates the

plasma:

Fiber optic

Figure from US Army/Ames

Elemental Analysis with Optical Spectroscopy

A comparison of the techniques the choice is not always clear!

Plasma Emission
(ICP-OES)

AA (Flame)

Atomic
Fluorescence

Dynamic Range

Wide

Limited

Wide

Qualitative Analysis

Good

Poor

Poor

Multielement Scan?

Good

Poor

Poor

Trace Analysis

Good

Good

Good

Small samples

Good

Good

Good

Matrix interferences

Low

High

Low

Spectral
interferences

High

Low

Low

Cost

Moderate

Low

Moderate

Speciated analysis: The analysis of atomic species, elements in

chemically distinguishable environments.

Examples of hyphenation to add speciation:

ICP-OES coupled to a HPLC
AA coupled to a GC

Homework Problems
Optical Electronic Spectroscopy
Chapter 8:
Problem 8-9
Chapter 10:
Problem 10-2

Further Reading
Review Skoog et al. Chapters 6-10
Review Cazes Chapters 3-4
Optical Electronic Spectroscopy
H. A. Strobel and W. R. Heineman, Chemical
Instrumentation: A Systematic Approach, 3 rd Ed.,
Wiley (1989).