6C.

Quantum-Mechanical Properties of Radiation

The photoelectrons are attracted to

the anode when it is positive with respect to
the cathode. When the anode is negative as
shown, the electrons are “stopped”, and no
current passes. The negative voltage
between the anode and the cathode when the
current is zero is the stopping potential
(V0).
Cont’d KEm = hv – ω
h: Planck’s constant = 6.6254 x 10-34 joule-sec.
- ω : work function
represents the minimum energy binding electron in
the metal.
E = hv = KEm + ω
E = hv = eV0 + ω E = h(c/λ) = eV0 + ω
FIGURE 6-14 Maximum kinetic energy of
photoelectrons emitted from three metal
surfaces as a function of radiation frequency.
The y-intercepts (-ω) are the work functions for
each metal. If incident photons do not have
energies of at least hv = ω, no photoelectrons
are emitted from the photocathode.
6C.2 Energy States of Chemical Species (atoms, ions, molecules)
Quantum theory:
1. Atoms, ions, and molecules can exist only in certain discrete states,
characterized by definite amounts of energy. (quantized)
2. When atoms, ions, and molecules absorb or emit radiation in making the
transition from one energy state to another, the frequency or wavelength of
the radiation is related to the energy difference between the states by :

• Atoms or ions: electronic states

• Molecules: electronic states, vibrational
states, rotational states. At room
temperature, chemical species are primarily
in their ground state.
6C.3 Interactions of Radiation and Matter

Emission or chemiluminescence
processes. In (a), the sample is excited by
the application of thermal, electrical, or
chemical energy. These processes do not
involve radiant energy and are hence called
non-radiative processes.
Cont’d

FIGURE 6-15(b) In the energy level diagram (b), the dashed lines with upward-
pointing arrows symbolize these non-radiative excitation processes, while the solid
lines with downward-pointing arrows indicate that the analyte loses its energy by
emission of a photon.
Cont’d

FIGURE 6-15(c) In (c), the resulting spectrum is shown as a measurement of the

radiant power emitted PE as a function of wavelength, λ.
• Emission spectroscopy Chemiluminescence sepctroscopy
• Photoluminescence spectroscopy (fluorescence, phosphorescence spectroscopy)
Cont’d
FIGURE 6-16 Absorption
Methods. Radiation of
incident radiant power P0 can
be absorbed by the analyte,
resulting in a transmitted
beam of lower radiant power
P. For absorption to occur, the
energy of the incident beam
must correspond to one of the
energy differences shown in
(b). The resulting absorption
spectrum is shown in (c).
Cont’d
Cont’d

FIGURE 6-17(a) Photoluminescence methods (fluorescence and

phosphorescence). Fluorescence and phosphorescence result from
absorption of electromagnetic radiation and then dissipation of the
energy emission of radiation (a).
Cont’d

FIGURE 6-17(b) In (b). the absorption can cause excitation of the

analyte to state 1 or state 2. Once excited, the excess energy ca be lost
by emission of a photon (Iuminescence, shown as solid line) or by non-
radiative processes (dashed lines).
Cont’d

FIGURE 6-17(c) The emission occurs over all angles, and the wavelengths
emitted (c) correspond to energy differences between levels. The major
distinction between fluorescence and phosphorescence is the time scale of
emission, with fluorescence being prompt and phosphorescence being
delayed.
Cont’d
Radiation scattering
1. Elastic scattering: the wavelength of the scattered radiation is the same as that of the source
radiation. (nephelometry, turbidimetry, particle size)
2. Inelastic scattering: for Raman spectroscopy (vibrational spectrum).
Cont’d

FIGURE 6-18(a) As incident radiation of frequency vex impinges on the sample,

molecules of the sample are excited from one of their ground vibrational states to a
higher so-called virtual state, indicated by the dashed level in (b).
Cont’d

FIGURE 6-18(b) When the molecule relaxes, it may return to the first vibrational as indicated and
emit a photon of energy E = h(vex – vv) where vv is the frequency of the vibrational transition.
Alternatively, if the molecule is in the first excited vibrational state, it may absorb a quantum of the
incident radiation, be excited to the virtual state, and relax back to the ground vibrational state. This
process produces an emitted photon of energy E = h(vex + vv). In both cases, the emitted radiation
differs in frequency from the incident radiation by the vibrational frequency of the molecule vv.
6C-4 Emission of Radiation
• Electromagnetic radiation produced when excited species (atoms,
ions, or molecules) relax to lower energy levels
• Excitation by light, heat, electricity, high speed particles, etc.
• Result is an emission spectrum of signal vs. λ or ν :
E.g., Line Spectra of atoms
Cont’d
Excited particles (atoms,
ions, or molecules) relax to
lower energy levels by giving
up excess energy as photons.

FIGURE 6-19 Emission spectrum of a brine

sample obtained with an oxyhydrogen flame.
The spectrum consists of the superimposed
line, band, and continuum spectra of the
constituents of the sample. The characteristic
wavelengths of the species contributing to the
spectrum are listed beside each feature.
Cont’d

FIGURE 6-21 Energy-level diagrams for (a) a sodium atom showing the source of
a line spectrum and (b) a simple molecule showing the source of a band spectrum.
6C-5 Absorption of Radiation
When radiation passes
through a layer of solid, liquid, or
gas, certain frequencies may be be
selectively removed by absorption.

Absorbance :
A = log(Po/P) = -log(P/Po) = -logT

Absorption spectra: influenced by

the complexity, the physical state,
and the environment of the
absorbing species.
Cont’d
• Atomic Absorption :
 Electronic process alone
 Occurs in UV-vis region
 Only a few well-defined frequencies observed
• Molecular Absorption
 E = Eelectronic + Evibrational + Erotational
 Complex spectra over a wide range of λ
• Absorption induced by Magnetic Field :
Nuclear magnetic resonance (NMR) electron spin resonance (ESR)
• In general, the larger the molecule the smaller the separations
Cont’d
• Absorptions (electronic
transitions):
vi = (E1 + ei’ - Eo)/h
i = 1, 2, 3,…., n
• Vibrational transitions:
vi = (ei – eo)/h
i = 1, 2, 3, …, k

FIGURE 6-24 Partial energy-level diagrams for a

fluorescent organic molecule.
 6C-6 Relaxation Processes
• Non-radiative Relaxation: Fig. 6-24(b)
• Fluorescence and Phosphorescence Relaxation:
Fluorescence Lifetimes (singlet):
excited electronic states: 10-8 sec excited vibrational states: 10-15 sec
Vibrational relaxation occurs before electronic relaxation.
• Stokes shift: the emitted wavelength has a lower frequency, or longer
wavelength, than the radiation that excited the fluorescence.
Lifetime of triplet state: > 10-5 sec (Phosphorescence)
6D Quantitative Aspects of Spectrochemical Measurements

• S = kP S: electrical signal
S = kP + kd kd: dark current
• S= k’c (Pe = kc)

TABLE 6-2 Major Classes of Spectrochemical Methods

Beer’s law:
A = abc
A = εbc
• a: absorptivity (L/g-cm)
• e: molar absorptivity
(L/mol-cm)

FIGURE 6-25 Attenuation of a beam of radiation by an absorbing

solution. The larger arrow on the incident beam signifies a higher radiant
power than is transmitted by the solution. The path length of the absorbing
solution is b, and the concentration is c.
Measurement of Transmittance and Absorbance

FIGURE 6-26 Single-beam photometer for absorption measurements in the visible region.