FUNDAMENTALS OF ATOMIC AND MOLECULAR

SPECTROSCOPY IN INSTRUMENTAL ANALYSIS

S. PAM •

1. INTRODUCTION

The atomic and molecular spectroscopy is a powerful tool to

analyse chemical composition or structure of a substance, which may
be a pure compound or a simply mixture or solution of two or more
different phases of a crystalline or amorphous material. The chemis-
try and industry people sometimes also talk of minerals, ores, and
pollutants, but these comprise the same crystalline or amorphous
structures. They are characterized using the same instrumental tech-
niques.

The various techniques explored to characterise these materials

using the atomic and molecular spectroscopy constitute a wide sub-
ject of basic and applied sciences. Those deal with the interaction
of electric or magnetic field or electromagnetic radiation (including the
electron beam) with matter through :

(i) spin or orbital motion of valence electron(s),

(ii) excitation of an electron from a core level of an atom or
molecule,
(iii) vibration of nuclie about their equilibrium positions in the
molecule, or
(iv) rotation of molecule about the symmetry axes.

The statistical distribution of the interaction probability over

the energy scale is called the spectrum and the discipline under which
these interactions are studied is called spectroscopy. Thus, according
• Materials Processing Division, National Metallurgical Laboratory, Jamshedpur-831 007.

V-1
to the nature or transition-energy of the interaction, the following main
branches of spectroscopy have been recognised:

(i) Vibrational (infrared) or electronic (optical) absorption

spectroscopy
(ii) Vibrational Raman scattering
(iii) Electronic Raman scattering
(iv) Emission (electronic, vibronic and robronic) spectroscopy
(v) Electronic fluorescence
(vi) Phosphorescence
(vii) X-ray scattering
(viii) X-ray photo-electron spectroscopy
(ix) X-ray fluorescence
(x) Magnetic resonance (EPR, NMR & FMR)
(xi) Mossbauer spectroscopy
(xii) Photoacaustic spectroscopy, and
(xiii) Neutron scattering

In neutron scattering spectroscopy, we measure intensity of a

neutron beans reflected from different nuclle as well as from electron
clouds of associated atoms of given crystal lattice. A neutron bean
having no electronic charge, but being a magnetic particle (with mag-
netic spin I = 1/2), easily pentrates the electron cloud and reaches
the nucleus. It is therefore more informative than the X-ray or elec-
tron scattering to provide accurate positions of different atoms in a
crystal lattice. Moreover, it measures also magnetic moments, if any,
of individual atoms in the crystal lattice.

In the following discussion, I will confine myself to basically

vibrational and electronic spectroscopy using typical examples of :

(i) inorganic or organic materials

(ii) glasses and composites, and
(iii) minerals and pollutants.
A basic advantage of these techniques is that they take into account
the short range interactions and thus successfully apply to structural
diagnosis of crystalline as well as amorphous materials, where X-
ray diffraction and most other aforesaid techniques failed. In this
sense, the vibrational or electronic spectroscopy Is very rewarding to
unambiguously determine and confirm the local stuctures, conform-
ers, hydrogen bonding vibrational or electronic coupling between the
structural units, if any, or electron-phonon coupling (including the
Jahn-Teller interactions).

II. ELECTRONIC SPECTROSCOPY

A. Atomic spectroscopy

Atomic spectrum of an element in solid, liquid or gas phase can

be studied by recording or photographing absorption, emission, fluo-
rescence or phosphorescence of the specimen, as defined in Fig-1.

If T
2

Absorption

S, f i I I

Fig-1 Different competitive processes in electronic excitation of a valence electron.

V-3
 Atomic absorption of a liquid or gas specimen is monitored by
measuring relative intensity of a continuous radiation transmitted
through the specimen as a function of wavelength, as shown in Fig.2.
The device is set-up and callibrated in a fashion that it measures the
absorption or transmission as a function of X. The spectrum of a solid
specimen can be measured in similar way but one has to optimise
with the absorption or transmittance of the specimen within the range
of the spectrophotometer, i.e. the sample should be appropriately thin
of less than - 1 mm or it should be diluted by mixing with certain
(transparent) additives to allow measurable transmission of the inci-
dent radiation through it.

Source
Monochromator

Fig-2 Schematic diagram of measuring absorption spectrum

The emission spectrum is recorded in similar fashion but excit-

ing the specimen in a gap by Arc, spark or discharge. In the fluo-
rescence or phosphorescence, the specimen is excited in a particular
electronic state, usually by a laser beam at a given X. and the spec-
trum in the transitions from that or lower energy levels to the ground
state levels is measured through a monochromater. This technique
is usually limited to insulators, i.e. oxides, halides, etc. It can not be
applied to metals or other conductors with electrons or holes as the
highly mobile charge carriers. They very rapidly (within 10-9s return
from an excited state to the grand state (through electronic conduc-
tion and non-radiative transitions) prior to the radiative transition (fluo-
rescence or phosphorescence) is recorded on a monochromator.

B. Hydrogen atom (IS')

Hydrogen is the simplest example to understand the electronic

spectrum of an atom or molecule having one or more free (or non-
bonding) electron(s). Such a system exhibits stationary states of
energies E„ of the free electrons, following the schrodinger relation

Hcp = Ecp (1)

where
1-I = (P2/8n2m) A2 + V (2)

is the Hamiltonian. The solution of relation (1) gives

E = Rz2ch/n2, (3)
with R = 27E2 me 4/ [ch,'(4nc)1]

the Rydberg constant. Other terms have their usual meanings.

Thus a moving electron in a stationary state cpn radiates an

energy

AE = En- m E (4)
= Rz2ch (1 /n2 -1/1112 ), or
=Rz2( 1/n2-1/m2) (v = E/ch) (5)

when it jumps from a state cpn to another state cp,n. Here, u is wave-
number (expressed in cm--1) and n and m are principal quantum num-
bers.

For hydrogen, with atomic number 1, z=1 and n=1 in the

>n
ground IS' ('S.) electronic state. In excited states T,,,./can assume any
integral values m=2,3,4 .... oo. Thus for n=1 and m = 2,3,4.... etc.,
i.e. If an electron jumps from an excited 'Pm state to ground state cpa ,
in eqn . (4) we get a series of different lines , called Lyman series. Simi-
larly, the cpm r...^,. (p. transitions result :

Balmer series
Paschen series
Brackett series, and

T. } (p5 Pfund series,

with m= n+1, n+2 .... etc., respectively. Other details are shown
in Fig.3.

Pfund

H(isi)

Fig.3 Emission spectrum of hydrogen.

C. Transition Metals

(i) Cr3+/Cr6+ spectrum

Most of the minerals, in which we might be interested for prac-

tical purposes, contain transition metals, rare-earths and actinide
series. These having 3d", 4f- & 5f'n (with n = 1--* 10 and m = 1
14) unfilled subshells of valence electrons exhibit d -4 d and f
f transitions lying in the region extending from far infrared to ultra-
voilet region of the electromagnetic spectrum. Unlike to hydrogen or
alkali and alkaline series, here the electron exclusively does not un-
der go a transition from a given subshell to another subshell but
exhibits well-resolved spectrum owing to transitions within the subshell
itself. In fact, these transitions are forbidden by the basic selection
rules. They become allowed in these particular examples due to
pecularly strong spin-lattice interactions, and thus exhibit reasonably
intense spectrum,

For example, Fig.4 shows absorption spectra of virgin and heat-

treated 50PbO-20Cr203-30B203 glasses. Two characteristically broad
bands, marked by arrows at (i) 890 nm and (ii) 694 nm, are observed
in the virgin glass (a). Annealing few hours at 500°C or 700°C in-
duces the absorption in the visible and uv regions (starts from 800
nm and grows continuously towards the uv region) at the expense of
the absorption in the near 1R region. This markes these glass-
ceramic products practically useful for opticl glasses/filters or
coating materials of different absorption grades for the visible
radiation and with almost transparent behaviour for the near
infrared radiation. Glasses (b) and (c) provide a sufficiently wide region
of practically constant absorption between 740 and 540 u n which was
not affected considerably on further heating at temperatures as high
as 700°C.
 1 00 (a)
(b)
In
(c)
C
(II)
('
U

/ - .1

^/,/_ -I", \
\ / / /
\ \
\

1000 900 800 700 600 500 600

Wavelength, A (nm)

Fig.4 absorption spectra of 50PbO- 20Cr203 - 30B203 glasses; (a) as-prepared

and (b ) and (c ) recrystallized 2h at. 500°C and 700°C respectively. Arrows
indicate aver --avege positions of the absorption maxima analysed using
Lorentzian shapes.

The two bands observed at 890 and 690 nm in the virgin glass
are assigned to two d-d transitations of Cr3+ (3d3) excited from ground
state 4A2 to first excited states 4T2and 2E, 2T2, respectively . Here, the
4A2 . - > 2E, 2T2 transitions are spin - forbidden but they surprisingly ex-
hibit ambiguously much stronger intensity than in the spin -allowed
4A2 _12 transition'.

It Is likely that the chromium in the present glasses exists in a

thermodynamic Cr3+ T ` Cr6+ equilibrium, with Cr3+ and Cr6+ oxidation
states. The presence of chromium in the different oxidation states
allows their intermixing, through the spin-couping, to reveal modified
energy levels of the coupled "Cr3+-Cr6+" ion-pairs. The energy levels
of the ground and excited states of isolated Cr3' and Cr6+ are
portrayed in Fig-5. The transition between ground state 4A2 and the
excited state 2E or 2T1 of Cr3+ or that between ground state 'Al
and the first excited state 3A2 of Cr6+ is forbidden by both symmetry
as well as spin . As the electrons of Cr3+ couple with those of Cr6+,
the transition between the excited and ground states becomes spin
allowed , as shown in Fig-5 for the "Cr3+- Cr6+ " compled pair, ac-
counting for the large intensity of the 694 nm bandgroup observed
in the present samples.

VZrr17r

I it)-" Schema tic diagram fur spin coupling between the ground
and 'A and 'F, 'T, excited stales of isolated Cr" ' and Cr'
'file slhaded area indicates the overlapping region between 'E and
'T, excited states of Cr"

Formation of similar coupled "ion-pairs " in Mn2+ doped RbMgF3

crystals2 led to the intensity of a spin forbbiden 6A1---4T1 transition of
Mn2+ enhanced by a factor of 105. In these crystals , the Mn2+
occupy two crystallographically different Mg2+ sites , and therefore
exhibit two distinctly different emission and excitation spectra. The
energies of the absorption and emission bands associated with these
sites are summarized in Table -I. These spectra are reproduced in Fig.6.
Fig.6 (a) shows a 710 n m emission band (dashed line) and its exci-
tation spectrum (solid line) with peaks at 420 and 600 rim. Fig 6(b)
shows an 870 urn emission band and its excitation spectrum with
peaks at 430 and 700 nm. Lifetimes ( i) measured for both transi-
tions are found to be ti - 20 ms. This is consistent with an oscilla-
tor strength of f - 10.3 determined using the relation :

f = 4.32 x 10-9 J E dv (6)

where the integral defines the area under the absorption curve.

Table-I. Absorption and emission bands of Mn2+: RbMgF3 crystals

Irradiated Irradiated & annealed

Site-I Site-II (in nm)
(in nm)
Absorption :

6A1 - > 4E. 4AI

420 430 410
'Al "T 1 600 700 700
Emission

4TI
- -> `'A1 710 870 870

A required condition for mixing of the free-ion wavefunctions with

those of the neighbour ions or the lattice vibrations is that the
symmetry associated with the centre of inversion be destroyed by the
neighbours. This is evident from our vibrational analysis of the
various glasses, shown in Table-II, where the degeneracies of v2(E)
and v3, v4(F2) vibrational modes of CrO42- are completely removed,
confirming a site symmetry for CrO42- lower than a Td symmetry3. This
can be accomplished both dynamically (via odd parity vibrations) and
statistically (as a result of the odd-parity distortions present in the

V-10
system ). A small 1 - 5 mol% addition of A1203 (acts as a glass network
modifier) in these glasses causes non-bridging oxygens and produces
heterogenous nucleation centres in the glass, reducing locally ordered
structure of CrO42- (and also borate) groups. It is clearly reflected in
significantly enhanced bandwith as well as the Intensity of absorp-
tion maximum at - 700 nm. This provides a good example of dynami-
cally induced intensity mechanism.

(a) (b)
4T1
4(E, A1) I (E, Al ) 4T1
I

4f 1 I
30000 10000 30000

Wavenumber (cm-)

Fig.6. (a ) 710 nni emission band ( dashed line) of Mn2': RbMgF3 . Its excitation
spectrum is shown by the solid line. (b) shows excitation spectrum of an
870 nm emission band.

Crystalline PbCrO4 or Pb2CrO5 developed in the heat-treated

glasses exhibit charge transfer bands of Cr042- chromophore, but they
lie far below in the uv region4. Moreover, Toda and Morita5-' reported
that Pb2CrO5 shows photoconduction with an optical bandgap-energy
EP - 2.1 eV (or 570 nm). Indeed a strong absorption band group
occurs around 600 nm, especially in Al203 added glasses, due to an
electronic excitation through this optical bandgap. The position of this
Table- II. IR and Raman bands (cm-') observed in Pb2CrO5 microcrys-
tals precipitated in PbOCr2O3, -B20 3 glasses*

IR Raman Cr02- bands Assessment

In H2O solution**

325 (vw) 330( w) 348 v2(E)

375 (ms) 373 ms) 368 v4(F2)

380 (w)

865 (vs) 860 (vs) 847 V1 (Ad)

890 (s) 890 (w)***

905 (ins) 884 v3(F2)

935 (sh )*** 933(vs)

* Samples are bleached in weak hydrochloric acid.

** Raman bands observed in aqueous K2CrO4 solution.
*** Bands are too weak and could be observed only at low (liquid
N2) temperatures. Relative intensities are given in the parenthe-
ses : w = weak, uw = very weak, s = strong, ms = medium
strong, vs = very strong, sh = shoulder.

bandgroup is very sensitive to the impurities incorporated in these

crystals during their crystallization from these glasses. A glass speci-
men achieved a significantly large 80% crystallized volume fraction of
Pb2CrO5 as the only crystallise phase thus exhibited an absorption
maximum at 578 nm, fairly consistent with the optical bandgap
determined by the photoconduction measurements on Pb2CrO5 single
crystals.
(ii) Fe2+ (3d6) spectrum

The d6 - electron spectrum of Fe2' ion In metals or metal salts

has been extensively studied". The ground state 5D (L = 2 and S =
2) of the free Fee` ion in Td symmetry is split into an orbital doublet
5E and a triplet 5T2 (separated by 0 = 10/Dq) by the crystal field.
Furthermore, the spin - orbit interaction removes degeneracy of the
ground state 5E, which Is ultimately spilt Into five different nearly
equally spaced levels (I , l4 , I - , , r5 and 12) separated by 6X 2/A,
with . _ -100 cm'' the spin-orbit interaction parameter, as shown
in Fig.7.

Fig-7 Crystal field splitting of Fee` free ion in Td symmetry

Optical transitions from the singlet F, ground state to levels of 5T2

have been seen near 2500cin-'. The transitions among the 5E split
levels (allowed by electric dipole are marked by the arrows in Fig.7)
appear in far IR region. For example, Fig.8 shows a typical spec-
trum of Fe2+ : Cd0 . 99 Fe0 0,Te. The lowest energy line in T-i _3 r4 transition
occurs at 18.6 cm-1. Electronic transitions inside the 5E multiplet are
strong function of the interaction (Jahn-Teller effect) between the
ds(Fe21) electrons and the lattice vibrations.
 X=0

X 001

z
w
U
Li_ T=5K
11..
W
C_)
(_)

10 30 50 70 90
WAVE NUMBER (cm 1 )

Fig.8. Far IR spectra of Cd,_XFe Te (x = o and 0 . 01 at 5K.

( iii) Fe3+ (3d5) spectrum

The ground state of iron in Fe3+ state is 6A1(S). It exhibits the

first absorption band at around 690 nm in the transition to the first
excited state 4T1(G). Obviously, the Fe 3+ is transparent to IR and near
IR radiations but strongly absorbs in visible region and very strongly
in the uv region with cut-off energy at about 350 nm. Thus it is
very easy to anambiguously distinguish from Fe 2+ centres.

4T1(G) excited state of Fe 3+ has a reasonably long lifetime of 25.2

ms. It therefore exhibits very intense fluorescence to the ground state
and associated vibronic states. The possible transitions of Fe 3+ are
therefore well-resolved in Fe3+ doped crystals such as ZnO (which does
not have its own absorption in this region9). These allowed accurate
analysis of the fine structure of T1(G) state and in-turn site symme-
try of Fe 3+ in the associated crystals.
(iv) Cu2+ (3d9) spectrum

I think there is no need to point out unlimited applications of

copper and copper materials in industry, technology as well as in basic
research. We have been using the copper in one or the other way
since the copper age. Their optical spectroscopy, with characteristi-
cally sharp and well-resolved d-d electronic transitions, is very sensi-
tive to unambiguously detect them in the minerals and salts even if
they are present at trace levels.

Of the 3d transition metals, Cu+2 (3d9) has one of the most simple
electron systems and is most amenable to testing posulates of crys-
tal field theory and the Jahn-Teller effect. It exhibits very low lying
energy levels in the infrared region. Those are useful to control and
vary the optical and electrical properties of the Cu+2 doped ZnO'o,
ZnS", CdS12, CdTe13 or ZnTe14 semiconductors. The Cu+2 doped lasers,
sensors and optical storage materials of the present decade are the
best cmpliments of these d-d electron transitions.

Figure 9 shows a typical absorption spectrum of Cue+: ZnTe, as

recently reported by Volz et al14 . The most intense peak at vo = 1069
cm-' is attributed to a zero-phonon transition from spin-orbit split
ground state 2T2 (F",) to the first excited state 2E ( fie), schematically
portrayed in Fig . 10. The set of absorption lines A begining at
1069cm- ' and ending at approximately 1200 cm-' is repeated in sets
B and C by a constant energy interval of 210 cm -'. This energy
interval corresponds to the a mode of the lattice vibration and com-
pares well with a value of 207 cm-' obtained from neutron, scattering
data's

The integrated (total area) intensities of the first peaks of each

set follow a Poisson distribution, expected for electron-phonon cou-
pling. The strength of the electron (LO)-phonon coupling measured
here is given by a Huang-Rhys factor S=0.8. However, the absorption
peaks under each set do not so satisfactorily follow the Poission dis-
tribution of their intensities.

V-15
 j 0.5
L
fa

0.3

800 1000 1200 1400 1600 1800 2000

Wavenumber (crn' )

Fig. 8. Infrared spectrum of Cu2+:ZnTe at 4.6 K.

Another set of absorption lines has been observed between 850

and 950 cm-1. It has same internal spacing as does the set of lines
A between 1050 and 1200 cm-'. These lines are attributed to the
anti-Stokes portion of the spectrum. Two zero-phonon lines are also
identified. In addition to the prominent zero-phonon line at 1069 cm',
a second zero-phonon line of considerably much lower intensity is
confirmed at 1002 cm-1. This zero-phonon line is assigned to the
transition 2T2 ()'8) 42E (r8). A complete diagram of these two transi-
tions is summarized in Fig.10.

The absorption spectrum measured on a rather high resolution

between 1050 and 1200cm-' is shown In Fig.11. It comprises six dif-
ferent irregularly spaced phonon modes. The third one lies only 4
cm-' away from the second. The bands observed in this region are
not in a sequence of constant-energy differences and do not exactly
 1069 c.n- I

Spin
Orbit

F ig.1u Energy-level diagram of the2D term split by a crystal

field of T1 syinnietry and spin-orbit coupling.

match with the lattice phonons. For example, the energy difference
between the zero-phonon line at 1069 cm--1 and the first su _ cecding
absorption line within the set is 32 cm', considerably less than the
value of a nearest phonon mode of 42 cm-1, determined by the
neutron scattering. This irregular nature of these phonon lines can
be understood by invoking the contribution of dynamic Jahn-Teller ef-
fect on these phonons.

D. Rare-earth cations

In this example, I discuss some peculiar features of rare-

earth compounds. The rare-earth(R) elements, which of course are
not rare in our country (we are the third largest producer of rare-
earth minerals in the world), have unfilled 4f subshells of electronic
configuration

R : 4P,(5S25P')6S2 (7)
 0.5

(0

CD
U
to 0.4
b

0.3

1050 1100 1150 1200

Wave number (cm"I)

Fig.11. High resolution IR absorption spectrum of Cus+: ZnTe (after Volz et.al 1992)

with n = 1414. They usually (except cerium which exists as Ce4+ and
Ce2+) exist in R3+ oxidation state having the electronic configuration

R3+: 4f ' (5S25P6) (8)

i.e. the 4P-1 electrons are shielded by 5S25P6 electrons and this is the
reason that the rare-earth salts (unlike the transition metal salts) usu-
ally exhibit characteristically sharp and well-resolved electronic tran-
sitions in absorption as well as in the emission spectrum. Also the
actinide series exhibits similar valence electrons (5?) and similarly
sharp 5f - 5f transitions.

(i) Eu9+ (4_F) spectrum

Fig.12 shows absorption spetrum of Eu3+ of a N, N- dimethyl-

diphenyl-phosphinamide (DDPA) adduct of europium perrhenate,
which is written as Eu(ReO4)3. 2DDPA. Some vibronic bands
associated with the eletronic transitions are accompanied by blue
shifted broad bands. These are makred by the plus (+) sign. The band

V-18
positions and oscillator strengths of the principal bandgroups
assigned for a few low-lying energy transitions are given in Table-III.

460 500 540 580

WAVELENGTH (nm)

Fig.12 Absorption spectrum (600=100 nm) of the

Eu(111) ion in Eu (ReO4)3 - 2DDPA at 300 K. (*) Ab-
surption of Re", ((D) vibronic bands.

The oscillator strengths of the bands have been calculated using the
integral area under the absorption curves (for details see Feuerhelm
et. al.16). Their values so obtained for the 7F --.i 5DJ (J = 0 - 4) bands
are of particular interest in elucidating the electric /magnetic dipole
characters and hence the 4f --- 4f radiative transition probabilities.
Amongest these transitions , only 7Fo -5D , satisfies the magnetic
dipole selection rules AJ = o, ± 1, with J = o k/-> o) in an intermedi-
ate coupling schemer7. The 7Fo-* 5D2 4 transitions are believed to be
primarily electric dipole in character. Their intensities are therefore
strongly dependent on crystal field effects. The 7F0-5D3 transition has
a mixed character, while the remaining 7F0-5D0 transition is regorously
forbidden for any magnetic/ electric dipole or electric quadrupole
transition. This transition usually appear in non-centrosymmetric
europium compounds.
Table-III. Principal absorption bands of Eu(III) In Eu(ReO4)3.2DDPA
observed at 300 K

Wavelength Oscillator strength Transitions

(nm) (f x 108)

590.0(16,950) 0.023 7F l-5D0

588.0(17,007)
578.4(17,.289) 0.010 7Fo_5 Do

570.0(17, 544) 0.013 Re4+ band

536.0(18,656) 1.014 1
_5D1

525.0(19,048) 0.50 7F 5D1

472.0(21,186) 0.010 5
1' D2

465.0(21,505) 0.35 7F
5D2
464.0(21,552)

459.0(21,786) vibronic bands

432.0(23,148)

420.0(23,895) 0.34 7 F1-5D3

416.0(24,038)

412.0(24,272) 0.005 7F 5D3

393.0(25,445) 35 7F - 5L6
384.0(26,042) 4.5 7F o 5L7
7
381.0(26,247) 2.5 F0- 5G 2.3.4

377.0(26,525)

365.0(27,397) 5.0 7Fo 5D4

Transition energies in cm-1 are given in the parentheses.

 Thermally excited 7F1 5D3 bandgroup at 420 nm exhibits -70
times larger intensity than in the 7F0 5D3 band excited from the ground
state 7F0 at 300 K. The intensity in the former band increases
exponentially and decreases in the latter following the Boltzmann
population distribution

N = N. exp (-AE/KT), (9)

with increasing temperature between 77 and 650K, confirming their

present assignments. Thermally excited bands to 5D 2 levels have also
been noted (cf. Table-III) but those are not so pronounced18.

2J+1 - fold degeneracies of 5D1 and 5D2 states are completely lifted-
up in the present compound as evident by the high resolution spec-
tra shown in Fig-13 . It means the Eu3+ in this compound bears a
sufficiently low site symmetry of C2,. C2, C. or C,.

20 40 r

0 'Fa D1 lPe
P7 ,
(A) E /a
(A) H la
- 1. 11 3. A4 30

(B) E/b 20 i

10

(C) E/c
) bLj (d
L H /I

) 0
21550 21500 19060 19j1 '
PHOTON ENERGY ( cn ' )

Fig-13 Polarized absorption spectra of the „-^ `D1

and 'h,) -^ SD, bands of the Eu(III) ion at -77 K. The
electric vector E for the 7F,) --+ `D, transition and the
magnetic vector 11 for the 7F11 -->• 5D, transition were
kept parallel to a, b, and c crystal axes in (A), (B), and
(C), respectively.
 It is interesting to note that intensity of absorption from ground
state 7F0 to first excited state 5D0 is very poor or zero but the most
intense fluorescence always occured from this (5D0) state to various
7FF (J = 0-6) levels as shown in Figs.14 and 15. Hence one should
be very careful in analysing concentration of Eu3+ cations in unknown
samples using these intensities.
Cm 1
17500 17000 16500 16000 15000 15000 14500 14000

IOt- I

(0,2)

(0.1)

(0,3)
(0,4)
50,0)

0 _} 1_
575 595 615 635 655
WAVELENGTH (nm)

Fig.14 Fluorescence spectrum of the EL(M) ion in Eu(12e(D.)) - 2UUPA at 77 K with the
emitting state W . \cxc = 488.0 nm Ar' laser.

c r,1

19500 19000 IB500 18000 17500

0.50

0 -I^ I I I l
515 535 555 575
WAVELENGTH (nm)

Fi(.15 Fluorescence spectrum of the Et(III) ion

corresponding to that of Fig.T3 with the principal emit-
ting state 1D1. Vibronic bands.

V-22
 Figure 16 summaries crystal-field levels splitant of 7FJ multiplets
deduced in the fluorescence from 5DJ (J=0,1,2 & 3) excited states.
Intensity distribution over them did not significantly differ in the dif-
ferent excitations. The fluorescence from 5DJ (J=0-3) levels exhib-
ited optimum intensities for the excitations made with 545.5, 488.0,
465.8 and 457.9 nm Ar+ laser lines respectively. None of the 5DJ
crystal field levels matches completely with any of these laser lines
and the fluorescence in each case was induced through excitation of
associated vibronic levels. The 5D0 remains the prominent fluorescence
state with all the excitations.
24380
3480
31
-7s 24300 (cni I)
-242404
/21561(9)
s d
324 21527* (c)
21482 (a)

190ss c)
19022 a 19040 (b)

3279(1)
/3201(h)
/ 31.7(9)
:3lo9(1)
r! 17289 (a)

w
z
w

394 (C)
-323(b) 200 400 600
^2es(a) TEMPERATURE (K)
0 (a)

V iq.16 Stark energy levels (not to scale) of the Eu(Ill) ion in Eu(ReO4)1 • 2DDPA at 77 K. (`) Data
taken From absorption spectrum. The inset ligure is the temperature variation of `D, (J = O 3)
fluorescence intensity. The intensity scale on the vertical axis is given for 'D„ fluorescence. This is to
be multiplied. by 10-2 and IO-3, respectively, for the `D, and `D;,) fluorescence intensities.

V-23
 A plot of the fluorescence intensity from various 5D, states
as a function of temperature is given in the inset Fig-16. The fluo-
rescence originating from 5D3, 5D2 and 5D, levels show large decrease
of intensity with increasing temperature. The rates at which the
intensities decrease fall in the order 5D3 > 5D2 > 5DI. On the other
hand, the intensity from 5Do state regularly increases with increasing
temerature. Obviously, the higher 5D.1>> levels release the associated
energies by a combination of radiative (to 7F. multiplet) and non-
radiative (to 5Do) transitions. The non-radiative transition responsible
for thermal quenching of 5DJ>1 states increases with increasing
temperature and leads to population of 5Do level, and results in the
enhanced 5D.7F. fluorescence.

The mechanism of fluorescence from a particular level is a

strong function of vibronic coupling. The vibronic coupling governs
radiative and nonradiative processes, as summerized in Fig.17 for
Eu2(SO4)3. 8H 20- Addition of a few drops of KI in aqeuous solution
of Eu2(SO4)3. 8H 20 quenches the fluorescence and manifested the elec-
tronic Raman transitions through the low lying 7FJ electronic-energy
levels. The H2O molecules in the aqueous solution are strongly
hydrogen bonded. The hydrogen bonding (inter as well as intramol-
ecular) is considerably reduced on the addition of KI due to the
formation of

K-1-I...H-0 I-I

1-1---0
H-..

bonds18. The effect has been directly reflected in - 3% increased

0-H strectching frequencies in the range 3130 - 3640cm-'.
(ii) Nd3a (4f3) Lasers

Neodymium is one of the most demanded rare-earth (R) element,

especially after the discovery of the high T,, superconductors and
high-energy-density R2Fe14B or R2T17N (where T is a transition
metal) magnets during the present decade. Nd3+ : YAG lasers and

502 ^2v C
-
v v _2 01 1 - 20720 ccm-1 H2O
- -v2(H2O)1
l^ ^j f l•[tr^l
v I CAS v1 u3%"2ur0
19435 cm-1 V1 41(SOI)1
^38 1 G_ N
5
) 0t

17270 9
*iT V2(HZQ)4

Q Cr
d
E
C or
o^
ix I

7F6 7F6 7F6

4

7F0

F i(1.17 Schematic energy level diagrams (not to scale ) showing

the Eu3+ fluorescence emission, electronic Raman scattering and
several non-radiative processes operative simultaneously in the
Eu2(SO„ )3 solutions. The emitting states 6D, • or 6Do are excited
through the associated vibronic levels, showing a prominent
fluorescence in (A) D20 for X.,C=465.8 nm and (B) H2O for K,, .c--
488.0 nm. (C) The fluorescence only from the 6Do is excited with
X,xc=514.5 nm. The vibronic levels are shown by the broken lines.
A subscript 0 or 1 outside the parentheses, e.g. v,(H20)0 or v;(H2C')1,
refers to the J value of the associated 6Dj electronic level. The
shaded region shows the spread of the vibronic levels.

R3Fe5o12 (RIG) garnets stem other thrust areas of advanced technol-

ogy of optical, magnetic and electronic devices. We are very fortunate
to have a plenty (about 0.4 M tonnes) of neodymium reserves in our
country. Table-IV compares world-wise reserves of neodymium.
Thus we are among the three richest countries of neodymium
resources. However, we are far away from competiting the aforesaid
technologies.

V-25
 Table - IV

Estimated reserves of neodymium in different countries

Country Reserves

(in tonnes)

China 4,600,000
USA 640.000
India 400.000
USSR 64.000
South Arfica 13,000
Brazil 4,000
Malaysia 4,000
Others 58.000

Figure 18 shows optical absorption spectra of singly or codoped

30BaF2-181nF,3-12GaF3-2OZuF2-(10-x-y)YF3-6ThF4-4ZrF4-xCrF3- yNdF3
(I3IGaZYTZr ) fluoride glasses with Cr3+ and Nd3+. The spectrum of
Cr3+ (0.2% singly doped glass (a) is characterized by two spin-allowed
broad bands, which can be identified as the vibronically broadened
transitions 4A2 -4T2 at - 655 nm and 4A2- "T1 at - 450 nm. The for-
mer band contains a fine structure due to the spin-forbidden 4A2_2 E,
2T1 transitions. This glass exhibits a broad structureless fluorescence
band centred at - 890 nm in 4T2 4A2 transition. This fluorescence
band exhibits a large Stokes shift - 4000cm-' and that strongly de-
creases with increasing temperature.

The decay kinetics of the broad fluorescence of Cr3+ in the fluo-

ride glass were studied as a function temperature and emission wave-
length. The decay of the intensity measured along the fluorescence
band using (1 "C - 655 rim, i.e. exactly the centre of the 4A2 -4T2 ab-
sorpt.lon, can be described by a double exponential function through-
out the studied temperature range 320-70K. This behaviour
persists even for lower Cr3+ concentrations upto 0.05%, demonstrat-
ing that Cr3+ .---- Cr3+ interactions are not very important here. The
intensity basically depends on the lifetime and population of the
fluorescent species in the fluorescent state. Both these parameters
exponentially decrease with increasing temperature in this range and
thus account for the observed variation of the fluorescence intensity
with the temperature.

4T,
0.2 - 1 4T, (a)

0.1

r-.
.^J

C 0.0
D

.f)
G5
O,4 1 2
r
ti
.^l

(c)

0.5 -

U
0.0
300 500 700 900
Wavelength (nm)

I i(J.1l1 Room-lcn)pcralure absorption spectra of (a) Cr3+

(0.2%) singly-doped Ill(iaZY'I7r fluoride glass, (b) Nd'+ (1%)
singly-duped III(iaZY'1"Zr fluoride glass, and (c) Cr3+
(0.2%):Nd'' (I %) codopcd fluoride glass.

V-27
 A small 0.05% addition of Nd3+ (of 2-3 times larger lifetimes 100-
500 is than for Cr3+) in this glass stabilizes the strong fluorescence
From ^'1'2 state of Cr"' adequate to use as a tunable laser. Nd3+ (4P)
exhibits characteristically sharper (reflects large lifetime) 4f - 4f tran-
sitions in the near IR and visible regions, as demonstrated by the
spectra of a purely Nd3+ (1%) doped fluoride glass in Fig.18b and a
codoped fluoride glass with 0.2% Cr3+ (1% Nd3') in Fig.18c. These
lines are useful to induce efficient lasers at selected wavelengths.

III. VIBRATIONAL SPECTROSCOPY

Polyatomic molecules exhibit vibrational as well as rotational

spectrum in addition to the electronic spectrum. Each electronic state
accompanies 3N-6 (or 3N-5 for linear molecules) fundamental modes
of vibration of a molecule of N atoms. In addition, the combination
and overtones of these fundamental vibrations also occur sometimes
but they usually present very low intensities. Resonance of frequency
(energy) as well as symmetry of a combination or overtone with those
of a fundamental vibration, or electron-phonon coupling, or Jahn-Teller
interactions quite often influence their expected intensity distribution.

Each vibrational state in a. given electronic state contains a cer-

tain number of rotational levels according to the J values. These are
rather closed spaced and can be resolved only at reasonably high
resolutions. Obviously, their analysis very precisely predicts the
electronic structure, isotope shifts, and site symmetry as well as point
group symmetry of the molecule (or the crystal unit cell) in the ques-
tion. However, there are several other constraints because of which
it is not in usual practice. It is mostly limited to basic research only.

Vibrational ( IR or Raman ) spectra of polyatomic molecules

usually lie in the range 10-4000 em -1. The low frequency range
10-600 cm' is called far infrared region and that between 200
and 4000 cm ' the mid infrared region. Organic molecules containing
closed rings or > CHO, >C=O, -OCH3, - CH3, >NH , -NH2, or -OH chro-
rnol elhores
V-28
strongly absorb over 300-4000 cnr-' through the characteristic group
frequencies. Inorganic molecules with no such functional groups
absorb over lower frequencies 100-800 emr'. Borate, silicate or
phosphate glasses, which form network structure, strongly absorb over
800-1500 cm-1.

(1) IR and Raman spectroscopy of 1-formyl -3-thiosemicarbazide

Figures 19 and 20 show infrared and Raman spectra of a typical

organic system of 1-formyl -3-thiosemicarbazide (FTSC) in the range
300-4000 cm-1. Its molecular structure is shown in Fig.21. This
particular compound is famous for exhibiting tuberculostatic, fungis-
tatic and antibacterial effects20. The C-H group vibrations are
unambiguously distinguished by studying deuterated compound
under the same conditions.

rig. 19

}t T

Cot
A' MULL

1400 800 1200 1600 2000 3 000 4000

Frequency (cm

i ii temperature (300 K)
fZ of i F I SC-do in (a) nnjc)l mull and ( b, c) KBr pellct. itno
liquid N. temperature (77 K).
 IIicj.21)

(b)

lu_ ^L J._L_ L^
500 (Y00 1500 2500 3000 3500

N I !.

t --I--_I_-' --j_i^-l
30X) 600 900 1200 1500 1800 216` 2700 3000 3300 3600
Roman shift (crnI)

Raman spcclrrrnr r,f I I S('-dr, at 095 K ) Ii'insc't are shown Raman slicclra of 1-I'SC-d4 recorded at
cli(fcrcnt intensity, scales ( say ii. wHh ', za I in region ( a) aril x - 5 in (b).

tS
\pl^ ^ H

I I i(1.21 blolrc•Ular !if rucLnrc of' 1 I5C

 FTSC- d0, in principle, exists in four planar conformers shown in
Fig.22. The prescnl. vibrational analysis confirmed the (aa) and (ba)

S S S

OIIC\ /I\ /Nil) it C Nil, OIIC 11

.4 N N

I I I I
H N11,
I

(b2) (°b) (bb)

F iq.22 Planar configurational isomers of FTSC-do

conformers to be the most stable ones. Those are peculiarly stabilized

by intermolecular H-bonded dimer.

I I -hoiolcd diiri'r,

Its
it
/C-o....II
21I1---! ,cllol R -N `-- R
I, cFIS(

H
Cyclic FTSC dime+

5
1 ,.II
where R-> -C - NH - NH2" part of FTSC. Other details about the
cyclic or open dimers can be found in Refs. 20-22.
1-i
To speculate on the dimer structure we make use of the -C=O
group vibration . The V (C=O) bands observed with considerable
intensities at - 1650 cm-' in the Raman spectrum (g-species charac-
ters) do not show their IR counterparts and vice-versa ( u-species

V-31
characters). This suggests a prominent abundance for the cyclic FTSC
dimer (a pseudo D2h molecular symmetry). The prominent Raman
band at 1666 cm-' (a band of lowest frequency among the four v(C=O)
bands) then can be assigned to the v(C=O) vibration in the cyclic
dimer. A large Raman intensity (75 units) as observed for this band
is expected for C=O bond oscillation in the above model structure.
The cyclic dimer is not so pronounced in the deuterated FTSC-d4,
showing a single and weak Raman band at 1658 cm-1. The bands
for open-cyclic dimer (a reasonably weak H-bonded system) would fall

(b)

(c )
1
C

D C
U In

U7
z 0
W to
r- to
Z

r)

to

ry

L 1

1900 1700 1500

n^

FREQUENCY (cm-')

I hhi.25 Typical i.r. spectra (I 500-1900 cni -') of FTSC in

ethanol solution . -I'he solution in (b) and (c) is diluted by -2
and 10 limes, respecticly , of that of a highly concentrated
solution in (a). Intensity is normalized to unity in each case.

V-32
at higher frequencies than for the cyclic dimer. These appear to be
stabilized in the nr.iJol samples [only one V(C=O) band at 1685 cnr-'
and two v(NII„) bands at 3100 and 3138 cnr-' are noticed).

Figure 23 shows IR spectrum of FI'SC studied in ethanol solu-

tion. The system basically exists in monomer dimer equilibrium
showing two V(C=O) bands at 1725 and 1650-1670 cm-1, respectively.
The half-bandwidth and peak intensity successively decreases for the
dimer band as the concentration of the solution decreases. In view
of the symmetry consideration, a.sharper (and weak) band is expected
to arise in the cyclic dimer (comprising an inherently higher symme-
try) structure. It is likely that both the open and cyclic FTSC dimer
structures exist in the solution, and the latter structure essentially
stabilizes on the lower concentrations.

(ii) Raman spectroscopy of metal -a semiconductor transition

in BaPb ,-, B1.0 3

BaPb,_x13i,O, displays a very interesting phenomenon. It under-

goes metal to semiconductor transition at x- 0.35. Here, Raman spec-
troscopy is very helpful to understand the structural transformation
taking place as a function of x.

Figure 24 summarizes Raman spectra of BaPb,_XBiXO3 single

crystals at low temperatures 26-31K. The crystal structure is orthor-
hombic for x < 0.95 and monoclinic for x > 0.95. The variation of
intensities of the characteristic peaks against x is given in Fig.25.

The peaks in the range 500-600 cm-' are assigned to ring breath-
ing mode of Pb(Bi)O6/2 octahedron as proposed by Suga123. In the
semiconducting region x > 0.4, two peaks are observed. The intensity
in the higher-frequency peak at - 600 cm-' regularly decreases with
 increasing x between 0.4 and 1.0, while regularly increases in the
lower frequency peak at - 560 cm-1. Peculiarly enhanced intensity
in 560 cm-' band occurs due to resonance Raman effect with the op-
tical bandgap at 2.15 eV. Fig.26 shows Raman spectrum of BaBiO3
at 39K measured with Xe= 514.5 nm (2.14 eV) Ar' laser line. As
expected, resonant peaks for multiple transitions of 566 cm-' pho-
non are observed upto the fifth order.

600

500

fln 7C' 300 400 500 600 700 100

ENERGY SHIM (cm-')

F ig-24 Raman spectra from BaPbl-.. Bi,O3 at low tempera-

tures. 0 07 0& 06 06 1

Fig.25 Phonon energies in BaPbi-zBi.O3 as a function of x.

The filled circles indicate the energies of Raman active modes at
about 27 K and the open circles at 273 K. The thick arrows
show the direction of increasing scattering intensity. The upper
edges of the shaded areas show the LO phonon energies and the
lower edges the TO phonon energies.

V-34
 IIi

BaBiO3

AI=5145 AA

32/. 507

1(5/. 1696

29^t^

51 111 1 11 1. 1 I IfiIP
I/. / 1 1 1_ t ..' 1 7260
99

c Q.t
LI _.L- L^_^ l__J___I_.1^L1MI I I I I 1 I I I I 1 I I I 1 1
500 1000 1 • 1500 2000 2500 3000
ENERGY SHIFT (cm-1)

I i(J.26 Resonant Roman spectra in BaBiO3 at 39 K.

(iii) IR and Raman spectroscopy of glasses

IR or Raman spectroscopy successfully applies to inorganic or

organic glasses (including the polymers), which do not have any or-
dered structures. For example, Fig.27 shows a typical IR absorption
spectrum of amorphous Si02 film begween 900 and 1400 cm''. Two
well resolved bandgroups at 1080 and 1240 cm-', assigned to TO and
LO modes of Si02 network, have been observed.
 Sputtered S:02
Annealed p pcl. (TO+LO)
D _ at 80011C ---- s pol. (TO)
-- after subtraction (LO)

900 1000 1100 1200 1300 1400

WAVE NUMBER (cm")

1R-absc^rhtion spectra of a pure Si O2- sputtered film

i()-27
in ea sur ed under 45° obliq ue incidence. Solid and broken lines
represent the spectra obtained with p- and s-polarized incident
liL,ht, respectively. The do tte d line is obtained by subtracting
t he spectrum for the s p o larization from that for the p p ol ariza-
t1C)11.

Figure 28 describes influence of a small addition of Ag20 or P205

additives in a 40BaO -25Fe2O3 - 35B203 glass . These additives help
formation of a purely amorphous structure of the present composi-
tion by reducing number of nonbridging oxygens (Fig.29) on boroxol
rings in the associated network . As a result , the frequencies of all
characteristic B-O stretching modes are enhanced by 3-4% while the
corresponding B-O bending frequency at - 740 cm-' (in Fig.30) is
consistently lowered by the same factor.

V-36
 1'lo P205 --1100

1310
1491
♦ A
` i I\

1715
11.110
1195

3*/.A920 v

None
,: eo
nao
uc0
..` r 1y` ._^\11110

1_--_ L 1 I
1800 1600 1400 1200 1000 800

Wavenumber (cn1l )

Fig.28 IR spectra of borate glass in 800-1800 cm-1 region.

Fig.29 Network structure of borate glass.

V -3 7
 1 *4 P205

770

718

None
740

464
1

I i I 1

800 640 480 320

Wavenumber (cnrl )

FIg.30 IR spectra of Fig.28 In 320- 800 cm-' region.

Obviously, the IR or Raman spectroscopy of these glasses is very

rewarding in unambiguously determining their structures, and hence
provides accurate analysis of their traces in minerals or other mate-
rials, not possible to trace out by X-ray diffractometry or other
techniques. It applied together .with differential scanning colorimetry
provides the kinetics and the kinetic parameters of impurity induced
structural transformation or thermal induced recrystallization of these
structureless materials. It is also useful to study the oxides inclu-
sions (which usually occur in finely dispersed amorphous or nanoc-
rystalline material) in metals and alloys.
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