Solid State Communications, Vol. 28, Pp. 243245.

Pergamon Press Ltd. 1978. Printed in Great Britain.

00381098/78/10150243 $02.0O/0

ABSORPTION SPECTRUM OF MANGANESE FORMATE DIHYDRATE

J.L. Rao
Physics Department, S.V. University, Tirupati-5 17502, India
(Received 7 June 1978 by A.R. Verma)
The absorption spectrum of manganese formate dihydrate has been studied at room
6A temperature. The observed bands are assigned as transitions2~
from
the
ion in a cubic
1(S)
crystalline
ground state
field.to
The
various
observed
excited
bandquartet
positions
levels
areoffitted
a Mnwith
four parameters B, C, Dq and a, and the values obtained for the parameters
areB = 800cm, C= 3098 cm ,Dq = 850 cm and a = 76 cm.

1. INTRODUCTION

number of doublet states of which 6Ai~lies lowest,

STUDIES on magnetic susceptibility [1, 2] ,proton

nuclear magnetic resonance [3] ESR [4] and heat
capacity [5] of manganese formate dthydrate have been
extensively made and reported in the literature. The
optical absorption spectrum of manganese formate dihydrate has not been reported earlier. It is studied for
the first time at room temperature and the results obtained are presented in this paper.
The space group of the crystal belongs to the monoclinic system. In manganese formate dihydrate, four
Mn2~ions are contained in the unit cell and equally
divided between two kinds of inequivalent sites [6].
Mn2~ions on A sites are surrounded octahedrally by six
oxygen atoms belonging to formate groups. Mn2~on B
sites are also surrounded by an octahedron composed of
four water molecules and two oxygen atoms which be2~can
long to formate
groups.
The site in
symmetry
Mn
therefore
be taken
as octahedral
the first of
approximation.
,

2. EXPERIMENTAL
The crystals were kindly supplied by Professor
J.M. Thomas of Edward Davies Chemical Laboratories
(U.K.). The optical absorption spectrum was recorded
with a Unicam SP-800 spectrophotometer at room temperature.

according to Hund~rule. The other excited electron configurations like t~geg,t~ge~

and t2ge give rise to
several doublet and quartet states. Thus all the absorption bands of Mn2~result from spin forbidden transitions.
4. RESULTS AND ANALYSIS
The observed spectrum at room temperature is
shown in Fig. 1. It has features characteristic of Mn2~
absorption. The spectrum consists of five bands located
at 18,200, 22,400, 25,000, 27,800 and 29,600 cm1 Of
these bands, the bands at 25,000 and 29,600 cm are
found to be sharp and intense. Ligand field bands are
sharp either when the energy expressions for the transitions are independent of Dq or when the number of
t
2 electrons
is the
same
in both
the excited
and ground
states
[7]. The
sharp
bands
are therefore
attributed
to
4Aig(G), 4Eg(G) and 4Eg(D) states respectively, as their
energy expressions are independent of Dq. Using the
TanabeSugano diagram [8] given for d5 configuration,
the other three bands at 18,200, 22,400 and 27,800
cm1 are attributed to 4Tig(G), 4T
4T
2g(G) and 2g(D)
states respectively. The wavelengths and the wavenumbers of the bands are given in Table 1, along with the
assignments.
.

5. DISCUSSION
Using the interelectronic repulsion parameters (B
the
correction
(a), splitting
the energy
levels are
calculated.
and Treed
C), the
crystal-field
parameter
(Dq)
and
Inclusion of Treed correction is found necessary for a
good agreement between the observed and calculated
values. The correction term introduced by it is relatively
small and therefore it is arbitrarily fixed at the free-ion
value of 76 cm. Because of the deformation of the
free-ion orbitals in the crystal, the free-ion values of B

3. THEORY
2~is
The
ground
state
electron
configuration
of
Mn
(A) 3d5 where A stands for the closed argon shell. In a
cubic crystalline field, these five d electrons are distributed in t2g and eg orbitals, with three in the former
and two in the latter. Thus the ground state configuration is written as t~ge.This configuration gives rise to
the electronic states 6A 4A
4E 4T 4T2g and a
lg, -11g,
g, lg
,

243

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ABSORPTION SPECTRUM OF MANGANESE FORMATE DIHYDRATE

Vol. 28, No. 3

0. ~

4A

4E(G)

:~TIG~

C)

~
0

0.2

I
3000

I
I

3500

4500

5500

6500

Fig. 1. The absorption spectrum of manganese formate dihydrate at room temperature.

30.0

Table 1. The experimental data and the analysis of the

absorption spectrum of manganeseformate dihydrate
(Dq = 850 cm, B = 800 cm1, C = 3098 cm and
a = 76 cm1)

4E~(D)

29.0
28.0

27.0

--

260

4T
2~(D)

Transition
6Aig(S)
4Tig(G)
4T
4Aig(G),4Eg(G)
2g(G)
4T
2g(D)
4Eg(D)

__________________

Observed
(A)
(cm~)

Calculated
(cnf)

5500

18,130

18,200

4000
4470

25,000
22,400

25,010
22,410

3600
3380

27,800
29,600

27,800
29,580

E 25.0

Aiq(G)
4E~(G)

,~

24.0

230

220

2L0

20.0

T
2q(G)

and C cannot be carried out over to the crystals. The

parameters B, C and Dq are treated as adjustable parameters
the calculation.
Theinenergy
values for quartet electronic states have

90
75 80
700-

4Tjg(G)
750

800

850~

900Ajq(S)

been calculated for different

values of Dq
with B =
1 anda=76
cm.Agraph
800cm,C=3098cm
between E and Dq is shown in Fig. 2. A good fit of the
experimentally observed band positions is obtained as is
seen from the graph forDq = 850 cm. It is interesting
to note that the observed and calculated values are in
good agreement justifying the assignments.
Acknowledgements Much of this research was done
while the author was a visiting scientist at the Van der
Waals Laboratorium, Universiteit Van Amsterdam,
Amsterdam. The author is greatly indebted to Professor
N.J. Trappeniers, Director of Van der Waals Laboratory

Dq

in cm

Fig. 2. The energy level diagram of Mn2~in a cubic field

showing the variation of the levels with Dq for a case
with B = 800 cm, C = 3098 cm and a = 76 cm.
The solid circles show the experimental energies.
for his constant encouragement and advice. Thanks are
also due to Dr. C.A. ten Seldam for much assistance in
the calculations. The author wishes to express his grateful thanks to Professor S.V.J. Lakshman for many helpful discussions and suggestions. The author expresses his
sincere thanks to Professor J.M. Thomas for his kind
gift of the crystals.

REFERENCES
1.

FLIPPEN R.B. & FRIEDBERG S.A.,J. Chem. Phys. 38,2652(1963).

2.

YAMAGATA K. & ABE H.,J. Phys. Soc. Japan 20,906 (1965).

3.
4.

ABE H. &MATSUURAM.,J. Phys. Soc. Japan 19, 1867 (1964).

ABE H., MORIGAKI H., MATSUURA M., TORII K. & YAMAGATA K.,J. Phys. Soc. Japan 19, 775 (1964).

Vol. 28, No.3

ABSORPTION SPECTRUM OF MANGANESE FORMATE DIHYDRATE

5.
6.

PIERCE R.D. & FRIEDBERG S.A.,Phys. Rev. (B) 165,680 (1968).

OSAKI K., NAKAI Y.&WATANABE T.,J. Phys. Soc. Japan 19,717(1964).

7.

BALLHAUSEN C.J., Introduction to Ligand Field Theory. McGraw-Hill, New York (1962).

8.

TANABE Y.& SUGANO S.,J. Phys. Soc. Japan 9,753 (1954).

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