Denning 1982

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The electronic structure of actinyl ions

a a b
R.G. Denning , J.O.W. Norris & D. Brown
a
Inorganic Chemistry Laboratory , South Parks Road, Oxford, OX1 3QR
b
A.E.R.E. , Harwell, Didcot, Oxon, England
Published online: 26 Oct 2007.
To cite this article: R.G. Denning , J.O.W. Norris & D. Brown (1982) The electronic structure of actinyl
ions, Molecular Physics: An International Journal at the Interface Between Chemistry and Physics, 46:2,
287-323, DOI: 10.1080/00268978200101261
To link to this article: http://dx.doi.org/10.1080/00268978200101261
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MOLECULAR P H Y S I C S , 1982, VOL. 46, No. 2, 287-323
The e l e c t r o n i c structure of actinyl ions

V. f - f transitions in [NpO2CI4] = and [NpOz(NO3)3]-
by R. G. D E N N I N G and J. O. W. N O R R I S
Inorganic Chemistry Laboratory, South Parks Road,
Oxford OX1 3QR
and D. B R O W N
A.E.R.E., Harwell, Didcot, Oxon, England
Downloaded by [Michigan State University] at 14:14 13 February 2015
(Received 4 December 1981 ; accepted 3 February 1982)
The polarized single crystal absorption spectra of Cs~U(Np)O2CI4 and

CsU(Np)O2(NO3)3 have been measured between 600 and 22 000 cm -1. In
the former material five f-f transitions associated with the NpO22+ ion have
been identified and in the latter material four such transitions. Zeeman effect
measurements and MCD spectra are also reported. A perturbation method
is used to assign parameters characterizing the f orbital energies, the spin-orbit
interaction and the equatorial ligand field. This model is tested against the
energies, transition intensities and magnetic properties associated with the
observed spectroscopic states.
1. I N T R O D U C T I O N
In parts I - I V of this series [1-4] a model of the electronic structure of

the uranyl ion UO22+ has been developed. If such a model is valid its main
features should be transferable to a discussion of the electronic structure of the
NpO~ 2+ ion which has an analogous chemistry. In particular the description of
the excited states of UO22+ involves the excitation of a bonding electron into the
non-bonding f orbitals, centred on uranium, and having D~_I,, ~, and ~, symmetry.
T h e interpretation of [3] relies on an empirical choice of the relative energies of
the ~u and q~u orbitals, and of the equatorial field perturbation acting upon them,
such that most of the observables are reasonably described. Nevertheless the
definition of these parameters also relies on a realistic choice for electron-electron
parameters. In NpO22+ t h e presence of a single f electron in the ground state
and the observation of f - f transitions allows a relatively simple evaluation of the
parameters affecting these orbitals.
In this paper we deliberately avoid using the results from the work on the
uranyl ion so that the conclusions generated from the study of NpO22+ can be
regarded as independent. T h e neptunyl ion can be studied conveniently by
dilution into analogous uranyl host crystals because the latter materials do not
absorb appreciably between 3000 cm -1 and 21 000 cm -1.
0026-8976/82/4602 0287 804.00 :(.(51982 Taylor & Francis Ltd
M.P. L
288 R . G . Denning et al.
2. EXPERIMENTAL
Solutions of NpO22+ were prepared by oxidizing a stock solution containing
primarily NpOz + with ozone at 90°C. Single crystals containing 3 per cent
237Np dilute in Cs2UO2C1 a as a host were grown by the evaporation of solution in
2 mol dm -3 HC1, under an atmosphere of chlorine, in a desiccator containing
calcium chloride. The neptunium to uranium ratio in the growth solution was
2 per cent but the neptunium was found to be preferentially concentrated in the
crystals. The crystals were brown and dichroic, having the characteristic
elongated habit of CszUO~C14 which has been described elsewhere [5].
Single crystals containing 1 per cent 237Np dilute in CsUQ(NO3)3 were
grown by evaporating solutions in 6-8 mol dm -a HNO~, in a desiccator containing
calcium chloride and sodium hydroxide. The crystal habit has been well
characterized [6] and the crystals were oriented under a polarizing microscope.
Equivalent crystals of both materials containing only neptunium were also pre-
pared.
Artificial faces were formed on both crystals with the aid of a specially
machined and grooved mitre block to which the crystals were glued with glycol-
phthalate. The crystals were cut with a damp silk thread running in the prepared
grooves. The sections were lapped, while confined to a close fitting depression
in a brass block, by rubbing on a filter paper wet with ethanol-water mixtures.
Normal lapping equipment could not be used because of the radioactivity.
The polished crystal sections were typically 3 mm x 6 m m × 1 mm and were
mounted in a specially designed copper block forming the tail of an Oxford
Instruments CF100 cryostat. The crystal was confined within this block by
silica cover plates to provide radiological containment. Special sample holders
were also designed for the Zeeman and M C D experiments, which used a Thor
Cryogenic 5.0 T split coil magnet, and for low temperature Raman scattering
experiments [7].
Absorption coefficients were obtained using the neptunium content deter-
mined by e~-counting and ~-spectrometry, the thickness of the crystals being
measured with a micrometer. Absorption spectra were recorded between
22 000 cm -1 and 9 400 cm -1 on a McPherson RS-10 double beam spectrophoto-
meter (0.01 nm resolution). Spectra in the range 10 000 cm -1 to 4000 cm -1 were
recorded using Cary 14 and Cary 17 instruments, while those between 4000 cm -1
and 600 cm -1 were measured on a Perkin-Elmer 180 spectrophotometer. M C D
measurements were made on an instrument of conventional design [8].
Zeeman splittings were obtainable in cases where the individual components
were unresolved with the aid of a scanning refractor plate, whose purpose was to
eliminate the mechanical irreproducibility of the wavelength drive of the mono-
chromator. The fused quartz plate is mounted within the monochromator and
is driven by a galvanometer-type mechanism, with a maximum scanning range of
5 A. The plate drive was calibrated against a mercury arc doublet. With the
ground state g-values observed here, the shift in the cold Zeeman component
could readily be determined.
3. CRYSTAL SYMMETRY
C%UO2C14 is monoclinic, space group C.,I, ,, and a full X-ray crystallographic
analysis has been made [9]. The face-centred monoclinic cell contains two
molecules of Cs.,UO2C14 but the primitive rhombohedral unit cell contains a single
f - f transitions in [Np02Cl4] = and [ N p O a ( N O z ) 3 ] - 289
molecule. T h e site s y m m e t r y of the uranium atom is Can but discrete UO2CI~=

units have approximate D4,~ symmetry. An axis system for this crystal is des-
cribed in [5] and we use the same nomenclature to describe spectroscopic
polarizations in this case. Cs2NpO2C14 has an X-ray structure, as yet incom-
pletely defined, which may be isostructural [10]. T h e spectroscopic data
confirm that crystals dilute in n e p t u n i u m are isostructural with C%UO2C14.
In this space group the optical polarizations are labelled with the propagation
axis, for example X, and the electric field polarization axis, for example (y), with
respect to molecular axes defined in [5].
Crystals of CsUO2(NO3) 3 have a trigonal space group RgC with two molecules
per unit cell. T h e crystal structure of CsUO2(NOz) 3 has been described by
Malcic and Manojovic [11]. It is isostructural with the rubidium analogue.
T h e structure of RbUO2(NO3)3 has been accurately established by neutron

diffraction [12]. RbNpOz(NO3) 3 is isostructural with the uranium c o m p o u n d
[10]. We infer from the spectroscopic data that CsU(Np)O2(NO3)a crystals are
also isostructural with the host compound. T h e site s y m m e t r y of the actinyl
unit is D 8 with three bidentate nitrate groups providing the equatorial coordina-
tion ; slight twisting of these groups out of the equatorial plane lowers the actual
s y m m e t r y from D3h. In this uniaxial space group three optical polarization
experiments are possible, a (axial), a and ~r (see, for example, [13] for definition).
4. VIBRATIONALSPECTROSCOPY
Following the procedures described in part I and part II of this series the
vibrational modes of Cs2NpO2CI4 can be classified in D4h and those of
CsNpO2(NO3) 3 in D3h. The mode labelling schemes are identica] to those
described in these sources.
Table 1. Ground state vibrational frequencies of Cs2UO,C14 and CsaNpO2C14.
Symmetry Wavenumber/cm-x
Mode in D4h Type of vibration Cs2UO2CI,t Cs2NpO2CI4
v~ Alg O-M-O sym.str. 832 802

v2 A2u O-M-O asym.str. 917 919
v3 Eu O-M-O bend 255 267
,,4 Alg M-CI sym.str. 264 257
v~ B2g M-CI str. 230 230
v6 Eu M-C1 str. 240 244
v7 Bxu M-C1 in plane bend 130 133
vs Eu M-C1 in plane bend 112 117
vo A2u M-C1 out of plane bend 112 117
rio Blu M-C1 out of plane bend Both Raman and I.R.
inactive
vn Eg O-M-O rock 200 185/190
vl + v2 A2u combination band 1745 1705~
t The spectra of both compounds were recorded on the same instrument as part of this
work.
Only measured in single crystals of Cs~U(Np)O~C14.
L2
290 R . G . D e n n i n g et al.
Table 2. Ground state vibrational frequencies of CsUO~(NO3)3 and CsNpO2(NO3)3.
(a) Internal actinyl modes

Symmetry Wavenumber/cm -x
Mode in Dab Description CsUOz(NO3)3~f CsNpO2(NO3)3
Vs A' x symmetric stretch 875 860

Va A"2 asymmetric stretch 956 960
Vb E' UO2 bend 264 268
Vr E" UOz rock 222 217/222/231
(b) Modes derived from internal nitrate vibrations
Wavenumber/cm-a~t
C2v nitrate mode Dab symmetry in MO2(NOn)3- CsUOa(NO,)3 CsNpO2(NO3),
vl (al) At', E' 1510 1504, 1510

v2 (a0 A'I, E' 1020, 1023 1020, 1023
va (al) AI', E' 738, 745 739, 747
v4 (b2) A'2, E' 1260 1263
v5 (b2) A'~, E' 708, 711 709, 711
v6 (bx) A"2, E" 804 803
~- The spectra of both compounds were recorded on the same instrument as part of this
work,
J~ W h e r e 2 frequencies are observed for a single Czv nitrate mode, b o t h are reported.
T h e infrared spectra of both pure n e p t u n i u m c o m p o u n d s were recorded in

mulls at room temperature. T h e Raman spectra were recorded on polycrystal-
line samples at 77 K. Excitation on Cs2NpO2C14 was at 674-6 n m and on
CsNpO2(NO3) 3 at 501.7 n m and 647.1 nm.
In general the vibrational frequencies are almost identical to those in the
analogous uranium compounds, the largest shifts being observed in those modes
which involve the atoms of the actinyl ion. Tables 1 and 2 summarize the fre-
quencies of those modes which are of importance in the analysis of the electronic
spectra. T h e variation in the actinyt frequencies between the uranium and
n e p t u n i u m c o m p o u n d s is in good agreement with the data reported by others [14].
5. SELECTION RULES
In the odd electron, fl, case the irreducible representations applicable to the
electronic states are usually two-valued representations o f the appropriate double
group. Although the data of part I require the use of Dzh site s y m m e t r y for
CszUO2C14, we prefer not to use the D2h* double group for the description of
Cs2NpO~C14. Because this group has only one two-valued representation there
are no differences between the selection rules for different [-f electronic tran-
sitions. However, the results show clear polarization differences in the various
[ - f transitions. T h e s e can be adequately described in D4h* so that this group is
used for the classification.
T h e relevant ungerade representations of Dah* are labelled P o- and ]77-.
Both representations are two-valued [15]. T h e i r relationships to the Do~h bases
are F6- , +1/2, +7/2, + 9 / 2 ; PT- , +3/2, +5/2, +11[2, +13/2. T h e evidence
f-f transitions in [NpO~Cl,] = and [NpO2( NO3)s]- 291
as to the nature of the ground state in C%NpO2CI 4 has been variously interpreted
[16, 17] and we therefore prefer at this point to keep open the possibility that it
has either P6- or Pv- symmetry. Nevertheless a clear distinction in the optical
polarizations is predictable dependent upon whether the ground and excited
electronic states span the same or different two-valued irreducible representations.
T h e outcome is contained in table 3 in which ~ and m refer to magnetic and
electric dipole transition moments, respectively. T h e only useful diagnostic
features are that the two states must have the same symmetry (a) if/xz is active or
(b) if A ~ modes (for example, va) are allowed by m~.
Table 3. Selection rules for Cs2NpO,C14 in D4n*.

Symmetry Transition moments for Vibrations allowing components of

of states electronic transitions the electric dipole transition moment
mg ~'tZx, m y
r a = rE (l~.., l~y), tx. Alu, A2u, Eu Alu, A2u, Blu, B2u, Eu

r e # rE (l~x, l~y) Blu, B2u, Eu Alu, A~u, Blu, B~u, Eu
In § 3 we have indicated that the site symmetry of Np in CsNpO2(NO3) a is

very close to D3h and we therefore employ the D3h* double group in this case.
T h e analysis will be simplified by a decision on the ground state symmetry. For
this purpose the observed value of g~ = 3.4 in the ground state, determined by
E.S.R. [18], can be compared with the values of g, for the various fl states in
D~oh symmetry. For this purpose we describe the Don states by a label An~
where A can be Z, II, A, qb, defining the value of A, the axial orbital angular
momentum, and f~ = 1/2, 2/3, 5/2, 7/2, defining the total axial angular m o m e n t u m .
Assuming only a first order spin-orbit interaction, the calculated values of g~ are
Zi/2u , 2-0 ; II1/~u, 0-0 ; l-I3/~u, 4-0 ; A3/2, , 2-0 ; As/2u, 6.0 ; ~5/2u, 4-0 ; ~7/2~, 8.0.
These values suggest that the ground state should be labelled either qbs/2u or
Ha/2u in D~h. T h e latter state is derived from the f, orbital and would be
expected to be antibonding with respect to oxygen p, orbitals, but the qbs/2~ state
is derived from the f0 orbital, which is non-bonding in this sense, q)5/2~ is
therefore assumed to be the ground state. A more comprehensive treatment by
Eisenstein and Pryce [19] reaches the same conclusion.
There are three two-valued representations in Dah* , F7, F s and P 9 [15].
These representations can be related to the basis functions in Dora by way of the
full rotation group compatibility table given in [15]. T h e full rotation group
representations are subscripted + or - according to the even or odd character
of the basis. We require the D 5- and associate M n with J. It will be necessary
to identify individual components of I'7, F8, and F 9 with particular values of Mn
in order to interpret measurements made in a magnetic field. For this purpose
we use the labelling system employed by Koster [15] and investigate the detailed
transformation properties of individual M a basis functions. The results are
indicated in the first two rows of table 4.
T h e selection rules for transitions from the ground state are also collected in
table 4 and are derived using' the coupling coefficients of table 67 in [15] where
/~±, m± are standard complex transition moment operators defined in the usual
way [20].
t'O
b~
Table 4. Transition moments for electronic transitions in CsNpO3(NO3)3.
Symmetry Excited state

D3h* r,(+ 1/2) r , ( - 1/2) rs( + 1/2) r s ( - 1/2) F0( + 1/2) 1"3(- 1/27
Dooh(Mn) - 5 / 2 , +7/2 +5/2, - 7 / 2 +1/2, - 1 1 / 2 - 1 / 2 , +11/2 - 3 / 2 , +9/2 +3/2, - 9 / 2
D3h* Dooh(Mn)
I'~( + 1 / 2 ) -- 5 / 2 , + 7 / 2 l~z t*+ rnz m+ i~_ m_

r~( - 1/2) + 5 / 2 , - 7/2 p._ p.z m_ mz m+ I-*+
fro
,.°
Table 5. Selection rules for CsNpO3(NOa)a in Dan*. o~
Symmetry of excited state (Dan*) F~ Fs Fa
Transition moments for electronic origins (~,~, ~v), ~ (m,~, my), m. (~,~, .v)(m,~, m~)
Predominant sign of MCD - (weak) - +
Vibrations allowing components of the
p., t,. t • • a t
electric dipole transition moment in mz A1, A 2, E A 1 , A 3 , E '• E,E
(D3h*) (rex, my) A . 1, A"3, E . , E" . A. ' I , A'3, E. , E A 1, A " 3, A " 1, A " 3, E', E "
Predominant sign of MCD for (rex, my) (-),(-),(+),(+, -) (-),(-),(+, - ) , (+) (+),(+),(+),(+),(-),(-)
f-f transitions in [NpO~Cl4] = and [NpO2(NOa)a]- 293
Table 5 contains a summary of the linear polarization selection rules for both
pure electronic transitions and vibrationally assisted transitions. Table 4
indicates that transitions allowed by/~± and m ± between the magnetic components
will be circularly polarized. In the presence of a magnetic field the lower energy
component of the ground state is ~-5/~u which we identify in table 4 with F 7
( + 1/2). As a consequence the magnetic circular dichroism (MCD) spectrum
will contain temperature dependent features reflecting the different thermal
populations of the PT(+ 1/2) and FT(-1/2) levels of the ground state. The
MCD spectrum measures (E1- %) and is positive for transitions allowed by left
circularly polarized light. The interaction with left circularly polarized light is
expressed in terms of the /~_ and m_ transition moment operators [20]. It
follows that the MCD of, for example, a P T ( + l / 2 ) ~ P a ( + 1/2) transition will
have a positive MCD signal. Because the population of 1"7(+ 1/2) exceeds that
of I'~(-1/2) the MCD of a F7~1" 9 transition will be predominantly positive.
The circular polarizations in table 4 are sufficient to identify the symmetry of the
excited states for the electric dipole allowed transitions in D3h* and will be im-
portant in the assignment of the spectra. The predicted signs of the MCD
signals are also given in table 5.
20
T
J
0
_A w
2O
0 w v
l'°ii
[o
E
6.500 6.600 6,700

Energy/¢m -1
F i g u r e 1. A b s o r p t i o n spectra of C s N p O z ( N O z ) z at 4.2 K. U p p e r p o r t i o n ~ polarization,

m i d d l e p o r t i o n o polarization, lower p o r t i o n ~r polarization.
6. ANALYSISOF THE SPECTRA

6.1. Classification of the spectra
The uranyl (VI) ion has a ground state which is a closed shell configuration
with 1Zg+ symmetry in Do~h. The neptunyl (VI) ion contains an extra electron
lying outside the closed shell which, from the E.S.R. results of Bleaney et al. [18],
has the angular momentum properties of an f electron. Two types of electronic
excitation may be anticipated for this configuration. On the one hand the f
electron may be promoted to excited states derived from orbitals of primarily
f character, while on the other hand transitions exactly analogous to those found
for the uranyl (VI) ion may also be expected. In the uranyl case these tran-
sitions are parity-forbidden and represent a charge-transfer from oxygen based
bonding orbitals to non-bonding f orbitals on uranium [3]. The change in the

bonding characteristics leads to progressions in the uranium oxygen symmetric
stretching frequency with a typical length of four quanta and a reduction in the
frequency of this mode (in for example C%UO~CI4) from ~830 cm -I in the
ground state to ~ 710 cm -a in the excited state.
The neptunyl (VI) ion is more oxidizing than the uranyl (VI) ion so that it
might be expected that the oxygen to actinide charge-transfer transitions would
be of somewhat lower energy in the neptunyl case, appearing in the visible and
near infrared. These transitions should also show the typical progressions
characteristic of their counterparts in the uranyl ion. By contrast f-f transitions
Figure 2. The effect of a 2.6 T magnetic field on the polarized single crystal absorption
spectra of CsNpO2(NO3)a in the region of origin I ; after figure 2 of reference [21J.
f-f transitions in [NpO~CI4] = and [NpOa(NOa)a]- 295
are expected to have a smaller influence on the neptunium-oxygen bonding, so
that progressions in the NpO~ symmetric stretching frequency should either be
absent or much attenuated. This difference will be exploited in the classification
of the observed transitions.
6.2. C s N p O 2 ( N 0 3 ) 3
6.2.1. Region from 600 cm-1 to 9400 cm -1 ; origin I, 6459 cm -1
Up to 4000 cm -1 there are no data available because vibrational features of the
host lattice obscure the spectrum. The a, 7r and a spectra for the region 6450 to
6800 cm -1 are shown in figure 1. The intensities Of the band at 6459 cm -1 in the
and ~ spectra are the same within experimental error. The same spectral region
was reported by Leung and Wong [21] who also measured this feature in a mag-
netic field. Their results, which were uninterpreted, are shown in figure 2.
Since both ground and excited states must be Kramers doublets in D3h*, it is
natural to interpret the central feature in the spectrum with the field parallel to
the NpO2 axis as a superimposition of two unresolved components. The
presence of four component transitions connecting the Kramers doublets is
particularly informative. To make the argument rigorous we examine the
selection rules in Dz*, the actual point group. In this group the ground state
forms a basis for the two-valued representation P 4 which correlates with the
Dab* representations P~ and P 8. There are two further conjugate but non-
equivalent representations of D3* , F 5 and F6, which are related by time reversal
symmetry and which together describe the components of a Kramers doublet
[15]. With the standard bases described by Koster [15] F 5 correlates with F 0
( + 1/2)(D~h* ) and P6 with P g ( - 1/2). A comparison of the coupling coefficients
in the two groups establishes the non-zero matrix elements in D3* as, for example,
(r4(a/2)l~_(r3(- X))lre> and (r,(1/Z)lm(r3(- The non-zero tran-
sition moment operators in D3* are then
r4(+1/2) r4(-1/2) I'5 re
I'4(+ 1/2) /~, m~ /~+, m+ m_ /~_
r 4 ( - 1/2) t~_, m_ /*z, mz i~+ m+
If the parallel component of either the electric dipole operator or the magnetic
dipole operator is selected only two component transitions are allowed between
Kramers doublets. The same statement is true of the perpendicular components
of the operators. On the other hand, if both electric and magnetic dipole
mechanisms are operative, remembering that t:. B = 0 all the component tran-
sitions can become allowed. The presence of four transitions in figure 2 implies
that more than one transition moment operator connects the ground state and the
excited state, one allowing the outer pair of lines which appear in both a and rr
polarization, the other allowing the central unresolved feature. In the cr
spectrum the only possible non-zero transition moments are rex.u and /~z.
Because the area of the outer two peaks equals that of the central feature, about
half of the overall intensity is magnetic dipole allowed and half is electric dipole
allowed.
In figure 1 the intensity of the unresolved origin at 6459 cm -1 is identical in
the ~ and a spectra. In the a-polarization the possible non-zero transition
moments are mx, u and/~,u" Since half of the intensity in the a case is due to
mx, u, this transition moment must account for similar intensity in the ~ spectrum.
It follows that the remainder of the intensity in the ~ spectrum is due to/~x,u,
which is also the predominant intensity source in the rr spectrum. To sum-
marize, the intensity in the band has three major sources. In the a spectrum
m~,u a n d / ~ contribute equally and in the ~ spectrum mx, y and/xx, y contribute
equally. Table 5 shows that the simultaneous presence of/zz and/~x,y implies an
excited state symmetry, I'7(D3h* ). The small m~,y contribution to the intensity
must arise from the deviation from D3h* symmetry. The important rble of the
magnetic dipole transition moment implies that this feature should be identified
as the pure electronic origin band. A group of low intensity vibrational side-
bands, all with frequencies less than 300 cm -z, are observed on this origin.
50 -
I]
l I
100
0
~TT
MO
feature
50
T[.
V3
i_i_I[.3,..
~+vs
nitrate
1 ]i.v3
nitrate~
i E'A;
L
nitr°V~e
0 "- "~--~ I I I I
,2oi
E
I
94
L J..d_
96
I--
9-8
""
10-0
I '~
10-2
I -
11:
~
10-4
'
E n e r g y / l O 3 c m -I
Figure 3. Absorption spectra o/c CsNpO2(NOa)3 at 4"2 K. Upper portion e~polarization,

middle portion o polarization, lower portion ~r polarization.
f-f transitions in [ N p 0 2 C I , ] = and [ N p O ~ ( N 0 3 ) 3 ] - 297
There are insufficient data to assign these at this point. We note the absence of
high frequency modes and of any progressions, which would be characteristic of a
change in the neptunium-oxygen bonding.
6.2.2. Region from 9400 cm -1 to 13 000 cm 4 ; origin 11, 9420.2 cm -1

The only features in this region occur between 9400 cm -1 and 10 500 cm -1
and are shown in figure 3.
The feature at 9420.2 cm -1 occurs in all three polarizations but is strongest in
the a spectrum indicating the dominant r61e of the/~z mechanism. This feature
is confirmed as an origin by the observation, at 50 K, of weak hot bands at
120 cm -1 and 240 cm -~. The detailed intensity mechanisms are clearly revealed
by interpreting the spectra taken in a magnetic field, which are collected in
figure 4. As argued for origin I, the presence of four lines indicates that the
intensity is derived from both electric and magnetic dipole mechanisms. The
BI!
- - 12.7K
....... 4-4K
5.6K
A
9 410 9 420 cm -1 9 430
Fnergy/cmq
B j_
.[
9420
Figure 4. The effect of a 5.0 T magnetic field on the polarized single crystal absorption
spectra of CsNpO2(NOa)a in the region of origin II.
identification of the transitions is simplified by the temperature dependence, also

shown in this figure, from which the ground and excited state g-values can be
directly obtained. We findg,, =3.32+0.05 for the ground state and 5.19+0.08
for the excited state. The observed splitting in a perpendicular magnetic field
gives a g-value of 2.17 + 0.04 which is a composite of the ground and excited state
values. Unfortunately the E.S.R. determination of the ground stateg-value [18]
has wide error limits and it is suggested that g l = 0-2 + 0.2 so that the excited state
value is g l = 2-17 + 0-44.
Comparison of the areas of the components in all three polarizations shown in
figure 4 shows that the intensity mechanisms are represented in the following
ratios/~, :mx, y :/~x,y-- 1.0 : 0.31 : 0-05. Table 5 shows that the dominant r61e of
/~ implies FT(D3h*) symmetry for this excited state.
All of the vibronic structure in the ~ and a spectra between 10 000 cm -1 and
10 700 cm -1 is readily assigned to internal nitrate modes, whose frequencies are
in good agreement with those included in table 2. Comparing the ~ and a spectra
the band at 10 166 cm -1 is seen to be magnetic dipole allowed and corresponds to
the A'I component of the va internal nitrate vibration. It lies 746.2 cm -a above
origin I I and corresponds to the'Raman active mode which has a frequency of
747 cm -~ in the ground state. The presence of this feature implies a distortion
in the electronic excited state in the sense of the normal coordinates of this mode
which can be described as a symmetric deformation within the equatorial plane
which modulates the O - N p - O angle within each bidentate nitrate group [7].
The vibronic structure lying within 300 cm -t of origin I I is very similar to
that shown in figure 1 with the striking exception of the single feature near
9647 cm -1, which is shown by its polarization to be magnetic dipole allowed.
This mode is also responsible for a progression reproducing the remainder of the
low frequency structure between 9700 cm -1 and 9950 cm -~. The selection rules
taken together with the presence of a progression imply that this mode has
d ' l ( D 3 h * ) symmetry. Only one A' 1 nitrate mode does not involve the internal
coordinates of the nitrate group and can be described as the symmetric in-plane
breathing of the three bidentate ligands [7].
The coupling of two totally symmetric modes to this electronic transition can
be rationalized in terms of a change in the neptunium-nitrate bonding as a result
of the electronic excitation. Subsequently we shall show that this is consistent
with an excitation from a predominantly a non-bonding f¢ orbital to a second [~
orbital with some antibonding character directed towards the nitrate oxygen.
Relaxation of this antibonding interaction can be achieved either by a stretching
of the Np-O distance or by changing the O - N p - O bond angle defined by the
nitrate group. By contrast there is no evidence in the spectrum for any relaxa-
tion in the Np-O distances within the neptunyl ion.
6.2.3. Region from 13 000 cm - t to 21 700 cm -1 ; origin V I , 17 843.6 cm -x ;

origin I X , 20 816.3 cm -a
This portion of the spectrum shows absorption beginning at 13 900 cm -1.
It is dominated by features which occur in progressions with intervals of approxi-
mately 750 cm -1 whose intensity distribution is very similar to that found in the
charge-transfer type transitions of the uranyl ion [2]. The spectrum can be
analysed in terms of five electronic transitions of this type which will form the
f-f transitions in [Np02Cl4] = and [NpO2(N03)3]- 299
substance of the accompanying paper, part VI in this series, and which we tem-
porarily ignore. Within this structure there is evidence for two electronic
transitions of a different nature. The regions in which the latter type of transition
is observed are shown in figures 5 and 6 which also contain the M C D spectra.
MCD
&o o
VI
150
II Vll
100
T
E
1
I
50
0 I
_ ~.~J ~ d ~ ~ L ~ ~-J~ ~-~-~
- I ] I I l I I I I
~0
E
I o
17.8 180 18'2 1~4 18'.6 ~e~8 ~go ~g,~ ~9.4 ~9.e ~g.8
Energy/lO3cm -1
Figure 5. Polarized single crystal absorption and M C D spectra of CsNpOz(NO3)3 at 4.2 K.
Upper portion MCD, middle portion o polarization, lower portion 7r polarization.
The nature of the progressions in this region is complicated by a phenomenon

which also appears in the absorption spectrum of CsUO2(NO3)3 [2]. Briefly, at
the nth quantum in the progression up to (n + 1) components separated by about
30 cm -1 are observed. With the aid of oxygen-18 substitution it has been shown
MCD
+
&oo
xll
Uranyl l
IX
150 0
I 100
IX
E *',5
50
150 IX* Uranyl

v26 .[
I"[
T 100
E
50 IX
IX ÷v3
I IX
0 - ~ -]
206 208 21-0 21 2 21.4 216
Energy/lO 3 cm-1
Figure 6. Polarized single crystal absorption and MCD spectra of CsNpO2(NO3)3 at 4.2 K.
Upper portion MCD, middle portion a polarization, lower portion *rpolarization.
f-f transitions in [Np02Cl4] = and [NpOz(NOz)z]- 301
that this is due to the presence of two totally symmetric A'I(D3h* ) modes, which
in isolation would be almost accidentally degenerate. One of these is the UO~
symmetric stretching mode which in the excited state has a frequency of
~-750 cm -1, reduced from 880 cm -1 in the electronic ground state, while the
other corresponds to the A ' t component of the va internal nitrate mode. T h e
latter mode has a frequency of 747 cm -1 in the ground state and 746 cm -1 in
association with origin I I. T h e vibrational hamiltonian strongly couples these
two modes and, on the assumption that the UO 2 symmetric stretching mode is the
sole source of the intensity, a satisfactory description of the observed intensities
is obtained [2].
Figure 5 illustrates how the same phenomenon is present in a charge-transfer-
type transition of the neptunyl ion. T h e features labelled V I I + vI and V I I + ve
represent the pattern expected when the contributing modes are essentially
degenerate. By contrast the pattern of intensity in the features labelled VI + vn
and VI + vt is clearly different. On the assumption that the interaction energy
between the modes, 16 cm -1, is identical to that found for CsUO2(NO3) 3 [2], the
frequencies (Vn° and vl°) of the unperturbed modes are calculated to be 751.3 em -1
and 812 cm -1, giving a predicted intensity ratio of 1 : 16 which is close to the
observed ratio. T h e value for v6° is close to the value of 747 cm -1 in the
electronic ground state, found from the Raman spectrum, while the value for vl°
lies between the ground state value of 860 cm -a and the value of ~ 750 cm -1 found
in a typical charge-transfer-type excited state.
T h e large difference in vl between origin VI and origin V I I is clearly illus-
trated in figure 5 by the much smaller separation between VI + vI and V I I + v1 as
compared with the separation between the origins themselves. A further striking
difference between these two origins is the complete absence of the second
q u a n t u m of the progression in v1 for origin VI whereas four quanta can be dis-
cerned for origi n V I I . Origin V I I is a typical charge-transfer-type transition.
It follows from the value of v1 and the observed F r a n c k - C o n d o n factors that
origin VI is due to an electronic excited state which involves a m u c h smaller
change in neptunium oxygen bonding. We opt to assign this as an f-f type
transition.
There is no observable difference between the e and o spectra in this region
and it follows that all the structure is mx. u electric dipole allowed. T h e strong
band at 17 843.6 cm -~ is taken as origin VI. Table 5 shows that the strong
negative M C D in this band implies P8 excited state symmetry. T h e vibrational
structure on origin VI is centred near 18 100 cm -1 and the vibrational intervals
and intensities are very similar to those observed on origin I I.
T h e Zeeman splitting of origin VI and vibrational features built on it is
sufficiently characteristic to allow their unambiguous separation from features
associated with origins V I I , IV and V, all of which appear in this region.
T h e symmetric stretching progression built on origin IX at 20 816.3 cm -1
(shown in figure 6) is very similar to that described for origin VI. T h e unper-
turbed frequencies are v6°=754.4 cm -1 and v1°=814.5 cm -t. Following the
same argument we identify this as an [-f transition. T h e M C D in figure 6 shows
the excited state symmetry to be 179. A comparison of the ~, ~r and o~spectra of
this origin recorded in a magnetic field shows that the intensity in the rr spectra
is due to/~x,y. Taken with the strong mx,y electric dipole intensity, this provides
further evidence, via the selection rules of table 5, for a Uo excited state. Intense
absorption by the host material, whose first origin is at 21 090 cm -1, prevents
further analysis of this region.
6.2.4. Low [requency vibrational structure

Origins I, II, VI and IX all show a group of vibronic sidebands with fre-
quencies between 200 cm -1 and 300 cm -1. While it is not possible to reach a
definitive assignment in every case, some important conclusions can be made.
Of the 26 internal modes of the complex anion 12 are essentially internal nitrate
modes with frequencies close to those given in table 2 lying above 700 cm -1.
Four more modes are associated with the motion of the NpO~ group, two at
frequencies near 800 cm 1 and two in the region of interest. Of the remaining
ten modes four may be classified as Np (NO3) stretches, while the remaining six
are deformations of the Np(NOa) a framework and are presumed to be lower in

frequency than 200 cm -1.
The Np-(NOa) stretching modes have A'I, A'= and E' symmetry and are
modes that either involve the symmetric stretching of each bidentate group with
respect to neptunium or asymmetric stretching. T h e modes can be described as
A' 1 (NO a symmetric), A' 2 (NO a asymmetric), E' (NO a symmetric) and E'
(NO3 asymmetric).
The A' 1 mode has already been identified in § 6.2.2 and has the frequency
226-4 cm -1 on origin I I. T h e A' 2 mode can be found by the sign of the M C D on
the vibronic features near 238 cm -1 which occur for both origins VI and IX.
On origin VI the negative M C D implies A'~, A'~ or E" vibrational symmetry and
on origin IX the positive M C D implies A'a, A'2, A"I or A" 2 symmetry. T h e
possible symmetries for this mode are therefore A'~ and A'~. If this feature were
the totally symmetric A' 1 mode then it would be anticipated that it would have
the same accompanying low frequency sideband structure found close to the true
origins. The mode 238.0 cm -1 above origin IX, at 21 054.3 cm -1, has no such
structure while the mode 237-5 cm -~ above origin VI, at 18 081.1 cm -~, has
accompanying structure with the opposite sign of M C D to that found close to the
origin itself. T h e preferred symmetry of this mode is A' 2.
T h e analogous mode of this symmetry in an excited state of CsUO2(NO~) 3 is
unambiguously identified from the polarization of a strong feature at 26 865 cm -1
and has a frequency of ~ 225 cm -1 [2].
It will be easier to characterize the remaining Np-(NO3) stretches after the
NpO2 bend and rocking modes have been identified. Origins I, I I and VI all
have a band between 258 cm -~ and 263 cm -a. On origins I and I I it appears in
both a and zr polarizations and must have A"I, A"~ or E' symmetry, while on
origin VI it has positive M C D implying E' or E" symmetry. The frequency of
this mode, which must, therefore, have E' symmetry, is close to that of the E'
NpO~ bending mode at 268 cm -1 in the electronic ground state and we assign it
accordingly. T h e actinyl rocking mode in uranyl compounds invariably lies
below the bending mode in both the ground state and electronic excited states.
If the Raman band at 222 cm -1 is assigned to this mode we believe that the
features near 205 cm -1 on all the origins may be due to this mode. T h e linear
polarization and M C D evidence do not contradict this assertion.
Two Np-(NO3) E' stretching modes remain to be assigned. In the infrared
spectrum of CsUO2(NO3)3 oxygen-18 substitution shows the virtual super-
"imposition of two modes, near 265 cm -1, which have different sensitivity to
f-f transitions in [Np02C14]= and [NpO2(N03)3]- 303
Table 6. Low frequency nitrate modes coupled to electronic transitions in CsNpO2(NOz)3.
Mode NpO~ rock Np(NO3)asym. Np(NO3)sym. Np(NOs)sym. Np(NO3)asym. NpO~bend

Symmetry E" E' A'x E' A'~ E'
Origin I/cm -1 207-2 224.5 -- 232 -- 259.1t

Origin II/cm -1 203.9 210.7, 215.3 226.4 234 -- 258.7
Origin VI/cm -1 202.3 -- -- -- 237-5 262.4
Origin IX/cm -1 204.9 210.0 -- -- 238.0 --
Ground State 222 218 -- 268~ -- 2685
t There is an unexplained feature at 285.4 cm -1 on this origin.

$ Assumes overlay of Np-(NO3) stretch and NpO~ bend indicated by uranyl data [6].
Table 7. Summary of observed electronic excited states in CsNpO2(NO3)a.
Origin Energy/cm -1 Symmetry gu g±
Ground State 0 F7 3.34+ 0-07 0.2 + 0-2

I 6459.0 I"7 Not observed Not observed
II 9420.2 F~ 5-29 + 0.10 2.17_+ 0"44
VI 17483.6 Fs 0.12+0-15 0"2 _+0"3
IX 20816-3 F9 4.11 _+0.09 0.2 _+0.35
isotopic substitution, and a third m o d e at 219 cm -1 which has a smaller sensitivity

[6]. T h i s indicates the presence of three modes, which include and have the
same s y m m e t r y as the E ' uranyl bend, whose influence is sensitive to oxygen-18
substitution. Possible frequencies for the analogous E ' N p - ( N O ~ ) stretching
modes in the n e p t u n y l excited states are included in table 6.
6.2.5. Summary of the electronic states of CsNp(NO3)z

T a b l e 7 contains the energies, s y m m e t r i e s and magnetic m o m e n t s of the
electronic excited states discussed in § 6.
6.3. CsNpO~Cl4
T h e rigorous site s y m m e t r y of the n e p t u n i u m atom in this material is Czh and
is centrosymmetric. F o r f - f transitions it follows that all pure electronic tran-
sitions will be electric dipole f o r b i d d e n but m a y be allowed by magnetic dipole or
electric quadrupole mechanisms. I n the spectra which follow the label Z(y)
indicates that the light propagates parallel to the NpO~ axis and that its electric
vector is parallel to the C 2 axis which bisects a C 1 - N p - C I angle, defining the
molecular y-axis [5]. Features which occur in Z(y) or X(y) but not in b o t h
m u s t be viewed as non-electric dipole transitions.
We now make a preliminary hypothesis, to be fully justified later, about the
s y m m e t r y of the ground state (in D4h* ). W h i c h e v e r of the n o n - b o n d i n g f
orbitals lies lowest in energy the lowest s p i n - o r b i t state m u s t be qb~/2 or
A3/2(D~h ). Both of these form a basis for F 7- in Dab* and we adopt this as the
ground state symmetry.
6.3.1. Region between 600 cm -~ and 4000 cm -1 ; origin I (c. 900-1050 cm -1)
Figure 7 compares the polarized spectra of Cs2UO2Cla with those of
Cs2U(Np)OzC1 a in which ~ 5 per cent of the uranium atoms are replaced by
neptunium. Four significant additional features are observed in the latter
crystal. The band at 1705 cm -1 is simply assigned to the NpO~ 2+ Vl+ v~ com-
bination band (cf. table 1). Because the neptunium and uranium frequencies in
table 1 are so similar, the remaining additional features in the neptunium con-
taining crystal, which are much more intense than possible combination bands,
indicate that they should be attributed to a new electronic state. These bands
are electric dipole allowed in the (y) polarization and occur at 1040, 1245 and
1530 cm -1. It has not proved possible to assign these features to reasonable
vibrational quanta coupled to an electronic origin. Nevertheless we believe that
the electronic origin lies between 900 cm -1 and 1040 cm -1. The lower limit is set
because a feature whose intensity is proportional to the neptunium content of the
lattice is observed at 915 cm -1 (a feature at 760 cm -x seems to be a hot band).
However, there is an alternative interpretation for this band ; it is at the same
frequency as the UO22+ v2mode which occurs in the opposite polarization and the
local perturbation caused by the substitution of the NpO22+ ion may relax the
polarization selection rule. A similar argument can be applied to the small
feature at 1745 cm -1 in X(y). There is no evidence of progressions in the
NpOz 2+ stretching mode so that we conclude that the electronic excited state
arises from an [-[ type transition.
6.3.2. Region between 4000cm -1 and 13200cm-1; origin II, 6880.4cm-1;

origin 111 (c. 7890 cm -1)
Figure 8 shows the only significant portion of the spectrum of
Cs2U(Np)O2C1 ~ in this region. Comparison of X(z), X ( y ) and Z(y) demon-
strates that the band at 6880.4 em -1 has identical intensity in X ( z ) and Z(y) and a
lower intensity in X(y). Bearing in mind that in the centrosymmetric case
optical transitions must be either electric dipole or magnetic dipole allowed, these
polarizations identify the mechanism as/zx, u, the X ( y ) intensity being due to t~.
This mechanism requires us to assign this band as the origin; a conclusion
supported by the observation of appropriate hot bands at room temperature.
The polarizations of the remaining features in the spectrum show them to be
electric dipole in character.
The assignment of the vibronic structure within 300 em -x of origin II is given
in the figure and is based on the frequencies and assignments in the uranyl case
[1]. The electric dipole band at 7799 cm -1 is 919 cm -x above the origin and is
assigned as II + v2, but there is no evidence for II + v1. The frequency of v~ is
identical to that in the ground state indicating no change in the Np-O bond, as
does the absence of v1. It follows that this transition is of t h e / ' - f type. The
magnetic dipole polarization and table 3 shows that the excited state for origin II
has the same symmetry as the ground state F7-. The same result is required by
the observation that II + v2 is electric dipole allowed by m~ (table 3).
f-f transitions in [NpO=Cl4] = and [NpO=(N03)3]- 305
Above 7900 cm -1 there are more electric dipole features. Because they are
strongly polarized they cannot be assigned as a repeat of the vibronic sidebands of
origin II which are almost unpolarized, and must be built on a new origin, III.
100°1o
X(y)
0 o/<
,~, k. , J~k,.
100°/o
x(z)
13
<
0 °[o
600 800 1ooo ' ,200 1;.oo ' ,c;oo 18'oo
100°to
1
X(y)
0%
J
100%
1
×( . . . . . 1
600 800 1000 1200 1400 1600 1800

Energy/cm -1
Figure 7. Polarized single crystal absorption spectra at 4.2 K of Cs~UO~CI4, u p p e r two

portions, and Cs~U(Np)O2C14, lower two portions. (Polarization notation is
explained in the text.)
306 R . G . D e n n i n g et al.
15
x(z)
l] U+v 9 l[l-v3
~ lo
£
O.v 2
I 5
Av
15 -If [] -v 3 x(y)
II.Vlo r[ . v 2
10 new struclure
built on 1|I
0 ^ A
I
15 II Z(y)
10
0 A
1
7.0 72 74 76 ?8 8.0 8.2 84 8-6 8-8

Energy I I 0 3 cm -1
Figure 8. Polarized single crystal absorption spectra of C%NpOzC14 at 4.2 K. Upper

portion X(z) polarization, middle portion X(y) polarization, lower portion Z(y)
polarization. Only the magnetic dipole features are labelled in the Z(y) polarization.
T a b l e 1 shows that the low frequency m o d e s of C%NpO2CI 4 in the g r o u n d

state divide into two groups, a group of ungerade m o d e s centred near 115 c m - I
and a second group centred at 255 cm -1. I n figure 8 the two groups of m o d e s
near 8100 cm -1 are separated by about 140 cm -1 and we infer that they corres-
p o n d to the groups observed in the ground state. T h e r e are insufficient data for a
full assignment but the origin m u s t lie close to 7890 c m -1. While the absence of
any progression based on this structure implies an f - f transition, there are no
criteria on which to assess the s y m m e t r y of this excited state.
f-f transitions in [NpO,C14] = and [NpO~(NOa)a]- 307
vn-r.
Eu modes
x(z)
40
vnl,~,
Eu modes
T
I 2o Vl/
I ~I,*~
V111 +2vI
/ V]1
+ Eu m o d e s
vm~ Vl]I
+E~ modes
Vm'.
VI L
JLA . . . . . A - -
I I I I I I
VllI+
40 - Eu modes vm'. vl +
Eo modes
V11 VII + x(y)
*v2 V 1 ÷V 2
12o_ v= vm÷2~
+ Eu modes
vn+
2~,v2
V]]I+ v~ VTII ÷ vl +v~
+ E u modes V~
0 ~
60
Z(y)
40
0 i 1 --- I - " I -- I I I I
17.2 17./. 17.6 17.8 18-0 18-2 18.4 18.6 18.8 19.0
E n e r g y / 1 0 3 cm - I
Figure 9. Polarized single crystal absorption spectra of C%NpO~CI4 at 4.2 K. Upper

308 R.G. Denning et al.
X(z)
40
Urpnyl
T
E X÷
Eo modes
12o
Eu modes
I i {
1 I 1 1
V3. G
X(y)
X+Vl* N I f~
40
T
£
12o
I I i [ I
Uronyl Uranyl
II It., v
Z(y)
40
o tl! tt
20-2 201-4 2& 2o'.8 2~!o 2~.2
E n e r g y / I 0 3 cm -1
Figure 10. Polarized single crystal absorption spectra of Cs2NpO2C14 at 4.2 K. Upper
(Neptunyl features are distinguished by arrows).
f-f transitions in [NpO~C14] = and [NpO~(N03)3]- 309
6.3.3. Region from 13 200 cm -x to 21 250 cm -1 ; origin V I I I , 17241-4 cm-1 ;

origin X, 20 080.8 cm -1
Just as the spectrum of CsNpO~(NOa)z has charge-transfer type transitions
in this region (§ 6.2.3 and following article) so does C%NpO2CI 4. They show a
strong resemblance to the analogous uranyl transitions and form progressions of
about four members, with intervals of ~710 cm -1. The complication in the
spectrum of CsNpO2(NOz) 3 caused by the presence of two interacting progression
forming modes is absent in C%NpO~CI 4.
Figure 9 illustrates the presence of two entirely different types of electronic
transition in the region between 17 200 cm -1 and 19 200 cm-L This is made
obvious by the progression frequencies in the X ( y ) polarization. While the
strong feature at 17 556 cm -x has a repeat frequency of 697.6 cm -~ the strong
feature lying close to it, at 17 457 cm -1, has a repeat frequency of 765.6 cm-L
The result is a much smaller separation between these features near i8 250 cm -~
and an inversion of their order near 19 000 cm-L The interval of 697.6 cm -~ is
characteristic of vx in combination with v2 and is smaller than the typical value of
v~ in association with the other internal modes in charge-transfer type transitions
( ~ 710 cm -1) as a result of the strong anharmonic coupling between vt and v~.
The much higher interval of 765.6 cm -1 must be assigned to an f-f type transition
since the excited state should be less antibonding. The frequency is reduced
from that in the ground state by almost the same factor as observed for the analo-
gous transition in CsNpO2(NO3) 3. The origin of this transition is a magnetic
dipole allowed band at 17 241.4 cm -~ with a repeat frequency of 767-4 cm-L
The mechanism is unambiguously established by its observation in both X ( z )
and Z(y).
The assignment of the principal vibronic structure is shown in figure 9.
The modes lying between 17 450 cm -I and 17 600 cm -1 are effectively un-
polarized and are repeated near 17 800 cm-L This second group lies about
500 cm -1 from the origin, has the same progression frequency in v1 and polariza-
tion as the first group, and lies 274 cm -1 above it. There are no fundamentals
near 500 cm -~ and we therefore interpret the second group as a progression
formed by a mode with a frequency of 274 cm -1. The only appropriate totally
symmetric mode is v4, •lv(D4h), the neptunium-chlorine stretch, which has a
frequency of 257 cm -~ in the ground state.
The presence of v4 coupled to this origin implies a distortion of the Np-C1
bond length. It would be natural to explain the progression in terms of a
strengthening of the Np-CI bond as implied by the change in the frequency of v~.
An f-f transition of type f± ~-->f±x excites an electron which is effectively localized
on neptunium and transfers it to an f, orbital which, because of its antibonding
overlap with oxygen orbitals, transfers electronic charge onto the oxygen atoms
of the NpO2 ~+. The increase in the positive charge on the neptunium atom
should, in turn, strengthen the neptunium-chlorine bond.
Figure 10 shows the region containing origin X. It is seriously overlaid by
the absorption of the host lattice which begins at 20 095 cm-L There are no
significant Zeeman shifts in the spectrum of the host, so that neptunyl features,
which are additional to the host features and are identified in the figure by arrows,
can be confirmed by their Zeeman splitting. The most obvious new features
in this region, which are not repeats of earlier structure, are the band at
20 300.4cm -1 and its repeat at 21 065.0 cm -1 in X ( z ) . The interval of
765.6 cm -1 is very comparable with the intervals on origin V I I I . The structure

is similar in detail to that appearing 200-300 cm -1 above origin V I I I and appears
near 21 100 cm -1 in both X(y) and X(z), where both polarizations are unob-
scured. It can be inferred, by analogy with V I I I , that the origin should be
observed near 20 080 cm-L A small sharp feature at 20 080.8 cm -x is observed
in X(z) and Z(y). The feature in Z(y) is partly obscured by adjoining electric
dipole structure. Nevertheless, careful comparison with X(y) leads us to believe
that this feature is magnetic dipole allowed. The interval between origin X and
the electric dipole structure at 20 299.4 cm -1, 218-6 cm -I, is very close to the
analogous interval on origin V I I I , 215-8 cm -1, and helps to confirm the close
relationship between both these transitions, which must be seen as f-f in type.
There are no data which enable the symmetries of excited states V I I I and X to
be determined.
6.3.4. Magneticproperties
In order to interpret the Zeeman splitting of the various excited states it is
essential to establish the g-values of the ground state. Although the g-values of
the ground state have been reported from E.S.R. measurements [17] there is a
large uncertainty in the value reported for g~, because the E.S.R. signal vanishes
as the field direction approaches the principal axis. The reported values are
g~, ~ 1.3 +0.3 and g_~= 1.32+0.02.
An improved value of g~ was determined optically by measuring the relative
areas of the hot and cold Zeeman components of a sharp line at 17 557.9 cm -1,
which shows a conveniently large splitting. The cold band appears at lower
energy so that the observed splitting must be interpreted as the difference of the
ground and excited state Zeeman splitting, that is gobs=g~s--ggs. Eight
measurements were made between 4.18 K and 14 K. The temperature was most
accurate for the 4.18 K measurement for which the sample was immersed in
liquid helium. We findg,, = 1-38_+ 0.07. The Zeeman splittings in a perpendi-
cular magnetic field were not large enough to allow a determination of g . for the
ground state with better precision than that available from E.S.R. and we use
g . = 1"32 ___0-02 in our analysis.
The g-values for states V I I I and X are included in table 8. This table also
summarizes the energies and symmetries of the f-f transitions in C%NpO2C14.
7. THEORY
7.1. Introduction
The model used here follows that of Eisenstein and Pryce [19, 22]. An
I orbital basis is assumed and a perturbation hamiltonian is defined with the form
/~--- ]~ax-]- ~L . ~-'}- ~req. (1)

Following the practice of [3] Vax is assumed to be the largest term and we adopt a
quantization scheme with respect to a cylindrical axis system. In this system
the basis functions are labelled ~, rr+, 8_+, ~_+ indicating the values of )~ and ma.
The relative order of the energies of the orbitals in the axial field is likely to be
o > ~r > 8 ~ ~b. These energies are denoted by %. The spin-orbit coupling takes
the standard form in this basis, while the appropriate forms of the equatorial field
f-f transitions in [Np02Cl4] = and [NpO2(NO3)3]- 311
Table 8. Summary of observed electronic excited states in Cs2NpO2C1,.
Origin Energy/cm-1 Symmetry gm g-
Ground State 0 F 7- 1.38 + 0.07 1-32 _+0.02

I ca. 900-1050 -- -- --
II 6880.4 F 7- -- --
Ill ca. 7890 -- -- --
VIII 17241.4 -- 0-6 _+0.45 0.2 _+0.3
X 20080-8 -- 3.8 -+0-4 0-1 -+0-5
for D 3 and D~h have been given in [3]. T h e only non-zero matrix elements
within this basis set are defined by the potentials
V3 = e q ( r 6 ) / z r . 231~1/2
47r%R7 \ ~ / 0"3405{Ye 6+ Ye-e},
Va= ,~0~eq[ ~ " \(~-"1835~1/2

] {Y44+ Y4-4} - ~ 7) " \(zr"
63~1/2104
] " {Y64+ Ye-4)] '
where V3 is evaluated from the positional parameters found in the crystal structure
of RbUO2(NO3) 3 [12], idealized to D3h , and V4 assumes the symmetry of
[NpO2C14] = is idealized to Dan. T h e full equatorial field will, of course, contain
axially symmetric components, which can be considered as part of the axial field
and are not separately parameterized. T h e parameterization of V3 and V4 is in
terms of ( B n ) = eq(rn)/4zreo Rn+l. T h e relevant non-zero matrix elements are
(331 v3t3 - 3) = 0.92(Be),
(321 v413 - 2) = - 0.53 (B4) + 0"37(Be),

(33 [ V413 - 1} = 0.41 (n4} + 0.24(Be}.
Diagonalizing the full matrix in equation (1) gives a set of eigenvalues. T h e

eigenvector matrix was used to transform the magnetic m o m e n t matrix to the
eigenbasis, providing both the g-values of the states and the magnetic dipole
transition moments.
T h e basis set predicts seven Kramers doublets and six optical transitions.
Four f-f transitions are observed in CsNpO2(NO3) 3 and five in Cs2NpO2C14.
A satisfactory analysis for both compounds will emerge if it is assumed that, as
expected from its antibonding character, the a u orbital lies higher in energy than
the optical region studied here.
7.2. CsNpO2(N03) s
Although the energy levels of CsNpO2(NO3) s are described by five parameters
and only four energies are experimentally available, the range of possible solutions
is limited by the requirement that the symmetry of the excited states should also
be correctly predicted. Two sets of energies for the excited states were calcu-
lated with different but fixed values of % - e ¢ , the remaining four parameters
being varied to optimize the agreement with the experimental energies. T h e
t.o
bO
T a b l e 9. Calculated and observed magnetic properties of electronic states in CsNpO2(NOa)3.
Calculated Observed
Fit I Fit I I
Symmetry Energy ~(ixz) ~(tXx,y) Energy ~(Ixz) ~(IXx,y) Symmetry Energy ~(tzz) [(gz,y)
Dan(Doon) / c m -1 g~ g.L /10 -s /10 -s /cm-* g,, g± /10 -s /10 -s Dab label / cm-x g,t g- /10 -8 /10 -s
FT(q)5/2u ) 0.0 3.78 0.30 -- -- 0.0 3.27 0.48 -- -- r7 0 0.0 3.34 0 . 2 t --

1"9(Aa/~u) 344.7 2-06 0.00 0.0 2.3 1105.9 2.06 0.00 0.0 8.2 -- n.o n.o n.o
1"7(As/~u) 6459.0 3.95 2.02 58.2 14-8 6459.0 3.60 2-14 85.0 23.8 F~ I 6459.0 3-7t 2"1t 50 48
1"s(¢7/2u) 9420.2 5-74 2.32 141.2 2-9 9420-2 4-87 2.62 226.9 2.0 F: II 9420.2 5.24 2.17 190 10
FT(IIx/~u ) 17843.5 0.00 0.26 0.0 0.0 17843.6 0.02 0.71 0.0 0.0 Fs VI 17843.6 0.12 0.0 masked
Fg(IIa/~u ) 20816.3 3.94 0.00 0.0 82-7 20816.2 3.94 0.00 0.0 58.3 I'9 IX 20816.3 4.11 0.05 masked 29
0~
Fs(Ya/~.) 119392.0 2.00 2.26 0.0 0.0 512~5 1.98 2.71 0.0 0.0 - - n.o n.o n.o
P a r a m e t e r s / c m -1
•~- ~ -2074.5 - 1366.0
¢.-¢~ 13847.0 14179.8
¢ ~ - ¢~ 114000.0 46000.0
2212.0 2047.3
<Be> 2402.3 2953.8
t Values taken f r o m [21].

f-f transitions in [Np02CI4] = and [NpOz(N03)3]- 313
results together with the parameters are shown in table 9. The table also in-
cludes calculated g-values and magnetic dipole transition moments. The choice
of %-E4 is constrained by the sensitivity of the calculated g-values to this
parameter. In particular the two chosen values for % - ~ 4 produce large
differences in the g-values of both the ground state and the excited state respon-
sible for origin II, such that they straddle the observed values. The constraint
justifies our assumption that the Ps(%/2u) excited state lies above the energies
which could be investigated in our experiments. The magnetic properties of the
observed P 8 state, which is the only other state of this symmetry, cannot be inter-
preted in terms of %/2u parentage. The two parameter sets both predict an
energy level between 340-1100 cm -1 which cannot be observed in the presence of
the vibrational transitions of the host material.
The magnetic dipole oscillator strengths can be calculated from the areas of
the magnetic dipole bands in the spectrum. Where they are observed these
quantities are included in table 9 and are in good agreement with the calculated
strengths. The excellent agreement of all the observables with their calculated
counterparts gives us confidence in this analysis. In particular, the way in which
the values for the two parameter sets straddle the observables indicates that
reasonable outer limits have been found for % - ¢ 4 and that the difference in the
remaining parameters between the two sets should be taken as good indications
of their precision.
7.3. Cs2Np02CI4
In the D4h field of the chloride ions the equatorial field has two non-zero
matrix elements < < l V , la_> and <¢+IV, and two radial parameters
(B4) and (Be) are needed to describe the perturbation. The joint operation of
this perturbation and the spin-orbit interaction will strongly mix the A3/2 and
005/2(D~h) parent states, if ea--E¢ is similar in magnitude to the value found
in CsNpO2(NOa)3.
Specifically the perturbations link 00+5/2 with A~3/2 so that the magnetic
properties of a given Kramers component is very sensitive to the degree of
mixing. We now define a general g-value as
g,, = (1/,B){(rT-(½) I,z Ir,-(½)) - < r 7 - ( - ~) l~. Ir 7 - ( - 1))} (2)
and
g . = (1/~*B){<r,-(-- k)l~*_lrT-(+ ~)> + <r~-(½)l~,+lV,-(-- ½)>}. (3)
The Doon basis functions form bases for P7- as follows, P7-(+ 1)= _ 3/2, + 5/2
and P 7 - ( - ½ ) = +3/2, - 5 / 2 . In the limit that the ground state is A+a/=,
equation (2) gives g,, = - 2 - 0 with A_3/= lying below A+3/2. At the opposite limit
the ground state is derived from 00+5/2 and equation (2) gives gH = +4.0 with
00-5/2 lying below 00+5/2. At both these limits g . = 0 . In the mixed rdgime g~
is strongly dependent on the detailed form of the wavefunction and can pass
through zero. In the same rdgime g± > 0 as a result of non-zero matrix elements
of the type (A+3/2]/, ]00+5/2) appearing in equation (3). It follows that the
observed g-values in table 8 place a relatively rigid constraint on the form of the
wavefunction and on the value o f , q - E ~ . The sensitivity of the g-values to
q - % is shown in figure 11, which is computed with the assumption that the
remaining parameters take the values given in fit 2 of table 10. The important
feature of this figure is that the crossing point occurs when [g, 1= [g-[ -~ 1.50
L~
T a b l e 10. Calculated and observed magnetic properties of electronic states in Cs2NpO2CI,.
Calculated Observed
Fit I Fit I I
Symmetry Energy f(~z) f(~x,v) Energy f(tzz) f(l~x,v) S y m m e t r y Energy f(tzz) f(l~x,y)
D4h*(Doon) / c m -1 g IJ g± /10 -s /lO-S / cm-x gll g± / 10-8 /10 -8 D ' a n label / c m -x g, g± /10 -8 /10 -s
FT-(Az/2u 0.0 1.38 1.50 0.0 1.38 1.53 -- -- FT- 0 0.0 1.38 •.32 --
+ O5/2u)
FT-(A3/2u 820-8 0.96 1.48 25.7 0.0 1301.5 0.89 1.50 39.6 0.0 I ca. 1000 n.o n.o.
+ Osl2u) ¢)
FT-(A5/~u) 6880.4 5.54 0.24 12.9 49.0 6880.4 5.50 0.38 17.8 47.7 F~- II 6880.4 not 35 40
measured
Fe-(OT/z~) 8236-0 7.76 0.00 0.0 0.2 7906.3 7.39 0.05 0-0 0.3 III ca. 7990 not 0 0
measured
1-'e-(H1/zu) 17241.4 0.24 0-25 0.0 173.1 17241.4 0.57 0.79 0.0 166-7 VIII 17241-4 0-6 0.2 0 55 o~
F~-(Ha/2u) 20080.8 3-87 0.21 22.0 38.5 20080.8 3.77 0.34 41.2 32-0 X 20080.8 3.8 0-1 f 8-3
Fe-(Xl/2~) 119351.2 2-0 2.25 45904.4 2.00 2.84 state not observed
Parameters/cm -1
~ 6 - ~¢ -1932.0 -1994.5
•. - ~ ¢ 13003.45 12626.0
E~- ~¢ 114000-0 40000.0
2196.1 2118.15
(B4) 2342"0 3788.9
(Be) 2400"0 3920.0
t > 0 but masked.

f-f transitions in [Np02Cl4] = and [NpO2(N03)3]- 315
(E 6 -E~)/cm-1
- 5000 - 2500 0 2500 5000
z.O , , '
2"0
00
-2.0
i i i
5000
~ >,
0 j / / /~ 3/2 o//~.
o~
o) /
q)sj2u
- 5000
5000 2;00 ; 2;00 sooo

E,>/cm,
Figure 11. The energies of A and q~states, and the g-values of the ground state, as afunction
of e~-Eo in Cs2NpO2C1,.
a result in good agreement with the experimental observations in table 8. V~ is

the link between q~a/2 and A3/2. As V4 decreases the range of values of Ee-e o
defining the mixed r6gime decreases, but the crossing point is quite insensitive to
the variation. This means that the g-values closely determine ee-E4 as
- 1 9 6 0 + 50 cm -1 and are virtually independent of the other parameters.
The appropriate perturbation matrix was diagonalized with the object of
fitting g rE= + 1.38 in the ground state and also the energies of the three optical
transitions for which the origin bands are actually observed. Two sets of
energies were calculated with two fixed values of E~-%, the remaining five
parameters being varied to optimize the agreement with the observed energies
and the value of g, in the ground state. The results are shown in table 10, which
also includes the magnetic moments and magnetic dipole transition moments.
Unlike the results for CsNpO2(NO3) 3 the magnetic properties are not very sensitive
to the variations in the parameters shown in table 10. Both fits predict origins
in the regions inferred in §§ 6.3.1. and 6.3.2. The calculated energies of the
level near 1000 cm -1 straddle the experimental range 900-1050 cm -1 suggesting
that Ee-e4 lies between the two values chosen for the fitting procedure. The
model is clearly capable of excellent predictions for all of the observable proper-
ties.
7.4. Parameter values

The spin-orbit coupling constants determined here lie between 2212 cm -1 and
2047cm -1. These values agree well with previous determinations for
neptunium, N p ( I I I ) 2070 em -1 [23], Np(IV) 2178 cm -1 [24], Np(V) 2090 cm -~
[25], Np(VI) 2248 cm -1 [19] and for neighbouring actinides.
The axial field parameters are in some cases controversial. E~-c 0 is poorly
determined. %-E~ is given as 15 800 cm -1 [26] or 14 558 cm -1 [19] in the
aquated neptunyl ion. In this work we find % - % ~ 12 800+200 cm -1 for
C%NpO~C14 and ~ 1 4 0 0 0 - + 2 0 0 c m -1 for CsNpO2(NO3) 3. The values of

Es-~4 are agreed to be in the range _+2000 cm -1 [19, 26]. We find e~-~O=
-1963_+31 cm -1 in Cs2NpO2C14 and -1720_+360 cm -1 in CsNpO2(NOs)3.
A comparable value for ~n- E4 has been deduced from the location of the excited
states of C%UO2C1a and CsNpO2(NO3) 3 [3], the range being - 1 5 0 0 cm -1 to
- 2700 cm -1.
The values of (B4) and (Be) in tables 9 and 10 are of a similar magnitude to
the wide range of values attributed to various aetinide species (see, for example,
table 7 of [3]. An interesting comparison can be made with the values derived
from the analogous uranyl compounds. For C%UO~CI4 (32] V413 - 2) = 655 cm -1
[3], while the two parameter sets used here cover the range 355-560 cm -1 for
this quantity in C%NpO2CI 4. For CsUO2(NO3) 3 ( 3 3 [ V 3 1 3 - 3 ) = 3 2 5 0 c m -1
whereas the analogous quantity for CsNpO2(NO3) 3 takes a value in the range
2210-2717 cm -1. It is not clear that the differences between the uranium and
neptunium compounds have real significance, although it is tempting to believe
that they indicate the contraction of the f orbitals toward lanthanide character ;
nevertheless it is encouraging that the ratio of the equatorial field parameters in
the two geometries is similar for both elements.
7.5. Electric dipole intensity

There are obvious detailed features of the spectra of both CsNpO2(NO3) 3 and
Cs2NpOaC14 which need further explanation. For example, CsNpOz(NOz) 3 is
effectively completely dichroic in some transitions, but has features in both
polarizations in other transitions. The vibrations of Cs~NpO~C1a couple in
different ways in the various transitions. In this section we offer a theoretical
model of the intensity mechanism which accounts for the majority of the observa-
tions.
It is assumed that the primary intensity source is within the isolated NpO2 z+
ion. If the ground state wavefunction is written as I~bg'z ~bum Yt), where n and m
signify the number of gerade and ungerade electrons in inner shells, the allowed
one-electron transitions will occur to excited states written as I lfi~-l~t,u ra 7f•'u),
[~g n ~um-1 7IV'g) and [~bg'~ ~bum 7'a). We now examine how the intensity of these
allowed transitions can be introduced into the forbidden ~-f excited states
[~bgn ~bumy'l). This process involves ungerade components of either the static
equatorial field (in the D3n case) or the dynamic perturbation associated with the
internal vibrations. In both cases the perturbation is a one-electron operator and
f-f transitions in [NpOzCl~] = and [NpOg.(NOa)a]- 317
requires that the allowed excited state differs from n m 7 ' 1 5 by only one
electron.
Initially we consider the [~bgn~bum-1 717'g) intensity source. Because
7'1 # 7/this wavefunction differs in more than one orbital from the excited states
of interest and can be dismissed. If the intensity source is [~bgn-1 ~b~,m 71V ' u), it
follows that there can be no intensity unless 7'~ = 7'1 and the allowed transition is
simply ~bg-->7'r If ~bg is interpreted as an oxygen based molecular orbital,
~bg=% or ~rg and, for CsNpO~(NOa)3, 7/=A~5/2u+A'~712u+A"~5/~ where
h > A' ~ A" and the A are the coefficients in the eigenvector.
In Dan the static intensity is introduced by terms in the potential dependent
on Ya+-a(V3u). We require the matrix elements (711V3ul~bg) to be non-zero and
mz
~bg=az/2g+h'Zrl/20. The allowed transitions from these ~bg are ~1/2g~ ~1/~,
mx,y mz rex,it
a1/2g--~Tq/2~, ~r3/~, or, since h" is small, more weakly ~rl/2g~rq/2~ , rr~/2g----~el/2~,
~a/z,. This mechanism correctly predicts the intense perpendicularly polarized
intensity in origins VI(IIl/e, ) and IX(H3/~ ) and explains the absence of appreci-
able electric dipole intensity in the other observed origins.
Vibronic intensity introduced by modes of E' symmetry can be described by a
perturbation with the symmetry properties of Y1+1. If (Tl[ Y1-+1 ]~g)¢0,
mz
~bg= ~a/2g and the intensity is introduced by transitions of the type 7ra/zg--->~ra/~,, or
m~.,~
zra/2g---+al/eu, ~5/2,,. The mechanism therefore predicts that such modes will
appear in the parallel polarization on origin IX and in the perpendicular polariza-
tion on origin I. Table 6 and the spectra show that this prediction is totally
inadequate.
E u vibrational modes introduce intensity into C%UO~C14 by a perturbation
which can also be described by YI +1. In this material the ground state is well
describedbyT/=h~/~u+h'~a/~,+~"~/~whereh~-h'>h ". If(),l[Yx-+~[~b~)~0
then ~bg= A~'~/2g+A%r~/~gand the intensity is introduced by transitions of the
mz ~nx,y ~tz~
type 7rl/2g-+~'X/~u, Zq/~g------~al/~g, ~a/Z~ and more weakly by ~'3/2g--Y~':3/2u,
mx,y
7"£3/2g-----+O'x/2u,~5/2u" This mechanism predicts that these modes will appear in
the parallel polarizations only in association with origins V I I I and X and in the
perpendicular polarization with origins I and II. Since these modes are
observed to be generally unpolarized, this mechanism fails to explain the principal
features of the spectrum.
The only remaining intensity source involves the excitation of the f electron
to a gerade orbital. We ignore the inner shell electrons ~bgn ~b,~m. A realistic
choice of the excited gerade orbital requires h ~<2, for example the 6d orbitals.
The route by which the intensity is introduced can be represented by a procedure
of the type described in Part I I I [3]. A primary intensity source is mixed either
with the ground state or with the excited state by an ungerade perturbation.
Intensity is thereby introduced into a limited subset of basis states and the
observed intensities can, in principle, be estimated from a knowledge of the
eigenvectors in the ground state and the excited states. The various intensity
sources and coupled states are shown in figures 12 and 13 which also show the
principal mechanisms for communicating this intensity to other observed states.
It transpires that it is impracticable to calculate the intensity directly from the
eigenvectors (a) because the relative energies of the source states are unknown
and (b) in the presence of the strong axial interaction of the oxygen atoms it is
Static Mechanisms Vibrational Mecl'~ar~isms
V3u links i n t e n s i t y source to A j~ m o d e s E ~ modes

Coupled s t a t e I Ground state
Parallel P o l a r i s a t ~on
Ground
& 5J2°046%) I ~5/2u(76 9"1,) @?12u(85"1.) A5/2u(lt, 6"/,) 5¢2u(146%) ~512u(14 6%)
State ~
Intensity
I \/ r I
A 5/2g i 1/2g ~ l12g 512g
Source
I I
Coupled Iql/2u I ~"1/2u I7 l/2u A 51~zu ( ~7/2u F]312u
State
L~
Dertved TI/2u ~512u RV2u ¢5~2u ¢712u nly2u ~5¢2u 5/2u l/2u &312u
Intensity LS LS O
¢712u A512u ~112u
Perpendicular PolartsatLon
0~
Ground
~)5.(76-9"1.)/%5.(146"/,)@7z (8 5"1,) / -- Izu sd,, 6",.~ %~6 5"1.1
State ~i5d76~'1.~
I ~° I ~° 12° °%~"~'1" °'%`~'''' ~ '''~'''
X/ r t t,,,. i
Intensity aaI
Source
Coupled u
I 1312 t ~2u R 112u I I'] 112u F] 312u A 3/2u ][ 112u iq112u ¢~512u A512u ~l12u {]312u @7/2u
State LS LS
Derived ~2u F1312u ~) 512u @ 512u rl 1~u @7/2u
Intensity ¢
®512u 0712u ~712u
Figure 12. Static and vibronic electric dipole intensity mechanisms in CsNpO~(NO3)a. For a particular excited state only the route involving
the least number of sequential perturbations is shown.
f-f transitions in [NpOzCl,] = and [NpO~(N03)3]- 319
not possible to express all of the transition moments and perturbation matrix
elements in terms of sufficiently few reduced matrix elements for a satisfactory
analysis to be completed. Nevertheless, where the intensity is derived by a
unique route its magnitude can be estimated by the number and size of the
sequential perturbations in that route. However, if the intensity is not uniquely
derived it is dependent on the relative magnitude and phase of the various con-
tributions and cannot be reliably estimated by our procedure.
Figure 12 shows the position for CsNpO2(NOa) 3 where both static and
vibronic mechanisms are relevant. The ground state eigenvector is dominated
by the 495/~(Doon) state and the most weight should therefore be given to routes
originating on this component. This component offers no route to an observed
directly coupled state for intensity in the parallel polarization and it is this gross
feature which leads to the strong dichroism of the spectra.

The spectra in figures 1, 3, 5 and 6 show that the static intensity is usually
dominant and that it is found primarily in the strong polarization on origins VI
and IX with, respectively, II1/2~, and II3/2u(D~l,) symmetry. Origins I and II
have F7(D3h) symmetry and are formally forbidden in both polarizations, whilst
origin IX has F9(D3h) symmetry and is formally forbidden in the parallel polariza-
tion. Figure 12 shows that in this polarization the H1/2u state (origin VI) can
draw its intensity from four routes, three of which originate from minor com-
ponents of the ground state. The remaining route, via the high energy E1/2u
coupled state, is also relatively ineffective. It is possible to show that the phases
of the contributions in these routes differ, the consequent cancellation further
reducing the overall intensity. These factors may well account for the weakness
of the transition. By contrast strong perpendicular intensity is predicted for both
the H1/2u and H3/~u states since they obtain static intensity directly from the
495/2, component of the ground state. However, the multiplicity of routes with
differing phases to these states does not allow their intensities to be compared.
The vibronic mechanism in the parallel polarization appears predominantly
through E' modes on origin IX(II3/2,,) and more weakly on origin II(@7/2~).
This situation is well described in figure 12, where these are shown to be the only
states directly coupled to the intensity source. These routes originate from a
minority component of the ground state. An equivalent situation would be
predicted for these two origins from figure 12. In addition, the majority ground
state component 495/2,` is anticipated to provide strong perpendicular intensity in
the H1/2,, state (origin VI). This is exactly what is observed.
In the spectrum of Cs2NpO2C1 ~ (figures 8, 9, 10) the vibronic structure is
dominated by E,, modes. The intensity appears in both polarizations almost
equally and is strong on origin V I I I and medium on origins II and X. This
pattern of intensity is identical to that found in the perpendicular polarization of
CsNpO2(NO3) a. Comparison of figures 12 and 13 shows that I~l/2u , H3/2uand
A5/2,, receive their intensity by similar mechanisms in both compounds. In
figure 13 in the parallel polarization the E,, modes introduce intensity from a
majority ground state component directly into H1/2,, whereas the intensity in
H3/z,, requires a further perturbation step and the intensity in Asia,, is derived
from the minority component of the ground state. As a result H~/2,, is predicted
to have strong intensity in its E,, modes in the parallel polarization whereas
As/2u and II3/2, are predicted to have less intensity in these modes. This again
agrees well with experimental results.
M.P. M
Parallel Polarisation
A2u modes (Y10) Blu modes (Y]) E u modes (YI 1)

Ground State A3/2u (4 2.9"/,) ~ 5/2u(l3.2 "1.)
1 / i3,2j,z.9",.~ /~s,2j,3.~',.~
Intensity Source /k 312g A 512g 312g /A~g --/k 512g
i 5t2g
Coupled State
I
A3/2u )" 1/2u )- 1/2u r~ 112u ( ) ~2u ~ 7/2u 17 312u
Derived /k 512u l-I 3/2u A 312u ~512u );'112u (~?/2u ,,~2u I 2u R1/2u(~512u A312u
Intensity )~I Ls
O712u " L~ 3y 2u O
Perpendicular Polar~sat ion
p..°
Ground State 0~
Intensity Source
I t
FIb2g ~ :)~2g I-I3~2g
/
2, 2
Coupled State n 1/2u ~ 3/2u n312u @EY2u E1/2u Rll2u (~712u
LS LS
Derived ~312u ~512u A 3~ u A 512u n 312u I-1 312u
Intensity LS
\
~)512u
Figure 13. Vibronic electric dipole intensity mechanisms in Cs2NpO2C14. For a particular excited state only the route involving the least number
of sequential perturbations is shown.
f-f transitions in [Np02CI4] = and [NpOz(N03)3]- 321
To summarize, the striking observation of strong parallel polarized intensity

in Cs~NpO~CI 4 and its absence in the equivalent excited states of CsNpO~(NO3)3,
is simply explicable in terms of the composition of the ground state, the crucial
element being the inclusion of the A3/2,, parent state in Cs2NpOaCl 4 which is a
direct consequence of the tetragonal equatorial field.
8. CONCLUSION
8.1. Comparison with previous work
The most comprehensive single crystal spectroscopy of the neptunyl ion is due
to Leung and Wong [21, 27]. For CsNpO~(NO3)3 a and rr polarized spectra at
4.2 K have been reported [21] between 5000 cm -1 and 22 000 cm -1. Four f-f
type transitions are assigned by these authors and correspond well to origins I, II,
VI and IX observed in this work. The polarization of features above origin IX
appears to be incorrect. An extra origin was assigned at 21 020.6 cm -t in the
polarization. We can find no comparable feature in the ~ polarization but do
observe a strong feature at this frequency in the 7r polarization, which we assign
to the E" UO~ rocking mode on origin IX. The g-values in [21] are of lower
precision that those reported here and in a number of cases considerably lower in
magnitude. The error in the values is probably due to the difficulty of aligning
the magnetic field with the neptunyl axis since the crystalline habit makes the
principal crystal axis difficult to recognize. Our measurements were made on a
uniaxial (~) section where no directional ambiguity is possible. There is no
attempt in [21] to assign the symmetries of the excited states.
An outline of the low temperature spectrum of CsaNpO~Cl~ is given by
Gorskhov et al. [16] but there is insufficient detail to allow a comparison with the
spectra reported here. A more comprehensive study is due to Staffsudd et al.
[27]. Unfortunately these workers used a twinned crystal and many of the data
were collected under low resolution at 77 K. Only the excited state near
6880 cm -x is attributed to an f-[ transition and only five transitions were
positively identified in all. There is a good general resemblance to the spectra
shown in § 6.3.
The model used in this work closely resembles that of Eisenstein and Pryce
[19, 22]. Their interpretation is based on the ESR data of Bleaney et al. [18], the
magnetic susceptibility data of Gruen and Hutchinson [28] and the solution
absorption spectra [29]. The solution spectra proved difficult to analyse
unambiguously and a number of options were considered in [19]. In the
aqueous system two bands near 20 000 cm -1 are attributed to the l-Ii/~u and
II3/2u excited states. The low energy states are placed in the order ~s/2~, (ground
state) < A3/2u< As/e~< ~7/2u and the energies give - 1700 cm -1 < c~-EO
< - 600 cm -1.
An alternative assignment of the aqueous solution has been proposed by
McGlynn and Smith [26], w h o interchange the order of the A5/2,, and (I)7/,u states.
This requires e e - E~~ 1500 cm -1. Whilst these parameters may not be transfer-
able to the crystalline state (there is some uncertainty as to the equatorial field
geometry in water) we prefer the analysis of Eisenstein and Pryce [19]. In
particular we find ee-E~ ~ - 2 0 0 0 cm -x for both our systems and in both cases
qbT/~ lies above As/~u.
M2
Finally we should comment on the interpretation by Leung and Wong [17] of

their E.S.R. data on Cs2NpO~CI 4. Their analysis ignores the equatorial field with
the result that ap or A ground states would be expected to show highly anisotropic
g-values with g ± = 0 (see § 7.3). The non-zero value of g± could only be ex-
plained if II1/~u and ~t/2,, are essentially degenerate and together constitute the
ground state wavefunction [17]. Such an ordering of the f orbitals seems
unreasonable and the data can be easily interpreted if the equatorial field is
propertly taken into account as in § 7.3.
8.2. Discussion
We believe that the spectra reported here have been unambiguously assigned
to particular electronic f - f transitions. The majority of the vibrational structure
is also fully understood both in terms of its frequency and polarization. There
remain a few unassigned or undetected bands in the far infrared whose assignment
could be clarified with the aid of oxygen-18 substitution.
In both CsNpO2(NO3) z and Cs2NpO2CI 4 parameters governing the orbital
energies show them to lie in the order Su < ~ , ~ Flu < au. This order is consistent
with the antibonding properties of the 7% and % orbitals with respect to oxygen.
The antibonding nature of the rru orbitals is confirmed by the drop in the fre-
quency of the N p - O stretching modes and the observation of progression in the
NpO 2 symmetric stretch. The %-E~ separation is about 14 000 cm -1 in
CsNpO2(NO3)3 and 12 800 cm -1 in Cs2NpO2C14 implying more antibonding
character in the former compound. This is consistent with the stronger N p - O
bond in CsNpO2(NOz) 3 as shown by the infrared stretching frequency of
960 cm -1 as compared to 919 cm -1 in C%NpO~CI~. The consistent observation
that the energy of ~ is below that of ~ suggests that the order of these orbitals is
predominantly controlled by the cylindrical component of the equatorial electro-
static field.
The model applied here gives an excellent account of the energies, magnetic
properties, transition moments and electric dipole intensities in the observed
spectra, and in consequence we believe that the parameters of the model can be
accepted with confidence. The parameters vary in a reasonable way between
Cs2NpO2C1 a and CsNpO,(NO3) 3. They provide independent support for the
values of E, - ~¢ and the equatorial field parameters which have been derived from
the spectra of the analogous uranyl compounds.
We wish to thank the Science Research Council for a C.A.S.E. award to

J.O.W.N. and A.E.R.E., Harwell, for an Extra-Mural Research Grant for the
support of some of the work in Oxford. We are indebted to Professor R. J. P.
Williams for access to the Cary 17 instrument.
REFERENCES
[1] DENNING, R. G., SNELLGROVE,T. R., and WOODWARK,D. R., 1976, Molec. Phys., 32,
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[5] DENNING,R. G., SNELLGROVE,T. R., and WOODWARK,D. R., 1975, Molec. Phys., 30,
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[6] WOODWARK,D. R., 1977, D.Phil. Thesis, Oxford.
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[8] DENNING, R. G., 1975, Electronic States o[ Inorganic Compounds: New Experimental
Techniques, edited by P. Day (D. Reidel).
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[10] ALCOCK,N. W., BROWN, D., and ROBERTS,M. (private communication).
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Thirty-two Point Groups (M.I.T. Press).
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Radio Khim., 17, 896.
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[18] BOWERS,K. D., and OWEN, J., 1955, Repo. Prog. Phys., 18, 304.
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Denning 1982

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On: 13 February 2015, At: 14:13

Molecular Physics: An International Journal

The electronic structure of actinyl ions

To link to this article: http://dx.doi.org/10.1080/00268978200101261

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The e l e c t r o n i c structure of actinyl ions

(Received 4 December 1981 ; accepted 3 February 1982)

The polarized single crystal absorption spectra of Cs~U(Np)O2CI4 and

In parts I - I V of this series [1-4] a model of the electronic structure of

molecule. T h e site s y m m e t r y of the uranium atom is Can but discrete UO2CI~=

T h e structure of RbUO2(NO3)3 has been accurately established by neutron

Table 1. Ground state vibrational frequencies of Cs2UO,C14 and CsaNpO2C14.

v~ Alg O-M-O sym.str. 832 802

Table 2. Ground state vibrational frequencies of CsUO~(NO3)3 and CsNpO2(NO3)3.

(a) Internal actinyl modes

Vs A' x symmetric stretch 875 860

C2v nitrate mode Dab symmetry in MO2(NOn)3- CsUOa(NO,)3 CsNpO2(NO3),

vl (al) At', E' 1510 1504, 1510

T h e infrared spectra of both pure n e p t u n i u m c o m p o u n d s were recorded in

Table 3. Selection rules for Cs2NpO,C14 in D4n*.

Symmetry Transition moments for Vibrations allowing components of

r a = rE (l~.., l~y), tx. Alu, A2u, Eu Alu, A2u, Blu, B2u, Eu

In § 3 we have indicated that the site symmetry of Np in CsNpO2(NO3) a is

Table 4. Transition moments for electronic transitions in CsNpO3(NO3)3.

Symmetry Excited state

I'~( + 1 / 2 ) -- 5 / 2 , + 7 / 2 l~z t*+ rnz m+ i~_ m_

Symmetry of excited state (Dan*) F~ Fs Fa

6.500 6.600 6,700

F i g u r e 1. A b s o r p t i o n spectra of C s N p O z ( N O z ) z at 4.2 K. U p p e r p o r t i o n ~ polarization,

6. ANALYSISOF THE SPECTRA

bonding orbitals to non-bonding f orbitals on uranium [3]. The change in the

Figure 3. Absorption spectra o/c CsNpO2(NOa)3 at 4"2 K. Upper portion e~polarization,

6.2.2. Region from 9400 cm -1 to 13 000 cm 4 ; origin 11, 9420.2 cm -1

identification of the transitions is simplified by the temperature dependence, also

6.2.3. Region from 13 000 cm - t to 21 700 cm -1 ; origin V I , 17 843.6 cm -x ;

The nature of the progressions in this region is complicated by a phenomenon

150 IX* Uranyl

6.2.4. Low [requency vibrational structure

are deformations of the Np(NOa) a framework and are presumed to be lower in

Table 6. Low frequency nitrate modes coupled to electronic transitions in CsNpO2(NOz)3.

Mode NpO~ rock Np(NO3)asym. Np(NO3)sym. Np(NOs)sym. Np(NO3)asym. NpO~bend

Origin I/cm -1 207-2 224.5 -- 232 -- 259.1t

t There is an unexplained feature at 285.4 cm -1 on this origin.

Table 7. Summary of observed electronic excited states in CsNpO2(NO3)a.

Origin Energy/cm -1 Symmetry gu g±

Ground State 0 F7 3.34+ 0-07 0.2 + 0-2

isotopic substitution, and a third m o d e at 219 cm -1 which has a smaller sensitivity

6.2.5. Summary of the electronic states of CsNp(NO3)z

6.3.2. Region between 4000cm -1 and 13200cm-1; origin II, 6880.4cm-1;

600 800 1000 1200 1400 1600 1800

Figure 7. Polarized single crystal absorption spectra at 4.2 K of Cs~UO~CI4, u p p e r two

7.0 72 74 76 ?8 8.0 8.2 84 8-6 8-8

Figure 8. Polarized single crystal absorption spectra of C%NpOzC14 at 4.2 K. Upper

T a b l e 1 shows that the low frequency m o d e s of C%NpO2CI 4 in the g r o u n d

Figure 9. Polarized single crystal absorption spectra of C%NpO~CI4 at 4.2 K. Upper

6.3.3. Region from 13 200 cm -x to 21 250 cm -1 ; origin V I I I , 17241-4 cm-1 ;

765.6 cm -1 is very comparable with the intervals on origin V I I I . The structure

/~--- ]~ax-]- ~L . ~-'}- ~req. (1)

Table 8. Summary of observed electronic excited states in Cs2NpO2C1,.

Origin Energy/cm-1 Symmetry gm g-

Ground State 0 F 7- 1.38 + 0.07 1-32 _+0.02

Va= ,~0~eq[ ~ " \(~-"1835~1/2