Photoluminescence and Optical Absorption of Cs2NaScF6:Cr3+

L. P. Sosmana,*, R.J. M. da Fonsecaa , A. Dias Tavares Jr.a, M. K. K. Nakaemab

a
Instituto de Física, Universidade do Estado do Rio de Janeiro, 20559-900, Rio de Janeiro,

RJ, Brazil
b
IFGW-DFESCM, Universidade Estadual de Campinas, Campinas, SP, Brazil

Abstract

In this work we have studied the photoluminescence and optical absorption of

Cs2NaScF6:Cr3+ single crystals. The 2 K, 77 K and room temperature near-infrared

luminescence spectra of Cr3+-centres are associated with 4T2 ( 4F)  4A2 ( 4F) transition

accompanied by a well-defined vibrational structure. The 2 K emission broad band is

described in terms of normal modes of the octahedral complex [CrF 6]3-. The lifetime

luminescence band at room and low temperature are measured and the Racah and crystal-

field parameters are calculated. The obtained results are similar to those previously

reported in other chromium doped elpasolites in octahedral sites.

PACS Codes: 78.55.-m; 78.55.Hx

Keywords: Fluorides; Transition metal ion ; Photoluminescence

*Corresponding author: Lilian Pantoja Sosman, IF-UERJ, Rua São Francisco Xavier 524,

sala 3030-D, Rio de Janeiro, RJ, CEP 20559-900, FAX 55 21 2587-7447, E-mail address:

sosman@uerj.br

1
1.Introduction

There is renewed interest in solid state optical materials that emit in the visible and

near infrared spectral region [1-7]. These transitions metal ions doped materials have been

studied due to their inherent tunability and possible applications such as signal

transmission, display devices, information storage or tunable laser materials [8,9].

Laser oscillation has been observed in the 3d n configurations, mainly several Cr3+-

doped materials has been exhaustively studied, because the Cr 3+ ion has strong visible

absorption and emission bands when incorporated into the octahedrally coordinated sites of

host materials. For example, much effort has been directed for alexandrite (BeAl2O4:Cr3+)

researching. Its dominant emission at room temperature is 4T2 ( 4F)  4A2 and its broad

tunable band presents a high quantum efficiency which is a very attractive laser property.

The unfilled 3d electronics shell of the Cr3+ ion has a number of low-lying energy

levels, among which optical transitions can occur generating luminescent emission. As the

3d electrons are outside of ion core, they interact strongly with nearby ions electric field

and therefore transition metal ions optical properties are directly affected by static and

dynamic properties of their environments. Both sharp transitions and broad emission bands

can occur at low temperature in the optical 3d ions spectra. Sharp transitions occur between

levels which do not depend on crystal field intensity. In Cr3+-fluoride samples these lines

are associated with transitions between purely electronic states, the zero-phonon lines.

These sharp lines are accompanied by vibrational sidebands which are observed in

2
luminescence at energies lower than the energy of purely electronic line and on the high-

energy side of the zero-phonon line in absorption spectra.

The broad bands are attributed to transitions between electronic states derived from

crystal field orbitals which present different dependences on crystal field strength. Level

energy separations are very sensitive to Dq parameter value and their transitions are

characterized by large values of the Huang-Rhys parameter [10]. These broad bands have a

great interest for tunable materials at room temperature. However the electron-phonon

coupling enhance non-radiative decay processes leading to a decrease in the luminescence

quantum yield. This fact becomes interesting to choose materials having phonon

frequencies much less than the energy gap between two adjacent transition levels in the

crystal, because in principle multi-phonon transitions give lines with small intensities [11].

The fluoride compounds present cut-off frequency phonons (maximum phonon energy)

lower than 600 cm-1 [2,10,12,13] and several studies on fluorides doped with transition

metal ions have been reported in the literature [14-21]. These materials present long upper-

state lifetimes, which is very interesting for using them as efficient amplifying media,

moreover the broad red absorption bands allow the direct diode pumping. Therefore the

aim of this work is the optical characterization of fluoride Cs 2NaScF6:Cr3+ through

luminescence and absorption techniques in order to verify a future application as a tunable

material.

The fluoride elpasolite Cs2NaScF6 belongs to group described as a class of A 2BMX6

materials, where A and B are monovalent alkali cations, M is a trivalent cation and X is a

monovalent anion [22]. In previous paper [23] the analogous system Cs 2NaAlF6 was solved

by both single crystal neutron and X-ray diffraction measurements. The Cs2NaAlF6:Cr3+

crystallizes as a hexagonal structure with R3m symmetry. In the hexagonal elpasolite the

3
trivalent cations are ordered and octahedrally surrounded by F anions. Units of MF6 linked

by faces to two octahedrons of BF6 characterize one site (I). The other site (II) is similar to

site I except that the octahedrons are linked by corners [22,23]. Additional X-ray and

neutron scattering experiments are in progress in order to investigate site symmetry,

coordination geometry and structural changes in Cs2NaScF6:Cr3+.

The optical results achieved in this work indicate that Cr3+ ions enter in octahedral

site replacing substitutionally the Sc3+ ions. We assign the energy levels of chromium ion in

host material from the phase-resolved emission and absorption spectra both measured at

room and low temperatures. Phase-resolved emission measurements performed in this

sample were not able to resolve the emission bands, which is consistent with assumption

that the Cr3+ ions are occupying only kind of site. From the observed spectra we have

calculated the crystal-field parameter Dq and Racah parameters B and C and established the

crystal field strength of Cr3+ ion.

2.Experimental details

The 2 K photoluminescence experiments were performed using a He-cryostat and

those at 77 K were done with an immersion cryostat. The exciting source was a cw 514.5

nm line from Coherent Radiation Ar-ion laser model 52. The excitation intensity was

switched on and off at a reference frequency using a SR 540 variable speed chopper (qual é

a marca???). The sample emission modulated at same chopper frequency (precisa dizer

isso???) was analysed with an Spex model 1870 spectrometer. A liquid N2 cooled RCA S1

photo-multiplier coupled to a SR 530 lock-in detected the optical signals at reference

frequency. The absorption measurements were achieved with a CAM SPEC M 330

4
spectrometer. Both emission and absorption measurements were corrected for the response

of the monochromator and detection system.

The utilized samples are Cs2NaScF6:Cr3+ single crystals grown by the hydrothermal

method [24] with 1.0 % of Cr3+ ion as impurity. The fluorides were synthesized by a direct

temperature-gradient method as a result of the reaction of aqueous solutions of CsF (30-35

mol %) and NaF. The mole ratio CsF/NaF changed from 4.8 to 5.2 with appropriate oxide

mixtures of Sc2O3 and Cr2O3 (99.995% pure) at a temperature about 750 K, a temperature

gradient of about 2 K/cm and pressures of 100-150 Mpa. The substitution of oxigen by

fluorine in oxides is easy due to the similar size of the O 2- and F- anions. The referred

structures for which the substitution can occur are rutile, perovskites and garnet, for

example [25]. For hydrothermal experiments, autoclaves with copper liners having a

volume of about 40 cm3 were utilized. Under these conditions, spontaneously nucleated

crystals up to 0.5 cm3 in size were grown in the upper region of the autoclave. The obtained

crystal phase homogeneity and the possible distortions of crystal lattice were tested by the

X-ray powder diffraction method. Considering that the most important factors for

substitution are the ionic radius (rSc3+ = 0.73 Å and rCr3+ = 0.615 Å) and the valence which

is the same for the Ga and Cr ions, we can argue that the Cr 3+ ions enter in host replacing

substitutionally the Sc3+ ions.

3.Results and Discussion

Figure 1 presents the Cs2NaScF6 photoluminescence spectra of 1.0 % Cr doped at

room temperature (a) and 77 K (b). The optical data were analyzed from the matrices of

Coulomb interaction for the 3d 3 configuration given by Tanabe and Sugano [26].

5
 The emission bands are identified as the phonon assisted 4
T2 (4F)  4A2 ( 4F)

transition of forbidden d-d crystal field levels of Cr3+ ions in octahedral fluoride sites.

Since the 4T2 state has a t22e configuration and 4A2 state has t23 configuration, 4T2 - 4A2

transition is broad. The relaxation process at room temperature originates a emission band

at 12626 cm-1 observed in Fig. 1(a). In this temperature, the luminescence lifetime

measured through the phase-sensitive detection was 117 s. Since it is not possible to

verify two different sites occupation by Cr3+ ions at room temperature, we assume this

decay time as an average value. The 77 K emission spectrum, Figure 1 (b), exhibits two

intense peaks at 13055 cm-1 and 12658 cm-1 and weaker emissions constituting a very rich

structure. For this emission the measured lifetime with phase-shift method was 414 s.

Similar energy position and band shape and also the measured lifetimes, which differ by a

only a factor 4, leads to the assignment that room temperature spectrum has the a same

origin of the low temperature spectrum, the 4T2 level. The room temperature quantum

efficiency can be obtained from  = (room temperature)/(low temperature) [1]. Assuming

that temperature quenching is only due to non-radiative decay and a quantum efficiency of

100 % at low temperatures, we can estimate a Cr 3+ emission quantum efficiency of about

0.3 at room temperature. In other closely related systems, such as Cs2NaAlF6:Cr3+ and

Cs2NaGaF6:Cr3+, the room temperature quantum efficiency is about 0.4 and 0.3,

respectively [23,27]. In according with results presented in literature [28], the radiationless

decay is more pronounced when the dopant ion enters in the host replacing substitutionally

larger ions. The ionic radius of dopant and host ions are rCr3+ = 0.615 Å, rSc3+ = 0.73 Å, rGa3+

= 0.62 Å and rAl3+ = 0.53 Å. Then, it is expected a higher room temperature luminescence

quantum efficiency for Cs2NaAlF6:Cr3+ and Cs2NaGaF6:Cr3+ than for Cs2NaScF6:Cr3+.

6
However, the efficiency is about the same for the Al, Ga and Sc materials. But decay times

are determined with accuracy of about 10%, an expected value for phase-shift method.

This fact can be explain the similar quantum efficiency values for the different samples.

The complete 2 K Cs2NaScF6 with 1.0 % Cr3+ luminescence spectrum is shown in

Fig. 2. The low temperature 4T2 (4F)  4A2 ( 4F) emission exhibit a very rich fine structure,

superposed into a broad vibronic band that extends from 13875 cm-1 to 11248 cm-1. The

luminescence spectrum has been analyzed in terms of the normal modes of vibration of

[CrF6]3- octahedral complex. This analysis is made by analogy with the similar Cr3+-doped

K2NaScF6 [2,17-19] that presents matchable luminescence spectra. In this measurement we

have used the phase-shift method in order to distinguish the transitions originated at non-

equivalent sites of occupation for Cr3+. When we have chosen the appropriated phase in the

lock-in amplifier that eliminates the line at 13875 cm-1 no lines remain in the spectrum,

showing all those lines presented closed lifetimes. This result shows that Cr3+ ions occupy

undistinguished octahedral sites in the host structure. The luminescence lifetime measured

for this transition is 443 s. This value is close to those obtained in previous papers [17-

19,29,30] for similar systems, where there is not radiative recombination. Then, the

measurements performed in this work indicate that the luminescence originates from

isolated impurity centers. The Huang-Rhys factor S is calculated from e -S = IZPL/I [1],

where I and IZPL are the integrated intensity in the broadband and zero-phonon line,

respectively. This parameter is 3,6 for the sample, compatible with a 4T2 (4F)  4A2 ( 4F)

assignment, for which Huang-Rhys factor can be bigger than 1. The S value is according

with the similar K2NaScF6:Cr3+ system [17,31].

7
 In Cs2NaScF6 :Cr3+ the dopant ion wave functions overlap with those of the six F -

nearly surrounding neighbors. This overlapping is represented, in the simplest form, by a

wave function that can be written as the combination of Cr3+ plus F-contributions, which

form the molecular orbital for the [CrF 6]3- octahedral complex. The transition metal central

ion uses 3d, 4s and 4p atomic orbitals. This molecular orbital is formed from Cr 3+ atomic

orbital 3d (t2g, eg), 4s (a1g), 4p (t1u) and F- group orbital 2p (a1g, t1u,, eg) , 2p (t1u, t2g,, t2u, t1g).

The normal vibrations modes of [CrF6]3- octahedral complex are given by vib = a1g, + eg

+ 2t1u + t2g + t2u [32].

In Fig. 2 we can observe the zero-phonon line (line 1) and vibrational lines

associated with 4T2 (4F)  4A2 ( 4F) transition. In this spectrum, the signal phase was

adjusted to obtain the maximum intensity for line 1, located at 13875 cm-1. The energy

stares of Cr3+ ion have the same parity. When the ion is in site with symmetry inversion,

the allowed electronic transitions are of magnetic dipole with weak intensity, although the

vibronic lines in the side band of zero-phonon line are mainly induced by odd vibrations

t1u and t2u which destroy symmetry inversion generating intense electronic dipole lines. The

more intense sidebands (lines 10 and 11) appear associated with electric dipole vibronic

transition, produced by odd-parity internal vibration of the complex [CrF6]3-, i.e., t1u ()

mode. By considering these observations for Cs2NaScF6:Cr3+, the four strong vibronic

peaks situated at 13651 (line 4), 13573 (line 5), 13470 (line 6) and 13369 cm -1 (line 7) can

be assigned as t2u(), t1u(), eg() and a1g() modes, respectively. The t2u() mode

corresponds to a nonbonding orbital and must have the lowest difference of energy among

all those possible. Moreover, the  orbitals are symmetric with respect to rotation around

bond direction while  orbitals do not present this characteristic. So, the energy position of

8
t1u() mode is expected to lie higher than that of t1u() mode, situated at 13291 cm-1 (line 8).

The relatively high intensity of eg() and a1g even modes can reflect the vicinity of 4T2 and
2
E states in Cs2NaScF6:Cr3+. Besides, t2g, eg and a1g are active Jahn-Teller effect modes, that

produce a reduction in ion site symmetry. In this case, the ion can be displaced from the

center of the octahedron [10,33]. This JT effect is more pronounced in E states than in T

states: the eg orbitals are directed towards ligands and are more respondent to non-

equivalency of interactions with the ligands than the t2g orbitals, directed between ligands.

Furthermore, the observation of electric dipole allowed eg() progressions on the odd

vibronic origins (lines 9 and 15) gives other evidence for this assignment. As for eg(), the

position of the mode a1g() is also confirmed by the combination with some others odd

origins (lines 10 and 11). Another interesting fact in this spectrum is the apparent absence

of the t2g() mode. This absence is normal when the introduction of the Cr3+ ions in

Cs2NaScF6 does not cause a great distortion in the Sc sites. Also, as the t2g electrons are

little affected by small changes in their environment, the relative intensities of vibrational

lines related to the transition of these electrons are very low, which can lies beyond the

sensibility of our detection system. Neverthless the occurrence of this mode has been

reported previously in a very similar system, the K2NaScF6:Cr3+, by Raman scattering

measurements [2]. That work describes as K2NaScF6:Cr3+ undergoes a phase transition to a

lower than octahedral symmetry below room temperatures. Thus, the t2g() in

Cs2NaScF6:Cr3+ can be associated, if confirmed by Raman scattering results, with the

shoulder on the low energy side of the t2u line [34]. Additional Raman measurements are in

progress in order to investigate this point. The vibronic modes frequencies, based on the

electronic transition at 13875 cm-1 are arranged in decreasing order and summarized in

9
Table I. In this table, only intense lines in the higher energy positions at 2 K emission

spectrum are identified. The weaker lines are associated to the multi-phonon sidebands.

The absorption spectrum of Cs2NaScF6 doped with 1.0 at. % Cr 3+ at room

temperature is shown in Fig. 3, where band identified as 4A2 ( 4F)  4

T1 ( 4F) has its

barycenter at 22050 cm-1 and lower energy band, identified as 4A2 (4F)  4
T2 (4F)

electronic transition of the Cr3+ center, has its barycenter at 15000 cm -1. The comparison

between energy positions in of the 4T2 ( 4F) - 4A2 (4F) absorption and emission bands leads

to a Stokes shift of 2374 cm-1, a reasonable value for fluoride hosts [35]. From energy

positions of 4
A2  4
T2 ( 4F) transition and Tanabe -Sugano matrices for Cr 3+ (3d 3)

octahedral environment [19], we can extract the cubic field splitting parameter 10Dq. From

the position of the 4A2  T1( 4F) absorption transition we can estimate the Racah parameter

B. In free ions the Racah parameters provide the term associated with Coulomb repulsion of

electrons but, in crystals, these parameters are influenced by ligand anions and metal

cations, indicating a measurement of bond covalency. Using band maximum energies at

room temperature absorption spectrum and equations are given in literature [33], the crystal

field strength Dq and Racah parameter B calculated for this sample are 1500 cm -1 and 754

cm-1, respectively. This Dq/B value is such that the 4

T2 and 2E states are very close in

energy. The mixture of 4T2 and 2E states cause a greater intensity of the eg and a1g modes

[10]. The features in the absorption spectrum are not identified. To explain this point, low

temperature absorption measurements are necessary, which lies beyond our present

instrument capabilities.

10
4.Conclusions

In this paper, the Cs2NaScF6 compound with 1.0 at % of Cr3+ has been investigated

by photoluminescence and optical absorption spectroscopies. The existence of only one

Cr3+ occupation site is confirmed by time resolved emission and optical absorption

measurements at 300, 77 and 2 K. The photoluminescence spectra show broad vibronic

bands in visible and near infrared spectral regions. The emission bands at room

temperature, 77 K and 2 K are identified as 4T2 ( 4F)  4A2 ( 4F) transition of Cr3+ ions in

octahedral sites. At room temperature, the luminescence lifetime measured through the

phase-sensitive detection was 117 s. The 2 K zero-phonon line is located at 13875 cm -1

and the luminescence lifetime measured for this transition was 443 s. The 4
A2 ( 4F) 

4
T2 ( 4F) absorption is favorable to the inverse transition even if the 4A2 ( 4F)  4T1 ( 4F)

absorption band is more intense. This fact is not significant because the 4
T1 ( 4F) and
4
T2 ( 4F) levels are not sufficiently near to permit reciprocal interaction.

The d-d transitions of Cr3+ ions are parity forbidden and the crystal field parameter

Dq obtained from optical spectra indicates that the impurity ion is situated in octahedrally

coordinated sites. Consequently, the observed transitions in Cs2NaScF6 :Cr3+ presents low

probability although an intense photoluminescence has been observed. The 2 K

measurements eliminate the majority of the vibrational modes. We have analyzed the

vibrational spectrum in terms of normal modes of the octahedral complex [CrF 6]3-. This

analysis leaded to the conclusion that the 4T2 ( 4F) excited state is displaced along the eg

and a1g coordinates. This state distortion is analogous to that observed earlier in other

fluoride compounds doped with Cr3+ ions and attributed to Cr3+ ions in sites octahedrally

11
coordinated by anions [34,35]. Based on these results, we believe that the Cr3+ ions in

Cs2NaScF6 substitute the Sc ions in octahedral sites. Additional X-ray, Raman and neutron

scattering experiments are in progress in order to investigate site symmetry, coordination

geometry and structural changes in Cs2NaScF6:Cr3+.

Acknowledgements

The authors are grateful to N. M. Khaidukov from the Institute of General and Inorganic

Chemistry, Moscow, Russia, for providing the single crystal materials, to F. Iikawa (IFGW-

UNICAMP) and A. S. Luna (IQ-UERJ) for their assistance with PL and absorption

measurements. This work was supported by FAPERJ, FINEP and CNPq.

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14
FIGURE CAPTIONS

Figure 1 – The photoluminescence spectra of Cs2NaScF6 doped with 1.0 at % Cr3+ at (a)

room temperature and (b) 77 K.

Figure 2 - The complete photoluminescence spectrum of Cs 2NaScF6 doped with 1.0 at %

Cr3+ at 2 K.

Figure 3 – Absorbance of Cs2NaScF6 doped with 1.0 at % Cr3+ at room temperature.

15
Table I. Assignment of the labeled peaks in the emission spectrum at 2 K of the
Cs2NaScF6:Cr3+. The peak energy is relative to that zero-phonon line.

Cs2NaScF6:Cr3+
_____________________________________________

Line E (cm-1) Assignment

_____________________________________________
1 0 Zero-phonon line
2 78 host
3 162 host
4 224 t2u ()
5 302 t1u ()
6 405 eg ()
7 506 a1g ()
8 584 t1u ()
9 626 t2u () + eg ()
10 724 t2u () + a1g ()
11 808 t2u () + a1g () + 78
12 911 eg () + a1g ()
13 1009 2 a1g ()
14 1129 a1g () + t2u () + eg ()
15 1223 t2u () + 2 a1g ()
16 1315 t1u ()
17 1417 2 a1g () + eg ()
18 1524 3a1g ()
19 1631 2 a1g () + t2u () + eg ()
20 1719 2 a1g () + t1u () + eg ()
__________________________________________________

16
Figure 1

17
Figure 2

18
Figure 3

19