1. Stabilizing several anions (F, O, OH, S) in the vicinity
of transition metals or rare earths
to tune the electronic properties
of new materials
Alain Demourgues
CNRS, Université de Bordeaux, ICMCB, UPR9048, F Pessac, France
GDR MEETICC
Matériaux, Etats ElecTronIques et Couplages non-Conventionnels
28-31 Mars 2017, AEROCAMPUS, Latresne(33)

2. The anions Xp- E (q) =  q +  q2 Mulliken-Jaffé (1935 – 1963)
(q) = E(q)/q =  + 2 q : Electronegativity
= 2E(q)/2q = 2 : Hardness= 1/Polarizability
(Pearson)
The anions Xp-
+ electronegative
(q)
S2-
N3-
Cl-
O2- F-
H OH-
* (Green apatites) H- + O2-  2e- + OH-
Ca5(PO4)3(F, OH, H) 
S2-
N3-
Cl-
O2- F-
+ hard
+ polarizable
* K. Hayashi and H. Hosono, J. Phys. Chem. Chem. Phys, 2016, 18, 323,

4. Hard-Soft Acid-Base (HSAB) theory
Ralph Pearson (1960)
Energy
H+(1s0), Ti4+(3d0),
K+, Ba2+, La3+
Hard acid :
Soft acid :
Fe2+(3d6), Cu+(3d10)
Soft base :
H-(1s2), S2-, I-,
SO42-, CO32-
Hard base :
F-, O2-, OH-, Cl-, NH3
Hard-Hard or Soft-Soft AB react faster leading to stronger bonds !

5. F Fluorine, a super-halogen ! The anomolous properties of Fluorine
Bond-Dissociation Energy (kJ.mol-1)
CH3X HX X2 F Cl Br I
300
Only for X2
240
160 4 6 F-
Fluorine is small in size and its supported charge is too high !

6. S2- The M-X chemical bonding and the effect of mixed anions
Mq+ : Partial density of charges and oxydation states
Point group ( Mq+ / Xp- ), anisotropy and networks
Crystal field, Polarization, Covalency
SO42- / PO43-
/ CO32-…?
N3-
Mq+
S2- F-
H+/H-
O2-
A way to tune the ionicity-covalency of the chemical bonding
and consequently the electronic properties !

7. Ti Ce From 2D layers to 3D tunnel networks OH- O2- F- S2- 22 58
Outline
Rare-Earth (Ce) oxy-fluoro-sulfides and Transition Metal (Ti) oxy-hydroxy-fluorides
Composition, Structural features and Energy Gap
From 2D layers to 3D tunnel networks
OH-
O2- F-
Ti4+(J=0)/Ti3+(J=3/2)
S2- Ti
[Ar] 4s23d2
Pauling : 1.4 22
The key role of Electronegativity (),
Charge (q+), Ionic radius (rion) of Mq+
to define local electrical field = (q)/ rion
Ce4+(J=0)/Ce3+(J=5/2)
Point group symmetry (M vs X),
Mixing empty d orbitals with filled ligand p orbitals,
Looking for non-bonding character
Lowering the band gap Ce
[Xe] 6s24f2
Pauling : 1.1 58
Second order Jahn-Teller distortion

8. -La2S3 LaF3 La2O3 175 nm 230 nm 440 nm 2.7 2.1 1.8 abs
The mixed anions systems : absorption k()
and refractive index n()
- Electronegativity  (Polarizability ) : F- > O2- > S2-
-La2S3
LaF3
La2O3
175 nm
230 nm
440 nm
2.7
2.1
1.8
abs
n(400 nm)
- Modulation of the chemical bond : Ln-S/O/F :
Variation of the absorption wavelength and refractive index
- Competitive bonds around metals : anisotropy,
modification of the chemical bonds and electronic properties

9. A new class of compounds : rare earth oxyfluorosulfides
LaSF : abs = 440 nm (Eg = 2.8 eV)
High absorption efficiency and refractive index
UV Absorbers : abs = 400 nm (Eg = 3.1 eV) ??
Modification of rare earth environment
Intergrowth of
How to change the
ionicity of blocks ?
Size +
Charge
Ionic blocks [Ln2F2]4+
Covalent blocks [S2]4-

10. X-Ray and Electron Diffraction
A new class of compounds : rare earth oxyfluorosulfides
Modification of the size (ionicity) of ‘[Ln-O,F]’ blocks : double sulphur sheets
Powder and
Single crystal
X-Ray and Electron Diffraction
analysis
[Ln3OF4]4+
[Ln2AF4]4+
[S2]4-
[S2]4-
2 LnSF + AF2
Ln2AF4S2 (A= Ca, Sr)
2 LnSF + LnOF
Ln3OF3S2
Tetragonal I4/mmm
a  4 Å, c  19 Å
Orthorhombic Pnnm
a  5.6 Å, c  19 Å
A. Demourgues et al. , J. Alloys Comp, 2001, 323,
D. Pauwels, A. Demourgues et al .Solid State Sciences, 2002, 4,

11. Powder X-ray and Neutron Diffraction analysis
A new class of compounds : rare earth oxyfluorosulfides
Modification of the charge (ionicity) of ‘[Ln-O,F]’ blocks : single sulphur sheet
Powder X-ray and Neutron Diffraction analysis
[Ln2O1.5F]2+
[S]2- a c
Ln2O1.5FS
Hexagonal P-3m1
a  4.1 Å, c  6.9 Å
D. Pauwels, A. Demourgues et al .Solid State Sciences, 2002, 4,

12. Rare earth oxyfluorosulfides and optical absorption properties
d(La-O)  2.45 Å  4
d(La-S)  3 Å  3
300
400
500
600
700
800 10 20 30 40 50 60 70 80 90
100
% Reflexion
Wavelength (nm)
La2CaF4S2
LaSF
La3OF3S2
La2SrF4S2
La2O1,5FS
La2O2S
La2O2S =La2O1.5FS
d(La-O)  2.5 Å  4
d(La-S)  3 Å  5
LaSF
La3OF3S2
La2AF4S2
A, Ln
Relaxation of
Sulphur sheets
S-S distances 
Optical band gap 
4f,5d(La)
Number of S atoms 
Optical band gap 
3p(S)
[La(A)-F,O] blocks
A/Ln-F/O bond distances 

13. The Ce valence states in fluorides, oxides and sulfides
J = 5/2
Low crystal field
J = 0
High crystal field
CeIII(4f1)
CeIV (4f0) F2 H2
CeF3
Ce2S3
CeO2
CeSF
CeOF
Ce4O4S3
Ce4+/Ce3+
F- : (Pauling) = 4
Hard base
O2- : (Pauling) = 3.5
Hard base
Ce4O2F2S3 - Ce4O3FS3
S2- : (Pauling) = 2.6
Soft base
High crystal field
High Madelung
Potential VO2-
Low crystal field
Low Madelung
Potential VF-, VS2-
Distorted
Polyhedron [9]
Ce-F = A
Cubic site [8]
Ce-O = 2.34 A
Two tetrahedra
surrounding Ce [8]
Ce-S = A

14. Which strategy to keep the Ce4+ valence state in oxyfluoride ?
From the composition and structural features of Ce compounds
to the optical absorption properties
5 eV
CeO2
Ce(5d)
O(2p)
4f0 Ce4+
3 eV
S(3p)
Ce(5d)
Ce2S3/CeSF
F(2p)
CeF3
4f1 Ce3+
Ce(5d)
F(2p)
2 eV
4f1 Ce3+
7 eV
5 eV
3 eV CTB
Which strategy to keep the Ce4+ valence state in oxyfluoride ?

15. Chemical analysis Ce1-xCaxO2-x-y/2Fy
Ca2+ content
F- rate
The solid solution CeO2 (a = 5.41Å ) - CaF2 (a = 5.46 Å) - CaO
Chemical analysis Ce1-xCaxO2-x-y/2Fy
5,4097 (1)  a (Å)  5,4217 (4)
Ce0,92Ca0,05Na0,03O1,91 Ce0,71Ca0,29O1,59F0.24
Diffuse reflectance %
Wavelength (nm)
% F, Ca  Ionic character of Ce4+-O2- chemical bonding 
F- [4] :
FCa2Ce2 and
FCa3Ce major sites
(19F MAS-NMR)
2p(O)  4f (Ce) Charge Transfer Band energy 
L. Sronek, A.. Demourgues et al. Chem. Mater. , 2007, 19, L. Sronek, A.. Demourgues et al. J. Phys. Chem. C, 2008, 112,

16. Structural relationships with RE TM PN O1-xFx oxypnictides
LaFS = PbFCl = BiOCl
Charge density into Layers ( LaO)+ -Fluorite- and ( FeAs)- -Anti Fluorite-
 e- Transfer : LaO1-xFxFeAs
LaO « réservoir » layer FeAs conducting layer
Takahashi, H. et al. Superconductivity at 43K in iron-based layered compound .LaO1-xFxFeAs. Nature, 2008, 453,
(LaF)2+ layer
(LaO)+ layer
(S)2- layer
(FeAs)- layer
: B.I. Zimmer , W. Jeitschko et al. J. Alloys and Comp, 1995, 229, 238

17. Structural parameters which influence superconducting
properties of REO1-xFxFeAs compounds
Parameters which influence Tc :
Doping with F-
Increasing of electron density into FeAs layers
Application of High Pressure
2D Structure and critical temperature Tc :
Converging to Tetrahedron FeAs4 [Td] Symmetry
Inter layers Fe2As2 distance increasing
Reduction of
cell parameters
Compounds Tc
CaFe1-xCox AsF
22 K
Sr0,8La0,2FeAsF
36 K
Sr0,5Sm0,5FeAsF
56 K 17

18. From rare earth to transition metal :
the Fe2+ (3d6) case stabilized in mixed anions environment
Sr2F2Fe2+2OS2
(Oh) FeO2S4
Sr2Fe2+CuO3Se
[Perovskite layers]
[5] FeO5 +
[AntiFluorite sheets]
[4] CuSe4
[Fluorite blocks]
[Sr2F2]2+ +
[ Anti CuO2 layers]
[Fe2O (S2) ] 2-
P4/nmm
p-type (Cu+)-SC + AFM (TN>300K)
H. Kabbour, L. Cario et al. J.A.C.S, 2008, 130, 8261
D. Berthebaud et al.
Sol. Stat. Sci. 2014, 36,
I4/mmm
SC + 2D Ising AFM (TN<110K)
S=2 AFM checkerboard spin lattice
CaOFe2+S
[Rocksalt blocks]
[6] CaO3S3 +
[Wutzite sheets]
[4] FeOS3
(Td) FeOS3
Polar structure (P63mc),
Magnetodielectric TN=35K
C. Dellacotte et al. Inorg. Chem.
2015, 54,

19. x
(q)
S2-
O2- F-
Polarizability
OH-
Transition Metal (Ti)

20. [F-] >  [O2-] > [OH-]
Ti-based hydroxy-fluorides with ReO3-derived network
and band gap
Ti vacancies
distorted Oh site
Stabilization of CB Ti(3d)
 electronegativity
[F-] >  [O2-] > [OH-]
(ReO3)
Ti0.75 0.25OH1.5F1.5
TiO2
BaTiO3
CB Ti(3d)
CB Ti(3d)
CB Ti(3d)
O [3] Ti-O = Å
CTB
O [2] Ti-O =
2.00 Å
O [2] Ti-OH-F = Å
CTB
CTB eV
3.2 eV
3.4 eV
VB OH(2p)
F(2p)
VB O(2p)
VB O(2p)
A. Demourgues et al. Chem. Mater. 21, 2009,

21. Ordered ReO3 supercell (SG : Pn-3m , a = 7.6177 A) Ti vacancies !
Ti-based hydroxy-fluoride with ReO3-derived network
Electron (SG : Pn-3m)
X Ray, Neutron (Atomic positions)
diffraction investigations c*
002
Ordered ReO3 supercell
(SG : Pn-3m , a = A)
Ti vacancies !
020 b*
[100]
1.90 A
1.95 A
1.90 A
1.95 A
1.90 A
[ Ti2/3 1/3 (OH/F)2 F/OH ]6 [Ti (F/OH)3]2
exp = 2.63 g.cm-3 (theo = 2.70 g.cm-3)
A. Demourgues et al. Chem. Mater. 21, 2009,

22. Structural features of Ti1-(O,OH,F)3 HTB
Ti0.93O0.7OH0.9F1.4, 0.27 H2O (TGA/density)
Pnma, a=7.5581(1) Å, b= 7.322(1) Å, c= (2) Å
Powder XRD Rietveld Refinement
(Cu Kα  = Å)
Powder Neutron Rietveld Refinement
(= Å, SINQ-SWI)
3 TiO2(OH,F)4 distorded octahedra (Neutrons) :
Ti Å F1/F2/O2
Ti Å F1/O3/F3
Ti Å O1/F2/F3- Ti vacancies

23. Energy gap and band diagram of Ti oxy-hydroxy-fluorides (HTB)
Solvothermal route : HTB- Ti0.93 0.07O0.7OH0.9F1.4
(Eg=3.42 eV)
S. F. Matar (DFT calculation)
Aqueous route : HTB-Ti0.8 0.2O0.2OH1.6F1.2
(Eg=3.35 eV)
ReO3- Ti0.75 0.25OH1.5F1.5
(Eg=3.22 eV)
CB Ti(3d)
CTB
OH(F)/Ti  (O2-  )  (Ti)   Oh distortion
O2-   Disorder   main species OH-/F- eV
VB OH(2p)/O(2p)
F(2p)
 Eg  , E/k  (direct transition)

24. V/Mo/W substitution into Ti1-(O,OH,F)3 HTB to tune the O content
and enhance the TM site distortion
Hydrothermal route (TiOCl2 , NH4VO3/(NH4)2MoO4/(NH4)6W12O39, aqueous HF(40%), R= HF/Ti= 1.7,
water as solvent, T=90°C)
x (0-5%)  (a,c,V)  and b  :  Ti and Oh distortion (SOJT) 

25. V/Mo/W substitution into Ti1-(O,OH,F)3 HTB
Structure refinement (Pnma hypothesis)
Unit cell parameters and reliability factors (SG : Pnma)
Undoped
Sol-Gel route
10% V
Aqueous route
10% Mo
10% W
a (Å)
b (Å)
c (Å)
7.5581(1)
7.3922(1)
(5)
7.5589(2)
7.3879(1)
(3)
7.5538(2)
7.3833(5)
12.780(1)
7.5479(3)
7.3827(2)
(8)
Volume (Å3)
(1)
713.89(1)
712.77(1)
710.19(1) Rp
Rwp
Bragg-R
Chi2
22.0
20.8
8.35
5.65
15.6
15.3
7.05
2.16
14.4
12.0
6.70
2.61
14.9
14.1
6.28
4.89
Enhancement of
TM (Ti4+/V5+) site distortion
with shorter bond distances 0%
10% V
10% Mo
10% W
Ti1 → F1
1.87(6)
Ti1 → F2
1.99(5)
Ti1 → O2
1.92(2)
1.76(1)
2.09(2)
1.931(6)
1.87(1)
1.92(1)
1.901(6)
1.79(1)
1.92(1)
1.875(4)
Ti2 → F1
1.93(7)
Ti2 → O3
2.13(3)
Ti2 → F3
2.01(6)
2.04(1)
1.907(5)
1.94(1)
1.95(1)
2.030(7)
2.05(1)
2.03(1)
2.255(8)
1.939(2)

26. 10% Mo 5% Mo Mo substitution into Ti1-(O,OH,F)3 HTB
Clear evidence of Mo5+ by ESR : 3 various sites (Pnma hypothesis)
10% Mo
5% Mo
10%Mo
The Mo5+ sites distribution in 3 various sites varies with the Mo rate
(low Mo content : stabilization in the most distorted octahedra)

27. From Ti-based oxy-hydroxy-fluorides with HTB-derived network
to blue conductive Anatase TiO2:F
The key role of structural/electronic defects :
ReO3 - Ti0.75(OH)1.5F1.5  TiO2 white (500°C-600°C)
HTB - Ti0.93O0.7OH0.9F1.4  TiO2: F blue (500°C-600°C)
TGA under Ar
+ Anatase

28. ESR analysis XPS analysis Blue conductive Anatase TiO2:F
Strong UV and NIR absorption, conduction e- and Ti3+.
ESR analysis
XPS analysis

29. %V  (e-) %Nb  (e-)(2%) then 
Blue conductive Anatase TiO2:F, V/Nb doped
Strong UV and NIR absorption,
%V  (e-)
%Nb  (e-)(2%) then 

30. Blue conductive Anatase TiO2:F, V/Nb doped
conduction e-
(VO)2+ species
(V4+, 3d1, I=7/2)
V-doped TiO2:F
XPS analysis
conduction e-
F1s
~685 eV
0.7% F and 2% Nb
(Ti3+, 3d1)
Nb-doped TiO2:F

31. Anatase-TiO2 and orbital molecular diagram :
Generation of defects induced by mixed anions compounds
* anti-bonding
Ti4+ (eg)
dxz
dyz
* anti-bonding
Ti4+ (t2g)
Non-bonding character of dxy orbitals,
4 interactions Ti4+ - Ti4+ at 3.04 Å
dxy
dxy non-bonding
dxy (Ti) and p (O) levels
with non-bonding character
O(p)
p non-bonding
Dense pellet obtained by SPS (82%)
(T=600°C, P=100 MPa)
TiO2: Nb (2%) / F (1%)
O(p)
 bonding
Conductivity (RT) = 0.2 -1cm-1
Seebeck coefficient (RT) = -77V/K
 bonding

32. Conclusions and future works
How to build mixed anions 2D network ?
The simple key role of electronegativity  and polarisability 1/ of elements
Hard-Hard and Soft-Soft Acid-Base rules
CN(X with higher ) = CN(M with lower )
The main networks :
Ionic blocks (F/O) vs covalent sheets (S/Se)
Fluorite, Perovskite, Rocksalt vs anti-Fluorite, anti-CuO2, Würtzite .
The key role of F- : the highest  and its anomalous properties !
Designing new compounds (tuning Mn+ oxidation states)
2D/3D Ribbons (S2-, O2-, F- ) vs 3D (OH-, O2-, F- ) tunnel networks
Tuning the band gap and opto-electronic properties
by playing with competitive bonds around Mn+
Precursors to generate defects into oxides

33. Acknowledgments Mathieu Duttine, ICMCB Laetitia Sronek,
PhD, ICMCB(2007)
Nicolas Penin,
ICMCB
Damien Dambournet,
PhD ICMCB(2008)
PHENIX, Paris
Madhu Chennabassapa,
Post-doc (2014) ICMCB
Belto Dieudonné,
Post-doc (2016) ICMCB
Damien Pauwels,
PhD, ICMCB (2003),
St Gobain
Etienne Durand,
ICMCB
Alain Tressaud,
ICMCB

34. Structural features of Ti1-(O,OH,F)3 HTB-Pnma
Atomic positions and bond distances
Distances (Å)
X-ray at T=293K
Neutron at T=293K
Ti1 → F1
1.87(6)
1.93(2)
Ti1 → F2
1.99(5)
Ti1 → O2
1.92(2)
1.88(1)
Ti2 → F1
1.93(7)
1.90(3)
Ti2 → O3
2.13(3)
1.96(1)
Ti2 → F3
2.01(6)
1.92(3)
Ti2 → H2
3.06(1)
3.06(5)
Ti3 → O1
1.87(13)/1.92(13)
1.70(10)/2.11(10)
Ti3 → F2
1.82(5)
1.94(5)
Ti3 → F3
1.82(6)
1.92(5)
Ti3 → H1
3.24(2)
3.20(10)
O1 → F2
2.58(13)/2.67(13)
2.57(4)/2.88(4)
O1 → F3
2.71(13)/2.56(13)
2.59(4)/2.82(4)
O1 → H1
3.10(4)
3.09(11)
F1 → F2
2.73(8)/2.74(9)
2.64(3)/2.82(3)
F1 → O2
2.68(9)/2.68(9)
2.70(2)/2.69(3)
F1 → O3
2.89(9)/2.86(9)
2.71(3)/2.75(32)
F1 → F3
2.74(8)/2.83(9)
2.78(3)/2.62(3)
F2 → O2
2.71(8)/2.82(8)
2.58(4)/2.88(3)
F2 → F3
2.62(8)
2.73(4)
F2 → O4
3.21(6)
3.04(3)
F2 → H1
2.38(5)
2.28(10)
O2 → H1
2.92(7)
3.06(12)
O3 → O4
3.01(9)/2.80(9)
3.08(5)
O3 → H1
2.70(7)
3.13(12)
O3 → H2
1.44(7)
1.78(7)
F3 → H1
3.17(6)/2.63(6)
2.51(10)
F3 → H2
2.55(5)
2.49(4)
O4 → H1
1.22(4)
0.88(12)
O4 → H2
1.37(5)
1.38(9)
H1 → H2
1.96(5)
1.96(14)
Atom
Site x y z
Occ
B (Å2)
Neutrons (T=293K), λ= Å
Space group : Pnma
Unit Cells : a= 7.554(1) Å, b= 7.383(2) Å, c= (3) Å,
Reliability factors : Rp= 25.1, Rwp = 18.6,
Bragg-R = 8.43, Chi^2 = 1.78
Ti1 4a
0.000
0.5
1.2(2)
Ti2 4b
0.500
Ti3 4c
0.016(12)
0.25
0.252(6)
0.34(5) O1
0.239(5)
0.269(2)
1.3(1) F1 8d
0.248(3)
-0.022(3)
0.480(1)
1.0 O2
-0.026(4)
0.976(2) F2
0.043(2)
0.068(3)
0.143(2) O3
0.536(4)
-0.046(3) F3
0.012(3)
-0.062(3)
0.646(2) O4
0.267(8)
0.744(3)
0.41(6)
2.8(9) H1
0.341(17)
0.158(15)
0.744(9) H2
0.628(9)
0.825(6)

35. Structural features of (Ti0.9M0.1)1-(O,OH,F)3 HTB-Pnma
(M=V, Mo, W) atomic positions and bond distances
Distances (Å)
X-ray at T=293K
Ti1 → F1
1.87(6)
Ti1 → F2
1.99(5)
Ti1 → O2
1.92(2)
Ti2 → F1
1.93(7)
Ti2 → O3
2.13(3)
Ti2 → F3
2.01(6)
Ti2 → H2
3.06(1)
Ti3 → O1
1.87(13)/1.92(13)
Ti3 → F2
1.82(5)
Ti3 → F3
1.82(6)
Ti3 → H1
3.24(2)
O1 → F2
2.58(13)/2.67(13)
O1 → F3
2.71(13)/2.56(13)
O1 → H1
3.10(4)
F1 → F2
2.73(8)/2.74(9)
F1 → O2
2.68(9)/2.68(9)
F1 → O3
2.89(9)/2.86(9)
F1 → F3
2.74(8)/2.83(9)
F2 → O2
2.71(8)/2.82(8)
F2 → F3
2.62(8)
F2 → O4
3.21(6)
F2 → H1
2.38(5)
O2 → H1
2.92(7)
O3 → O4
3.01(9)/2.80(9)
O3 → H1
2.70(7)
O3 → H2
1.44(7)
F3 → H1
3.17(6)/2.63(6)
F3 → H2
2.55(5)
O4 → H1
1.22(4)
O4 → H2
1.37(5)
H1 → H2
1.96(5)
Distances (Å)
M = V
M = Mo
M = W
Ti1/M1 → F1
1.76(1)
1.87(1)
1.79(1)
Ti1/M1 → F2
2.09(2)
1.92(1)
Ti1/M1 → O2
1.931(6)
1.901(6)
1.875(4)
Ti2/M2 → F1
2.04(1)
1.95(1)
2.03(1)
Ti2/M2 → O3
1.907(5)
2.030(7)
2.255(8)
Ti2/M2 → F3
1.94(1)
2.05(1)
1.939(2)
Ti2/M2 → H2
3.060(1)
3.058(1)
3.053(1)
Ti3/M3 → O1
1.81(1)/1.97(1)
1.75(2)/2.03(2)
1.86(4)/1.95(4)
Ti3/M3 → F2
1.78(1)
1.89(2)
Ti3/M3 → F3
1.91(1)
1.82(1)
1.86(1)
O1 → F2
2.53(1)/2.69(1)
2.66(2)/2.71(2)
2.58(3)/2.84(3)
O1 → F3
2.82(1)/2.50(2)
2.71(2)/2.48(2)
2.80(3)/2.52(3)
O1 → H1
3.088(3)
3.092(5)
3.093(8)
F1 → F2
2.64(1)/2.83(1)
2.61(1)/2.74(2)
2.51(1)/2.74(1)
F1 → O2
2.54(1)/2.68(1)
2.76(2)/2.56(2)
2.72(2)/2.46(2)
F1 → O3
2.77(1)/2.82(1)
2.90(2)/2.74(2)
3.08(2)/2.98(2)
F1 → F3
2.87(1)/2.77(1)
2.89(1)/2.77(2)
2.85(2)/2.76(2)
F2 → O2
2.75(1)/2.75(1)
2.67(3)/2.73(2)
2.55(2)/2.81(1)
F2 → F3
2.53(2)
2.62(2)
2.69(3)
F2 → O4
3.06(1)
3.26(1)
3.06(2)
F2 → H1
2.27(1)
2.37(1)
2.30(1)
O2 → H1
2.88(1)
2.97(2)
3.08(2)
O3 → O4
3.34(2)/3.38(2)
3.04(3)/3.03(1)
2.73(3)/2.65(3)
O3 → H1
3.20(2)
2.86(2)
2.55(2)/3.04(1)
O3 → H2
1.96(2)
1.62(2)
1.19(2)
F3 → H1
3.20(1)/2.65(1)
3.14(1)/2.65(1)
2.50(2)
F3 → H2
2.55(1)
2.56(2)
2.57(1)
O4 → H1
1.15(1)
1.02(2)
0.840(9)
O4 → H2
3.13(1)/1.39(1)
3.01(2)/1.41(1)
2.82(2)/1.43(3)
H1 → H2
2.49/1.96
2.492/1.960
2.489/1.958