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1 Titel Y-Achse Intensity Electronic Supplementary Material (ESI) for Dalton Transactions Supplementary Material 2000 Isotropic Raman profile of the O-H band of HOD/D 2 O of a moll -1 Ca(ClO 4 ) 2 in heavy water plus D 2 O. Given are the measured rpfile, the sum curve of the fit and the band components Data: CA2DOV2HOD_isoCa2D Model: Gauss Chi^2 = R^2 = y0 15 ±0 xc ±1.19 w ±0.586 A ± xc ± w ± A ± xc ± w ± A ± Raman shift / cm -1 Figure S Isotropic Raman spectrum of the OH band of HOD/D 2 O of a 3.33 moll -1 Ca(ClO 4 ) 2 in heavy water plus HDO. Given are the measured curve, the sum curve of the plot and the band componnets Data: CADHOD_ISO Model: Gauss Chi^2 = R^2 = y0 48 ±0 xc ±1.521 w ± A ± xc ± w ± A ± Raman shift / cm -1 Figure S2.

2 Intensity Electronic Supplementary Material (ESI) for Dalton Transactions HDO/D2O_isotropic scattering Model: 2GauLor Chi^2 = R^2 = i a ± w ± bl ± bg ± h ± w ± bl ± bg ± h ± Raman shift / cm -1 Fig. S3. Band fit of the O-H band of HOD/D 2 O (~5 % HDO).

3 res. Intensity / R Electronic Supplementary Material (ESI) for Dalton Transactions Raman shift / cm -1 Figure S4. The baseline corrected, isotropic Raman mode of the symmetric stretch of Ca-O, ν 1 Ca-O of an aqueous mol L -1 Ca(ClO 4 ) 2 solution. The lower panel presents the residual curve of the difference between the measured and the fitted spectrum of ν 1 Ca-O.

4 Figure S4. Fully optimized structure of the contact ion pair, [Ca(OH 2 ) 5 Cl] +.

5 Table S1 DFT frequencies at the B3LYP/ G(d,p) level of theory for the hexahydrate of Ca 2+, Ca(OH 2 ) 6 2+ and Ca(OD 2 ) 6 2+ with additional solvation shell (PCM model) symmetry T h mode (T h ) skeletal CaO 6 modes (O h ) frequ. (cm -1 ) Ca(OH 2 ) 6 2+ assignment frequ. (cm -1 ) Ca(OD 2 ) 6 2+ assignment r = 1 f u i.r. ν 6(f 2u ) δ CaO δ CaO f g Ra ν 5(f 2g ) Ra 67.7 δ CaO δ CaO f u i.r. ν 3(f 1u ) i.r 77.9 δ CaO δ CaO e g 83.0 τ HOH 58.7 τ DOD f g Ra τ HOH 98.3 τ DOD a g τ HOH τ DOD e g Ra ν 2(e g ) Ra ν s CaO ν s CaO f g Ra ω H-O-H ω DOD f u i.r ω H-O-H ω DOD a g Ra ν 1 (a 1g ) Ra ν s CaO ν s CaO f u i.r. ν 4(f 1u ) i.r ν as CaO ν as CaO f g Ra ρ HOH ρ DOD f u i.r ρ HOH ρ DOD f u i.r δ HOH δ DOD e g Ra δ HOH δ DOD a g Ra δ HOH δ DOD e g Ra ν s OH ν s OD f u i.r ν s OH ν s OD a g Ra ν s OH ν s OD f g Ra ν as OH ν as OD f u i.r ν as OH ν as OD Ca(OH 2 2) 6 Ca(OD 2 2) 6 isotopic frequency shift: An important indicator of the frequency mode and its symmetry is given by comparison of the vibrational frequencies in deuterated and undeuterated solutions. For the cluster [Ca(OH 2 ) 6 ] 2+ and [Ca(OD 2 ) 6 ] 2+ this ratio r is given in the last row of Table S1 For the modes identified as skeletal modes, the water molecules do not vibrate. The lowest values with about are obtained for the symmetric stretching vibrations of the cluster. For these modes the water molecules translate along the Ca O bond stretching, the ratio r is determined by the mass ratio D/H and can be obtained using equ. (7). The other skeletal modes involve in addition rotations of the water molecules and the ratio r also depends on the different moments of inertia of the undeuterated/deuterated cluster ions. Whereas for the skeletal deformation modes (modes 1-3) the water molecules rotate around axes through the Ca 2+ ion, the largest ratios r are obtained for twist movements of the water molecules around the fixed skeletal Ca O axes (modes 4-6).

6 Table S2 DFT frequencies at the B3LYP/ G(d,p) level of theory for the octadecahydrate Ca(OH 2 ) 18 ] 2+ or better written as [Ca(OH 2 ) 6 (OH 2 ) 12 ] 2+ with symmetry T. frequ. symm. mode frequ. symm. mode cm -1 cm F Ra rot. (H 2 O) A Ra τ, ρ HOH 34.2 A Ra rot. (H 2 O) A Ra τ, ρ HOH 42.3 E Ra trans. (H 2 O) F i.r. Ra ω, ρ HOH 53.5 F i.r. Ra trans. (H 2 O) 3,CaO F i.r. Ra ω HOH 75.3 F i.r. Ra rot. (H 2 O) 3,CaO E Ra ω, τ HOH 84.0 F i.r. Ra rot. (H 2 O) 3,CaO F i.r. Ra ω, τ HOH 93.0 F i.r. Ra rot. (H 2 O) 3 + δ CaO F i.r. Ra ρ HOH E Ra rot. (H 2 O) 3 + ν as CaO F i.r. Ra ρ HOH F i.r. Ra trans. (H 2 O) 3 + δ CaO F i.r. Ra ω HOH A Ra trans. (H 2 O) A Ra ω HOH F i.r. Ra trans. (H 2 O) 3 + δ CaO F i.r. Ra δ HOH F i.r. Ra trans. (H 2 O) 3 + δ CaO E Ra δ HOH F i.r. Ra trans. (H 2 O) 3 + δ CaO F i.r. Ra δ HOH E Ra trans. (H 2 O) F i.r. Ra δ HOH F i.r. Ra trans. (H 2 O) A Ra δ HOH A Ra trans. (H 2 O) E Ra δ HOH F Ra δ CaO 6 + trans. (H 2 O) F i.r. Ra δ HOH F i.r. Ra δ CaO 6 + trans. (H 2 O) A Ra δ HOH E Ra ν as CaO E Ra ν s OH A Ra ν s CaO F i.r. Ra ν s OH F i.r. Ra ρ HOH A i.r. Ra ν s OH F i.r. Ra ν as CaO 6 + ρ HOH F i.r. Ra ν s OH E Ra ρ HOH F i.r. Ra ν s OH F i.r. Ra ν as CaO 6 + ρ HOH A i.r. Ra ν s OH F i.r. Ra ρ HOH F i.r. Ra ν s OH+ ν as OH A i.r. Ra ω HOH E Ra ν s OH F i.r. Ra ρ HOH F i.r. Ra ν s OH+ ν as OH F i.r. Ra ρ HOH F i.r. Ra ν s OH+ ν as OH E Ra ρ HOH F i.r. Ra ν as OH F i.r. Ra τ HOH F i.r. Ra ν as OH F i.r. Ra τ HOH E Ra ν as OH E Ra τ HOH F i.r. Ra ν as OH F i.r. Ra τ, ρ HOH A Ra ν as OH

7 Table S3 DFT geometrical parameters from DFT caclulations at the B3LYP/ G(d,p) level for the octadecahydrate Ca(OH 2 ) 18 ] 2+ or better written as [Ca(OH 2 ) 6 (OH 2 ) 12 ] 2+ with symmetry T. structural parameter Ca(OH 2 ) Ca O (inner sphere) (Å) O H (inner sphere) (Å) H-O-H (inner sphere) ( ) Ca O (outer sphere) (Å) O H(A) (outer sphere) (Å) O H(B) (outer sphere) (Å) H-O-H (outer sphere) ( ) H OH bond length (Å) 1.879

8 Table S4 DFT frequencies at the HF/ G(d,p) level of theory for the cluster [Ca(OH 2 ) 5 Cl] +, symmetry C 2v vibration freq. mode vibration freq. mode cm -1 cm -1 1 B 1 i.r. Ra 60.1 δ OCaCl 24 A 2 Ra ρ HOH 2 B 2 i.r. Ra 64.5 δ OCaCl 25 B 2 i.r. Ra ω HOH 3 B 2 Ra 80.3 δ OCaO 26 B 1 i.r. Ra ω HOH 4 B 2 i.r. Ra 93.4 δ OCaO 27 B 1 i.r. Ra ρ HOH 5 B 1 i.r.ra 94.4 δ OCaO 28 B 2 i.r. Ra ρ HOH 6 A 1 i.r. Ra δ OCaO 29 A 1 i.r. Ra ω HOH 7 B 1 i.r.ra δ OCaO 30 A 1 i.r. Ra ρ HOH 8 B 2 i.r.ra δ OCaO 31 A 2 Ra δ HOH 9 A 1 i.r. Ra δ OCaO 32 B 1 i.r. Ra δ HOH 10 A 1 i.r. Ra ν s OCaCl 33 B 2 i.r. Ra δ HOH 11 A 2 Ra ν s OCaO 34 A 1 i.r. Ra δ HOH 12 A 1 i.r.ra ν s OCaCl 35 A 1 i.r. Ra δ HOH 13 B 1 i.r. Ra ν as OCaO 36 A 2 Ra ν s OH 14 B 2 i.r. Ra ν as OCaO 37 B 1 i.r. Ra ν s OH 15 A 1 i.r.ra ν as OCaCl 38 B 2 i.r. Ra ν s OH 16 A 2 Ra τ HOH 39 A 1 i.r. Ra ν s OH 17 A 2 Ra τ HOH 40 A 1 i.r. Ra ν s OH 18 A 1 i.r. Ra τ HOH 41 B 2 i.r. Ra ν as OH 19 B 1 i.r. Ra τ HOH 42 A 2 Ra ν as OH 20 A 1 i.r. Ra τ HOH 43 B 2 i.r. Ra ν as OH 21 A 2 Ra ω HOH 44 B 1 i.r. Ra ν as OH 22 B 1 i.r. Ra ω HOH 45 A 1 i.r. Ra ν as OH 23 B 2 i.r. Ra ρ HOH

9 Table S5. Structural parameters for the cluster from DFT calculations at the HF/ G(d,p) level of theory for the cluster[ca(oh 2 ) 5 Cl] + ; symmetry C 2v. bond length (in Å) angle (deg) Ca Cl O(2)- Ca - Cl Ca O(4) O(2)-Ca - O(5) Ca O(2,3,5,6) H(7)- O(2)- H(8) O(3) H(9) H(11)- O(4)- H(12) O(3) H(10) Ca - O(2) - H(7) O(4) H(11)

CHAPTER-IV. FT-IR and FT-Raman investigation on m-xylol using ab-initio HF and DFT calculations

CHAPTER-IV. FT-IR and FT-Raman investigation on m-xylol using ab-initio HF and DFT calculations 4.1. Introduction CHAPTER-IV FT-IR and FT-Raman investigation on m-xylol using ab-initio HF and DFT calculations m-xylol is a material for thermally stable aramid fibers or alkyd resins [1]. In recent