CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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Fig. 3.3 64 Calculated scaled IR spectra at BHHLYP/6-311++G(d,p) level for (A) Cl 2•¯.H 2 O and (B) Cl 2•¯.2H 2 O. The scaling factor is taken as 0.92 to account for the anharmonic nature of stretching vibrations. Lorentzian line shape has been applied with peak half-width of 20 cm -1 . Fig. 3.4 66 (I) FT-DACF IR spectra of Cl •− 2 .3H 2 O at 100K. (II) Weighted average scaled IR spectra (red line) of (A) Cl •− 2 .3H 2 O, (B) Cl •− 2 .4H 2 O and (C) Cl •− 2 .5H 2 O at BHHLYP/6- 311++G(d,p) level of theory. The black line denotes the experimental IR spectra and is reproduced from ref.24 with the permission from the American Chemical Society. The weight factor is calculated based on Boltzmann population at 100K. Lorentzian line shape has been applied with peak half-width of 5 cm -1 for Cl •− 2 .3H 2 O and Cl •− 2 .5H 2 O and 10 cm -1 for Cl •− 2 .4H 2 O. Fig. 3.5 67 Weighted average scaled IR spectra for (A) CO •− 3 . 5H 2 O, (B) NO − 3 . 5H 2 O and (C) CO 2− 3 . 5H 2 O at B3LYP/6-311++G(d,p) level of theory. The weight factor is calculated based on Boltzmann population at 100K. Lorentzian line shape has been applied with peak half-width of 10 cm -1 . Fig. 4.1 74-76 The fully optimized most stable structures calculated applying BHHLYP functional with 6-311++G(d,p) set of split valence basis function (6-311 basis set is used for iodine) for (IA) Cl 2 .H 2 O; (IB) Br 2 .H 2 O, (IC) I 2 .H 2 O; (IIA) Cl 2 .2H 2 O; (IIB) Br 2 .2H 2 O (IIC) I 2 .2H 2 O; xxiv
(IIIA) Cl 2 .3H 2 O; (IIIB) Br 2 .3H 2 O, (IIIC) I 2 .3H 2 O; (IVA) Cl 2 .4H 2 O; (IVB) Br 2 .4H 2 O, (IVC) I 2 .4H 2 O; (VA) Cl 2 .5H 2 O; (VB) Br 2 .5H 2 O, (VC) I 2 .5H 2 O; (VIA) Cl 2 .6H 2 O; (VIB) Br 2 .6H 2 O, (VIC) I 2 .6H 2 O; (VIIA) Cl 2 .7H 2 O; (VIIB) Br 2 .7H 2 O, (VIIC) I 2 .7H 2 O; (VIIIA) Cl 2 .8H 2 O, (VIIIB) Br 2 .8H 2 O and (VIIIC) I 2 .8H 2 O. Cl, Br and I atoms are shown by marked spheres, the smallest ‘white’ colour spheres refer to H atoms and the rest (red colour) corresponds to O atoms in each structure. Fig. 4.2 81 Plot of calculated interaction energy, E int and solvent stabilization energy, E solv at MP2/6- 311++G(d,p) level in kcal/mol vs. n, number of water molecules for (A) Cl 2 .nH 2 O, (B) Br 2 .nH 2 O and (C) I 2 .nH 2 O clusters. Fig. 5.1 87 Fully optimized global minimum energy structures at BHHLYP/6-311++G(d,p) level of theory for (A) Cl 2•¯.H 2 O, (B) Cl 2•¯.2H 2 O, (C) Cl 2•¯.3H 2 O, (D) Cl 2•¯.4H 2 O, (E) Cl 2•¯.5H 2 O, (F) Cl 2•¯.6H 2 O, (G) Cl 2•¯.7H 2 O, (H) Cl 2•¯.8H 2 O, (I) Cl 2•¯.9H 2 O, (J) Cl 2•¯.10H 2 O and (K) Cl 2•¯.11H 2 O clusters. Cl atoms are shown by the largest green colour spheres, the smallest spheres refer to H atoms and the rest (red in colour) corresponds to O atoms in each structure shown in the figure. Fig. 5.2 88 Fully optimized global minimum energy structures at B3LYP/6-311++G(d,p) level of theory for (A) CO 3•¯.H 2 O, (B) CO 3•¯.2H 2 O, (C) CO 3•¯.3H 2 O, (D) CO 3•¯.4H 2 O, (E) CO 3•¯.5H 2 O, (F) CO 3•¯.6H 2 O, (G) CO 3•¯.7H 2 O and (H) CO 3•¯.8H 2 O. C atoms are shown by the grey colour spheres, the smallest spheres refer to H atoms and the rest xxv
Page 1 and 2: MICROSOLVATION OF CHARGED AND NEUTR
Page 3 and 4: STATEMENT BY AUTHOR This dissertati
Page 5 and 6: Dedicated to my Daughter, Wife and
Page 7 and 8: CONTENTS Page No. SYNOPSIS LIST OF
Page 9 and 10: CHAPTER 4 Solubility of Halogen Gas
Page 11 and 12: 7.3.4. IR and Raman Spectra 117-121
Page 13 and 14: S Macroscopic Microscopic Dual leve
Page 15 and 16: molecular level interaction during
Page 17 and 18: Chapter 3: This chapter describes I
Page 19 and 20: In this system the conformers of a
Page 21 and 22: LIST OF FIGURES Page No. Fig. 1.1 2
Page 23: Fig. 2.6 54 (I) Plot of calculated
Page 27 and 28: Fig. 6.3 104-105 Calculated scaled
Page 29 and 30: LIST OF TABLES Page No. Table. 2.1
Page 31 and 32: CHAPTER 1 Introduction 1.1. Microso
Page 33 and 34: 1.2. Motivation 1.2.1. Macrosolvati
Page 35 and 36: ulk water and pure neutral water cl
Page 37 and 38: insight about the electronic struct
Page 39 and 40: Newton -Raphson (NR) method expand
Page 41 and 42: potential energy surface for these
Page 43 and 44: terms, the energy can be written in
Page 45 and 46: Boyd proposed the use of Gaussian t
Page 47 and 48: eported experimental findings. Theo
Page 49 and 50: hydrated halide series, X¯.nH 2 O,
Page 51 and 52: anions (Cl •− 2 , Br •− 2 &
Page 53 and 54: geometrical parameters close to MP2
Page 55 and 56: symmetrical DHB, SHB or WHB arrange
Page 57 and 58: of I-I axis and having the least I-
Page 59 and 60: Br •− 2 .nH 2 O hydrated cluste
Page 61 and 62: VI-F VI-G VII-A VII-B VII-C VII-D V
Page 63 and 64: To see the effect of hydration on t
Page 65 and 66: Five minimum energy structures disp
Page 67 and 68: arrangements. In total, it has one
Page 69 and 70: NO 3 − .nH2 O (n ≥ 6), a few eq
Page 71 and 72: V-E V-F V-G V-H V-I VI-A VI-B VI-C
Page 73 and 74: VII-D VII-E VII-F VII-G VII-H VII-I
Page 75 and 76:
VIII-K VIII-L Fig.2.2. Fully optimi
Page 77 and 78:
clusters. Hydrated cluster having c
Page 79 and 80:
However, these calculations do not
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Table 2.1. Weighted average energy
Page 83 and 84:
Where, E[I •− 2 .nH 2 O] is the
Page 85 and 86:
The variation of the weighted avera
Page 87 and 88:
CHAPTER 3 IR Spectra of Water Embed
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ecome more meaningful. At present,
Page 91 and 92:
I-A II-A II-B III-A III-B III-C III
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Cluster experiments are carried out
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3350-3500 cm -1 (scaling factor ~0.
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these systems, X. nH 2 O (X= Br 2
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CHAPTER 4 Solubility of Halogen Gas
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including polarized and diffuse fun
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and I 2 systems. The most stable st
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Cl Cl Br Br I I VA VB VC Cl Cl Br B
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(Br δ+ -Br δ- ) in the studied hy
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stabilization energy does not follo
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80 Cl 2 .nH 2 O (n=1-8) 80 Br 2 .nH
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separated ion pair in presence of s
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adical ( • OH) reacts with HCO 3
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most stable conformer for each size
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The structures of the hydrated clus
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Table 5.1. Calculated absorption ma
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molar extinction coefficient value
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ammonia. 61-62 Hydrogen bonded wate
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stable minimum energy structure is
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IV-A IV-B V-A V-B V-C VI-A VI-B VI-
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6.3.3. Vertical Ionization Potentia
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311++G(2d,2p) level, the scaling fa
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K(NH 3 ) 4 K(NH 3 ) 5 IR Intensity
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CHAPTER 7 Structure, Energetics and
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Thus Monte Carlo based simulated an
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I I I I I I I I A B C D I I I I I I
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interaction as well as solvent-solv
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Table 7.1. Various energy parameter
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change in VDE is observed. This is
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symmetric C-O stretching mode of CO
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to the maximum charge transfer of t
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CHAPTER 8 A Generalized Microscopic
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possible breakdown of these laws ma
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P 7 P , , P , ,, 1 ∂ 2
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M DE = (r, ω)C DE , (r,
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known. However, for most of the com
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The calculated bulk detachment ener
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espect to experimentally measured v
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References 1. Ohtaki, H.; Radani, T
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29. Turi, L.; Sheu, W.; Rossky,P.J.
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61. (a) Ehrler, O. T.; Neumark, D.
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LIST OF PUBLICATIONS *1. “σ/σ
Page 175 and 176:
13. “Vibrational analysis of I
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CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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