CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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used to refer different minimum energy conformers for each hydrated cluster size arranged in order of stability showing ‘A’ as the most stable one. Fig. 2.3 45-46 Fully optimized most stable 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 correspond to O atoms in each structure shown in the figure. Yellow colour spheres refer to the carbonate O atoms and rest (red in colour) for water O atoms. Fig. 2.4 48 Fully optimized most stable structures at B3LYP/6-311++G(d,p) level of theory for (A) CO 3 2− .H 2 O, (B) CO 3 2− .2H 2 O, (C) CO 3 2− .3H 2 O, (D) CO 3 2− .4H 2 O, (E) CO 3 2− .5H 2 O, and (F) CO 3 2− .6H 2 O. C atoms are shown by the grey colour spheres, the smallest spheres refer to H atoms and the rest correspond to O atoms in each structure shown in the figure. Yellow colour spheres refer to the carbonate O atoms and rest (red in colour) for water O atoms. Fig. 2.5 52 solv Plot of calculated weighted average (a) solvent stabilization energy ( E w ) and (b) interaction energy (E w int ) in kcal/mol vs. number of water molecules (n) in I 2 •¯.nH 2 O (n=1- 8) cluster at BHHLYP/6-311++G(d,p) level of theory. To estimate E w solv and E w int the weight factor is calculated based on the statistical population of all the conformers of each size cluster at 150 K. xxii
Fig. 2.6 54 (I) Plot of calculated weighted average vertical detachment energy (VDE w ) in eV vs. number of water molecules (n) in I 2•¯.nH 2 O (n=1-8) cluster at BHHLYP/6-311++G(d,p) level of theory (II) Plot of calculated weighted average (a) interaction, int Ew in eV vs. weighted in eV for the hydrated cluster, I 2•¯.nH 2 O (n ≤ 8) showing a linear relationship and (b) solvation energy, E w solv in eV vs. weighted average vertical detachment energy (VDE w ) in eV for the hydrated cluster, I 2•¯.nH 2 O (n ≤ 8). Fig. 3.1 60 Calculated scaled IR spectra at BHHLYP/6-311++G(d,p) level free H 2 O molecule. 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 10 cm -1 . Fig. 3.2 61-62 Fully optimized minimum energy structures at BHHLYP/6-311++G(d,p) level of theory for (I) Cl 2•¯.H 2 O, (II) Cl 2•¯.2H 2 O, (III) Cl 2•¯.3H 2 O, (IV) Cl 2•¯.4H 2 O and (V) Cl 2•¯.5H 2 O clusters. Marked alphabets in the upper case are used to refer different minimum energy conformers for each size of the hydrated cluster arranged in order of stability showing ‘A’ as the most stable one. 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. In each case, the distance between the two Cl atoms is ~ 2.6 Å, the distance between Cl and H-bonded H atoms is 2.3-2.8 Å and the distance between O and H atoms in inter water network is ~ 2.0 Å. xxiii
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: LIST OF FIGURES Page No. Fig. 1.1 2
Page 25 and 26: (IIIA) Cl 2 .3H 2 O; (IIIB) Br 2 .3
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
Page 81 and 82:
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
Page 89 and 90:
ecome more meaningful. At present,
Page 91 and 92:
I-A II-A II-B III-A III-B III-C III
Page 93 and 94:
Cluster experiments are carried out
Page 95 and 96:
3350-3500 cm -1 (scaling factor ~0.
Page 97 and 98:
these systems, X. nH 2 O (X= Br 2
Page 99 and 100:
CHAPTER 4 Solubility of Halogen Gas
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including polarized and diffuse fun
Page 103 and 104:
and I 2 systems. The most stable st
Page 105 and 106:
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
Page 109 and 110:
stabilization energy does not follo
Page 111 and 112:
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
Page 117 and 118:
most stable conformer for each size
Page 119 and 120:
The structures of the hydrated clus
Page 121 and 122:
Table 5.1. Calculated absorption ma
Page 123 and 124:
molar extinction coefficient value
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ammonia. 61-62 Hydrogen bonded wate
Page 127 and 128:
stable minimum energy structure is
Page 129 and 130:
IV-A IV-B V-A V-B V-C VI-A VI-B VI-
Page 131 and 132:
6.3.3. Vertical Ionization Potentia
Page 133 and 134:
311++G(2d,2p) level, the scaling fa
Page 135 and 136:
K(NH 3 ) 4 K(NH 3 ) 5 IR Intensity
Page 137 and 138:
CHAPTER 7 Structure, Energetics and
Page 139 and 140:
Thus Monte Carlo based simulated an
Page 141 and 142:
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
Page 145 and 146:
Table 7.1. Various energy parameter
Page 147 and 148:
change in VDE is observed. This is
Page 149 and 150:
symmetric C-O stretching mode of CO
Page 151 and 152:
to the maximum charge transfer of t
Page 153 and 154:
CHAPTER 8 A Generalized Microscopic
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possible breakdown of these laws ma
Page 157 and 158:
P 7 P , , P , ,, 1 ∂ 2
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M DE = (r, ω)C DE , (r,
Page 161 and 162:
known. However, for most of the com
Page 163 and 164:
The calculated bulk detachment ener
Page 165 and 166:
espect to experimentally measured v
Page 167 and 168:
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.
Page 173 and 174:
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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