CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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structure with lower in energy has been accepted while structures with higher energies have been accepted at a probability determined by the Boltzmann factor. Random structures have been generated by carrying out Monte Carlo steps at a high temperature (2,000 K) for more than 8000 steps. Both configuration interaction with single electron excitation (CIS) method and time dependent density functional theory (TDDFT) has been adopted for predicting a few low lying excited states of all the clusters, reported in this chapter. 5.3. Results and Discussion 5.3.1. Structure Various possible initial structures of Cl •− 2 .nH 2 O clusters (n=1-11) are considered for global geometry optimization and a number of minimum energy structures (conformers) are obtained. The global minimum energy structure of each size of hydrated cluster, Cl •− 2 .nH 2 O (n=1-11) at BHHLYP/6-311++G(d,p) is displayed in Fig. 5.1. Structures of Cl •− 2 .nH 2 O clusters (n=1-5) are also very close to the reported structures by Johnson and co-workers. 24 It is observed that the Cl •− 2 .nH 2 O clusters are stabilized by double hydrogen bonding (DHB), single hydrogen bonding (SHB) and inter water hydrogen bonding (WHB). Conformation having H-bonded water network (WHB arrangements) are more stable over the other structures where H 2 O units are connected to the anion moiety independently either by SHB or DHB for a particular size of cluster. H- bonded water network having two, three or four H 2 O units are present in the different conformers of these clusters. Hydrated cluster having cyclic water network units is the 86
most stable conformer for each size cluster. These observations are very similar to that of Cl •− 2 .nH 2 O clusters as discussed in Chapter 2 and 3. Cl •− 2 .nH 2 O clusters (n=4-11) contain at least one four member water ring. 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 (SHB and DHB bond) and the distance between O and H atoms in inter water network is A B C D E F G H I J K Fig. 5.1. 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. 87
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MICROSOLVATION OF CHARGED AND NEUTR
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STATEMENT BY AUTHOR This dissertati
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Dedicated to my Daughter, Wife and
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CONTENTS Page No. SYNOPSIS LIST OF
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CHAPTER 4 Solubility of Halogen Gas
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7.3.4. IR and Raman Spectra 117-121
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S Macroscopic Microscopic Dual leve
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molecular level interaction during
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Chapter 3: This chapter describes I
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In this system the conformers of a
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LIST OF FIGURES Page No. Fig. 1.1 2
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Fig. 2.6 54 (I) Plot of calculated
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(IIIA) Cl 2 .3H 2 O; (IIIB) Br 2 .3
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Fig. 6.3 104-105 Calculated scaled
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LIST OF TABLES Page No. Table. 2.1
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CHAPTER 1 Introduction 1.1. Microso
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1.2. Motivation 1.2.1. Macrosolvati
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ulk water and pure neutral water cl
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insight about the electronic struct
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Newton -Raphson (NR) method expand
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potential energy surface for these
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terms, the energy can be written in
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Boyd proposed the use of Gaussian t
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eported experimental findings. Theo
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hydrated halide series, X¯.nH 2 O,
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anions (Cl •− 2 , Br •− 2 &
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geometrical parameters close to MP2
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symmetrical DHB, SHB or WHB arrange
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of I-I axis and having the least I-
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Br •− 2 .nH 2 O hydrated cluste
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VI-F VI-G VII-A VII-B VII-C VII-D V
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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
Page 101 and 102: 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
Page 107 and 108: (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
Page 113 and 114: separated ion pair in presence of s
Page 115: adical ( • OH) reacts with HCO 3
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
Page 125 and 126: 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
Page 143 and 144: 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
Page 155 and 156: possible breakdown of these laws ma
Page 157 and 158: P 7 P , , P , ,, 1 ∂ 2
Page 159 and 160: 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
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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
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13. “Vibrational analysis of I
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CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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