CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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molecules in an asymmetric fashion. 74 This may be due to inaccurate treatment of solutesolvent and solvent-solvent interactions in these anionic clusters favoring induced dipoleinduced dipole interaction between two solvent CO 2 molecules over ion-induced dipole interaction between the solute I •− 2 and solvent CO 2 molecules. To verify the influence of spin-orbit coupling in the equilibrium structure of these solvated clusters, geometry optimizations of the equilibrium structures are repeated including spin orbit interaction at the same level of theory for n=1 and 6 as test cases with no significant change in the optimized structures. In summary, the calculated I…I bond distance is shorter than the isolated solute I •− 2 (3.334 Å) unit in all the solvated clusters, I •− 2 .nCO 2 (n=1-10). On each successive addition of solvent CO 2 units, I…I distance decreases in all these solvated clusters. On the addition of ten solvent CO 2 molecules to the iodine dimer radical anion system, I •− 2 a decrease of ~ 0.3 Å in I…I bond distance is occurred. In all these cases, the structures obtained on full optimization applying Newton Raphson procedure are further optimized using Monte Carlo simulated annealing method to look for the global minimum energy structures. However, in all the cases the global structures predicted are very close to those obtained by applying Newton Raphson procedure. On refining these global minimum energy structures applying BHHLYP method, the same structures are obtained. This confirms that the predicted structures are truly global minimum energy structures. To see the effect of solvation on the distribution of the excess electron in iodine dimer radical anion, I •− 2 , Mulliken atomic spin (a-b) population over different atoms is calculated in I •− 2 .nCO 2 clusters (n=1-10). It is observed that the odd electron spin is mostly populated over two I atoms in case of mono solvated cluster, I •− 2 .CO 2 . 110
I I I I I I I I A B C D I I I I I I E F G I I I I I I H I J Fig. 7.1. Fully optimized global minimum energy structures calculated at BHHLYP/6-311+G(d) level of theory for (A) I 2•¯.CO 2 , (B) I 2•¯.2CO 2 , (C) I 2•¯.3CO 2 , (D) I 2•¯.4CO 2 , (E) I 2•¯.5CO 2 , (F) I 2•¯.6CO 2 , (G) I 2•¯.7CO 2 , (H) I 2•¯.8CO 2 , (I) I 2•¯.9CO 2 and (J) I 2•¯.10CO 2 clusters (I atom is treated by 6-311G(d) basis set). I atoms are shown by the largest violet spheres, the grey spheres correspond to C atoms and the red spheres refer to O atoms of solvent CO 2 units in each structure of the solvated cluster. In each case, the distance between the two I atoms is ~ 3.3 –3.0 Å, the distance between C and I atoms is ~ 3.9-4.9Å. 111
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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
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Five minimum energy structures disp
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arrangements. In total, it has one
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NO 3 − .nH2 O (n ≥ 6), a few eq
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V-E V-F V-G V-H V-I VI-A VI-B VI-C
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VII-D VII-E VII-F VII-G VII-H VII-I
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VIII-K VIII-L Fig.2.2. Fully optimi
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clusters. Hydrated cluster having c
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However, these calculations do not
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Table 2.1. Weighted average energy
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Where, E[I •− 2 .nH 2 O] is the
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The variation of the weighted avera
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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 and 116: 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
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: Thus Monte Carlo based simulated an
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
Page 167 and 168: References 1. Ohtaki, H.; Radani, T
Page 169 and 170: 29. Turi, L.; Sheu, W.; Rossky,P.J.
Page 171 and 172: 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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