CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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CO 2 : IR CO 2 : Raman A B I 2 .- : Raman I 2 .- .CO 2 : IR Intensity Intensity Intensity Intensity 0 500 1000 1500 2000 2500 Frequency (cm -1 ) 0 500 1000 1500 2000 2500 Raman Shift (cm -1 ) 0 500 1000 1500 2000 2500 Raman Shift (cm -1 ) 0 500 1000 1500 2000 2500 Frequency (cm -1 ) C D I 2 .- .CO 2 : Raman I 2 .- .9CO 2 : Raman Intensity new peak 2200 2300 2400 2500 new peak Intensity 2200 2300 2400 2500 0 500 1000 1500 2000 2500 Raman Shift (cm -1 ) 0 500 1000 1500 2000 2500 Raman Shift (cm -1 ) E F Fig. 7.3. Scaled (A) IR and (B) Raman spectra of CO 2 molecule. Scaled (C) IR and (B) Raman spectra of I •− 2 .CO 2 and (D) Raman spectra I •− 2 .9CO 2 cluster. A scaling factor of 0.93 is applied to account the anharmonic nature of vibration. Lorentzian line shape has been applied with peak half-width of 10 cm -1 for all the vibrational spectra plots. 120
to the maximum charge transfer of the excess electron to the solvent CO 2 units in this particular cluster. In summary, degeneracy of bending mode of free solvent CO 2 unit is lost when it interacts with charged solute I •− 2 to form a molecular cluster. Two vibrational bands are observed at the bending region (~ 650 cm -1 ) of CO 2 in normal mode analysis. Both the stretching modes of CO 2 are red shifted compared to the free molecule but the bending mode is both red and blue shifted compared to the free molecule in these solvated clusters. IR spectra plot of I •− 2 nCO 2 (n=1-10) clusters show similar features. Vibrational band at the bending region of CO 2 (~ 650 cm -1 ) in Raman spectra is a characteristic feature for the formation of I •− 2 .CO 2 cluster. A weak band in the asymmetric stretching region (~ 2330 cm -1 ) of CO 2 vibration appears in the Raman spectra in these solvated clusters and the band is most intense for I •− 2 9CO 2 cluster. 7.4. Conclusions Structure, energy and spectra of I •− 2 .nCO 2 clusters (n=1-10) are reported to study the process of microsolvation of the negatively charged solute, I •− 2 in carbon dioxide. Hybrid density functional (BHHLYP) is applied to study the structural aspects of the present solvated clusters with a split valence 6-311+G(d) basis function. Monte Carlo based simulated annealing procedure is also applied to find out the global minimum energy structure. Solvent stabilization and interaction energies are calculated applying MP2 as well as CCSD(T) theory. It is observed that both the solvent stabilization as well as interaction energy continuously increases with the successive addition of solvent CO 2 units. It is clearly seen that the VDE values is blue-shifted with increasing cluster size 121
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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
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ecome more meaningful. At present,
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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
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 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: symmetric C-O stretching mode of CO
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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