CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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In all the clusters, K.nNH 3 (n=1-6) the K-N distance varies from 2.8–3.0 Å. The energy of K..NH 3 interaction is calculated to vary from 5-6 kcal/mol and the energy due to hydrogen bonding between two NH 3 molecules is ~1 kcal/mol. Thus, the ammoniated cluster is dominantly stabilized by the solute-solvent interaction rather than solventsolvent interaction. The solvent-solvent interaction energy plays significant role in the larger size clusters though. 6.3.2. Solvent Stabilization Energy The solvent stabilization energy of K.nNH 3 clusters can be expressed as solv E = EK. nNH − ( nENH + EK ), 3 3 where E K. nNH , E 3 NH3 and E K refer to the total energy of the optimized cluster, K.nNH 3 , the energy of a single NH 3 molecule at equilibrium geometrical and the energy of K atom, respectively. Thus, calculated E solv essentially refers to the total interaction energy of the solute with n solvent NH 3 units around it in the ammoniated cluster of size n. The calculated weighted average solvent stabilization energy ( E solv w ) of the K.nNH 3 (n=1-6) clusters are supplied in Table 6.1. The plot for the variation of E solv w vs. n is shown in Fig. 6.2-A. The weight factor of a minimum energy structure within a particular size (n) of cluster is calculated based on the statistical population of the conformer at 150 K. The best-fitted linear plot having correlation coefficient greater than 0.99 is E solv w = 2.06 + 5.35 n, where E solv w is expressed in kcal/mol and n is the cluster size. 100
6.3.3. Vertical Ionization Potential Vertical ionization potential (VIP) of the ammoniated clusters, K.nNH 3 can be calculated based on the relation, VIP = E[K.nNH 3 ] - E s [K + .nNH 3 ], where E[K.nNH 3 ] is the energy of the optimized K.nNH 3 cluster and E s [K + nNH 3 ] is the single point energy of the K.nNH 3 obtained by removing one electron from the optimized K.nNH 3 cluster. VIP is the energy required to remove an electron from the neutral clusters. The weighted average VIP (VIP w ) values are also calculated and listed in Table 6.1. The plot for the variation of VIP w vs. n is displayed in Fig. 6.2-B showing gradual decrease in energy with the size of the cluster (n). Table 6.1. Calculated weighted average energy parameter of K.nNH 3 clusters (n=1-6) at BHHLYP/6- 311++G(2d,2p) level of theory. Species Weighted average solvent stabilization energy, E w solv (kcal/mol) Weighted average vertical ionization potential, VIP w (eV) K.NH 3 6.21 3.75 K.2NH 3 12.41 3.28 K.3NH 3 19.22 2.94 K.4NH 3 25.52 2.76 K.5NH 3 28.74 2.75 K.6NH 3 32.6 2.60 101
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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
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 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: IV-A IV-B V-A V-B V-C VI-A VI-B VI-
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
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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