CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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eappear. Both the bending and inversion mode is seen in the weighted average scaled IR spectra of K.5NH 3 cluster (see Fig.6.3-E). The IR spectra of K.5NH 3 cluster also consists of strong peak at N-H stretching region. The features of the weighted average scaled IR spectra of K.6NH 3 cluster (see Fig.6.3-F) is very similar to that of K.6NH 3 cluster. In all the IR spectra of K.6NH 3 cluster (n =1-6) the bending and stretching bands are red shifted (Δν = -) and inversion band is blue shifted (Δν = +) compare to that of free ammonia molecule. It is also interesting to observe that in the N-H stretching region the major contribution to the peak is from symmetric mode for all the ammoniated clusters, K.6NH 3 (n =1-6). On the other hand the major contribution to the peak due to N-H stretching for free NH 3 molecule is due to the asymmetric mode. NH 3 K(NH 3 ) IR Intensity 0 1000 2000 3000 4000 Frequency (cm -1 ) A B K(NH 3 ) 2 K(NH 3 ) 3 IR Intensity IR Intensity IR Intensity 0 1000 2000 3000 4000 Frequency (cm -1 ) 0 1000 2000 3000 4000 Frequency (cm -1 ) C 0 1000 2000 3000 4000 Frequency (cm -1 ) D Fig. 6.3 (Contd.) 104
K(NH 3 ) 4 K(NH 3 ) 5 IR Intensity IR Intensity 0 1000 2000 3000 4000 Frequency (cm -1 ) E 0 1000 2000 3000 4000 Frequency (cm -1 ) F K(NH 3 ) 6 IR Intensity 0 1000 2000 3000 4000 Frequency (cm -1 ) G Fig. 6.3. Calculated scaled IR spectra at BHHLYP/6-311++G(2d,2p) level of theory for (A) free NH 3 molecule, and for the ammoniated cluster, K.nNH 3 (n=1-3), (B) K.NH 3 ; (C) K.2NH 3 ; (D) K.3NH 3 . Calculated scaled weighted average IR spectra at same level for the ammoniated cluster, K.nNH 3 (n=4-6), (E) K.4NH 3 ; (F) K.5NH 3 ; (G) K.6NH 3 . The scaling factor is taken as 0.93 to account the anharmonic nature of vibrations. The weight factor is calculated based on statistical population of individual conformer at 150 K. Lorentzian line shape has been considered with peak half-width of 20 cm -1 for all the IR plots. 6.4. Conclusions Structure and energy of ammoniated clusters, K.nNH 3 (n=1-6) are reported to study the micro-solvent stabilization of potassium atom in ammoniated environment. Becke’s half and half hybrid exchange-correlation functional (BHHLYP) has been applied to study the present systems with a Pople triple split valence 6-311++G(2d,2p) basis function. Various initial guess structures are taken for each size of cluster and full 105
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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
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 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: 311++G(2d,2p) level, the scaling fa
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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