CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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molecules (n) of I 2•¯.nCO 2 cluster (n=1-8) (a) at MP2/6-311+G(d) level without SOC corrections , (b) at MP2/6-311+G(d) level with SOC corrections and (c) at experimental level. (I is treated by 6-311G(d) basis set). Fig. 7.3 120 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. Fig. 8.1 134 (A) Plot of ΔΕ VDE (n) vs. (n) -1 for I − . nH 2 O systems. The result based on new relation are shown by solid line, and the solid squares (■ ) represent the experimental values taken from ref. 86. (B) Plot of ΔΕ ADE (n) vs (n+σ) -1 (σ=8) for SO −2 4 .nH 2 O. The result based on new relation are shown by solid line, and the open circle (○) represent the experimental values taken from ref. 31. xxviii
LIST OF TABLES Page No. Table. 2.1 51 Weighted average energy values for I 2•¯.nH 2 O clusters (n=1-8) at BHHLYP/6- 311++G(d,p) level of theory (for I atom split valence 6-311 basis set is used). Table. 3.1 65 Population (P i ) of the conformers of clusters of each size have been calculated based on free energy change at 100 K (T) following Boltzmann distribution. Structures are shown in Fig. 3.2. Table. 4.1 80 Calculated solvent stabilization and interaction energy in kcal/mol for X 2 .nH 2 O systems (X=Cl, Br & I; n=1-8) at MP2/6-311++G(d,p) level of theory. 6-311 basis set is applied for I atom. Table. 5.1 91 Calculated absorption maxima (λ max ) in nm at CIS/6-311++G(d,p) level of theory for Cl • 2 ⎯.nH 2 O (n=1-11) clusters and at TDDFT-B3LYP/6-311++G(d,p) level of theory for CO • 3 ⎯.nH 2 O (n=1-8) clusters. Table. 6.1 101 Calculated weighted average energy parameter of K.nNH 3 clusters (n=1-6) at BHHLYP/6-311++G(2d,2p) level of theory. Table. 7.1 115 Various energy parameters in eV of the most stable conformer for each size cluster of I 2•¯.nCO 2 (n=1-10) at MP2/6-311+G(d) level of theory. xxix
Page 1 and 2: MICROSOLVATION OF CHARGED AND NEUTR
Page 3 and 4: STATEMENT BY AUTHOR This dissertati
Page 5 and 6: Dedicated to my Daughter, Wife and
Page 7 and 8: CONTENTS Page No. SYNOPSIS LIST OF
Page 9 and 10: CHAPTER 4 Solubility of Halogen Gas
Page 11 and 12: 7.3.4. IR and Raman Spectra 117-121
Page 13 and 14: S Macroscopic Microscopic Dual leve
Page 15 and 16: molecular level interaction during
Page 17 and 18: Chapter 3: This chapter describes I
Page 19 and 20: In this system the conformers of a
Page 21 and 22: LIST OF FIGURES Page No. Fig. 1.1 2
Page 23 and 24: Fig. 2.6 54 (I) Plot of calculated
Page 25 and 26: (IIIA) Cl 2 .3H 2 O; (IIIB) Br 2 .3
Page 27: Fig. 6.3 104-105 Calculated scaled
Page 31 and 32: CHAPTER 1 Introduction 1.1. Microso
Page 33 and 34: 1.2. Motivation 1.2.1. Macrosolvati
Page 35 and 36: ulk water and pure neutral water cl
Page 37 and 38: insight about the electronic struct
Page 39 and 40: Newton -Raphson (NR) method expand
Page 41 and 42: potential energy surface for these
Page 43 and 44: terms, the energy can be written in
Page 45 and 46: Boyd proposed the use of Gaussian t
Page 47 and 48: eported experimental findings. Theo
Page 49 and 50: hydrated halide series, X¯.nH 2 O,
Page 51 and 52: anions (Cl •− 2 , Br •− 2 &
Page 53 and 54: geometrical parameters close to MP2
Page 55 and 56: symmetrical DHB, SHB or WHB arrange
Page 57 and 58: of I-I axis and having the least I-
Page 59 and 60: Br •− 2 .nH 2 O hydrated cluste
Page 61 and 62: VI-F VI-G VII-A VII-B VII-C VII-D V
Page 63 and 64: 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 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 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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