CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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Chapter 5: This chapter predicts the UV-Vis spectra of various radical anion systems (Cl •− 2 , Br •− 2 , I •− 2 & CO •− 3 ) in water and compare with the reported experimental UV-Vis spectra. It is also discussed that treating the solvent molecule explicitly is important (microhydration) to describe measured absorption profile as macrosolvation fails to describe reported absorption profile for such systems. Based on a few calculated low lying excited states, the UV-Vis spectra of these hydrated clusters are simulated. It is observed that UV-Vis spectra of certain hydrated cluster (e. g. Cl •− 2 .10H 2 O) is in excellent agreement with the measured aqueous phase spectra of that system. Chapter 6: Up to chapter 5, discussions about microhydration have been given. This chapter describes about microsolvation of solute in a less polar medium like ammonia. Potassium atom is taken for such study. Structure, energy (solvation energy) and spectra are calculated for studying the microsolvation of potassium in ammoniated environment. This study is important with respect to the solvated electron problem. Structures having potassium–nitrogen interactions are more stable compared to those of hydrogen bonded structures. As several closely spaced minimum energy structures are obtained for larger clusters (n>3), weighted average energy parameters are also calculated based on the statistical population at 150 K. Chapter 7: To understand the microsolvation of solutes, studies are carried out even in nonpolar medium like carbon dioxide. In this chapter, structure, energy and spectra of I •− 2 .nCO 2 clusters (n=1-10) are reported. This study is important to follow photo recombination and dissociation dynamics in order to model complex chemical reaction. xviii
In this system the conformers of a particular size of cluster is in very close in energy and have near equal statistical contribution. Monte Carlo based simulated annealing procedure is applied to find out the global minimum energy structures. Solvent stabilization and interaction energies are also calculated. It is observed that both the solvent stabilization as well as interaction energy continuously increases with the successive addition of solvent CO 2 units as in the case of more polar solvents like NH 3 or H 2 O. Chapter 8: Development of an extrapolation model based on microscopic theory to predict bulk detachment energy of excess electron from finite size cluster results is discussed in this chapter. A new relation connecting the size dependence of electron detachment energy of finite size hydrated anionic clusters is derived based on a microscopic theory. The relation is tested over a large number of different types of clusters and an excellent agreement with experimental results is observed. More importantly, an extrapolation is shown to provide a route to obtain the bulk property and again an excellent agreement with the experimental results is observed where existing empirical law fails completely. References 1. Ohtaki, H.; Radani, T. Chem. Rev. 1993, 93, 1157. 2. Delahay, P. Acc. Chem. Res. 1982, 15, 40. 3. Nagarajan, V.; Fessenden, R. W. J. Phys. Chem.1985, 89, 2330. 4. Cramer, C. J.; Truhlar, D. G. Chem. Rev. 1999, 99, 2161. xix
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: Chapter 3: This chapter describes I
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 and 28: Fig. 6.3 104-105 Calculated scaled
Page 29 and 30: LIST OF TABLES Page No. Table. 2.1
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
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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
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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
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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
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(Br δ+ -Br δ- ) in the studied hy
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stabilization energy does not follo
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80 Cl 2 .nH 2 O (n=1-8) 80 Br 2 .nH
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separated ion pair in presence of s
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adical ( • OH) reacts with HCO 3
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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
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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
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311++G(2d,2p) level, the scaling fa
Page 135 and 136:
K(NH 3 ) 4 K(NH 3 ) 5 IR Intensity
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CHAPTER 7 Structure, Energetics and
Page 139 and 140:
Thus Monte Carlo based simulated an
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I I I I I I I I A B C D I I I I I I
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interaction as well as solvent-solv
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Table 7.1. Various energy parameter
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change in VDE is observed. This is
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symmetric C-O stretching mode of CO
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to the maximum charge transfer of t
Page 153 and 154:
CHAPTER 8 A Generalized Microscopic
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possible breakdown of these laws ma
Page 157 and 158:
P 7 P , , P , ,, 1 ∂ 2
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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
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29. Turi, L.; Sheu, W.; Rossky,P.J.
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61. (a) Ehrler, O. T.; Neumark, D.
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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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