CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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VIII-A VIII-B VIII-C VIII-D VIII-E VIII-F VIII-G VIII-H VIII-I Fig. 2.1. Fully optimized minimum energy structures at BHHLYP/6-311++G(d,p) level of theory for (I) I 2•¯.H 2 O, (II) I 2•¯.2H 2 O, (III) I 2•¯.3H 2 O, (IV) I 2•¯.4H 2 O, (V) I 2•¯.5H 2 O, (VI) I 2•¯.6H 2 O, (VII) I 2•¯.7H 2 O, and (VIII) I 2•¯.8H 2 O clusters. I atoms are shown by the largest green colour spheres, the smallest spheres refer to H atoms and the rest (red in colour) corresponds to O atoms in each structure shown in the figure. Marked alphabets in upper case are used to refer different minimum energy conformers for each hydrated cluster size arranged in order of stability showing ‘A’ as the most stable one. 32
To see the effect of hydration on the distribution of the excess electron in iodine dimer radical anion, I •− 2 , Mulliken atomic spin (a-b) population over different atoms is calculated in the hydrated cluster, I •− 2 .nH 2 O clusters (n=0-8). It is clearly observed that the odd electron spin is localized over the two I atoms only. Results suggest that the spin distribution of the odd electron does not change significantly on successive addition of solvent H 2 O molecules in I •− 2 .nH 2 O clusters (n=1-8). The nature of σ type hemi bond (2c- 3e) between two I atoms in I •− 2 remains the same even after addition of successive water molecules. This observation is true for Cl •− 2 .nH 2 O and Br •− 2 .nH 2 O systems too. 2.3.1.2. Structure of X.nH 2 O (X= NO − 3 and CO •− 3 ) Clusters In the previous section, structures of diatomic anionic systems are discussed. In this section, structure of hydrated clusters of carbonate radical anion (CO 3•¯ ) and nitrate anion (NO − 3 ) is reported. To choose a suitable level of theoretical method for geometry search in these systems, geometrical parameters of mono-, di and tri-hydrated clusters of NO − 3 and CO 3•¯ are carried out following 30 correlated density functionals (hybrid, pure and meta generalized gradient approximation density functionals). The caculated geometrical parameters are compared to that at MP2 theory adopting 6-311++G(d,p) basis functions. It is observed that Becke’s three parameter non-local exchange (B3) and Lee-Yang-Parr (LYP) non-local correlation functionals (B3LYP) performs well to describe these clusters producing geometrical parameters close to MP2 results. Various possible initial structures of NO 3¯.nH 2 O and CO 3•¯.nH 2 O clusters (n=1-8) are considered for geometry optimization and a number of minimum energy structures (conformers) are obtained for each size cluster as expected. 33
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MICROSOLVATION OF CHARGED AND NEUTR
Page 3 and 4:
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
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 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: VI-F VI-G VII-A VII-B VII-C VII-D V
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
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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
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The structures of the hydrated clus
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Table 5.1. Calculated absorption ma
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molar extinction coefficient value
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ammonia. 61-62 Hydrogen bonded wate
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stable minimum energy structure is
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IV-A IV-B V-A V-B V-C VI-A VI-B VI-
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6.3.3. Vertical Ionization Potentia
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311++G(2d,2p) level, the scaling fa
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K(NH 3 ) 4 K(NH 3 ) 5 IR Intensity
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CHAPTER 7 Structure, Energetics and
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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
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CHAPTER 8 A Generalized Microscopic
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possible breakdown of these laws ma
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P 7 P , , P , ,, 1 ∂ 2
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M DE = (r, ω)C DE , (r,
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known. However, for most of the com
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The calculated bulk detachment ener
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espect to experimentally measured v
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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
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13. “Vibrational analysis of I
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CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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