CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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profiles show saturation behaviour with the successive addition of solvent H 2 O units for I 2 •− .nH 2 O (n =1-8) clusters. E w (kcal/mol) 100 75 50 25 I 2 .- .nH 2 O (n=1-8) a b 0 0 2 4 6 8 n solv Fig. 2.5. Plot of calculated weighted average (a) solvent stabilization energy ( E w ) and (b) interaction int energy ( E w ) in kcal/mol vs. number of water molecules (n) in I 2•¯.nH 2 O (n=1-8) cluster at BHHLYP/6- solv int 311++G(d,p) level of theory. To estimate E w and E w the weight factor is calculated based on the statistical population of all the conformers of each size cluster at 150 K. The variation of weighted average solvation energy and weighted average interaction energy with the size of the cluster is similar for all other hydrated cluster, X. nH 2 O (X= Cl 2 •− , Br 2 •− , CO 3 •− , NO 3 − and CO 3 2− ). 2.3.3. Vertical Detachment Energy Vertical detachment energy (VDE) of the hydrated clusters, I •− 2 .nH 2 O can be defined by the relation: VDE = E[I •− 2 .nH 2 O] - E s [I 2 .nH 2 O] 52
Where, E[I •− 2 .nH 2 O] is the energy of the optimized I •− 2 .nH 2 O cluster and E s [I 2 .nH 2 O] is the single point energy of the I 2 .nH 2 O obtained by removing the extra electron from the optimized I •− 2 .nH 2 O cluster. VDE is the energy required to remove an electron from the anionic hydrated clusters. It is clearly observed that the conformer that has higher interaction energy, E int has higher VDE in each size (n) cluster. The weighted average VDE (VDE w ) is also calculated based on the statistical population of different conformers for each size (n) cluster and displayed in Table 2.1. Fig. 2.6-I displays the plot of VDE w vs. n showing the similar nature of shell closing at n=4 and n=8 as in case of E w int plot. It is worthwhile to mention that the variation of weighted average vertical detachment energy with the size of the cluster is similar for all other hydrated cluster, X. nH 2 O (X= Cl •− 2 , Br •− 2 , CO •− 3 , NO − 3 and CO 2− 3 ). As it is discussed, the plot of interaction energy (E int ) and vertical detachment energy (VDE) vs. number of water molecules (n) in these hydrated clusters (I •− 2 .nH 2 O) behave in a similar way. So it is interesting to test if there is any direct correlation between these two energy terms. For I •− 2 .nH 2 O clusters (n=1-8), weighted average interaction energy, E w int is related to the statistical weighted average vertical detachment energy, VDE w by a simple linear relation, E w int = -4.64 + 1.13 VDE w Where, both E w int and VDE w are expressed in eV. The best fit linear plot with the graphical data points are shown in Fig. 2.6-II(a). 53
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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
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: Table 2.1. Weighted average energy
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
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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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