CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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A DACF IR Intensity IR Intensity B C 3000 3200 3400 3600 3800 4000 Photon Energy (cm -1 ) I II Fig. 3.4. (I) FT-DACF IR spectra of Cl •− 2 .3H 2 O at 100K. (II) Weighted average scaled IR spectra (red line) of (A) Cl •− 2 .3H 2 O, (B) Cl •− 2 .4H 2 O and (C) Cl •− 2 .5H 2 O at BHHLYP/6-311++G(d,p) level of theory. The black line denotes the experimental IR spectra and is reproduced from ref.24 with the permission from the American Chemical Society. The weight factor is calculated based on Boltzmann population at 100K. Lorentzian line shape has been applied with peak half-width of 5 cm -1 for Cl •− 2 .3H 2 O and Cl •− 2 .5H 2 O and 10 cm -1 for Cl •− 2 .4H 2 O. IR spectra of X. nH 2 O (X= Br 2 •− and I 2 •− ) clusters are calculated at BHHLYP/6- 311++G(d,p) and X. nH 2 O (X= CO 3 •− , NO 3 − and CO 3 2− ) clusters are calculated at B3LYP/6-311++G(d,p) level of theory. Weighted average IR spectra based on Boltzmann population factor is also generated for all the systems. It is observed that the clustering makes the shifting of O-H stretching mode of water in a similar fashion for all the halogen dimer radical anion system, X. nH 2 O (X= Cl •− 2 , Br •− 2 and I •− 2 ). The weighted average IR spectra for X. 5H 2 O (X= CO 3 •− , NO 3 − and CO 3 2− ) clusters is shown in Fig. 3.5 (A-C), respectively as a representative result. However, the calculated IR spectra for 66
these systems, X. nH 2 O (X= Br 2 •− , I 2 •− , CO 3 •− , NO 3 − and CO 3 2− ) cannot be validated due to unavailability of experimentally measured IR spectra. CO 3 .- .5H2 O NO 3 - .5H2 O Intensity 2000 2500 3000 3500 4000 Frequency (cm -1 ) A B CO 3 2- .5H 2 O Intensity IR Intensity 2000 2500 3000 3500 4000 Frequency (cm -1 ) 2000 2500 3000 3500 4000 Frequency (cm -1 ) C Fig. 3.5. Weighted average scaled IR spectra for (A) CO 3 •− . 5H2 O, (B) NO 3 − . 5H2 O and (C) CO 3 2− . 5H2 O at B3LYP/6-311++G(d,p) level of theory. The weight factor is calculated based on Boltzmann population at 100K. Lorentzian line shape has been applied with peak half-width of 10 cm -1 . It is observed that the IR spectra of each clusters, X. nH 2 O (X= Cl 2 •− , Br 2 •− , I 2 •− , CO 3 •− , NO 3 − and CO 3 2− ) are characterized by large shift of O-H (~300 cm -1 ) stretching 67
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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
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: 3350-3500 cm -1 (scaling factor ~0.
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
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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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