CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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1.9-2.1 Å (WHB bond). It is also observed that the nature of σ type hemi bond (2c-3e) between two Cl atoms is remaining same as in case bare Cl 2 •− . These observations are also similar for hemi bonded Br 2 •− .nH 2 O and I 2 •− .nH 2 O clusters. A B C D E F G H Fig.5.2. Fully optimized global minimum energy structures at B3LYP/6-311++G(d,p) level of theory for (A) CO 3•¯.H 2 O, (B) CO 3•¯.2H 2 O, (C) CO 3•¯.3H 2 O, (D) CO 3•¯.4H 2 O, (E) CO 3•¯.5H 2 O, (F) CO 3•¯.6H 2 O, (G) CO 3•¯.7H 2 O and (H) CO 3•¯.8H 2 O. C atoms are shown by the grey colour spheres, the smallest spheres refer to H atoms and the rest corresponds to O atoms in each structure shown in the figure. Yellow colour spheres refer to the carbonate O atoms and rest (red in colour) for water O atoms. 88
The structures of the hydrated cluster, CO • 3 ⎯.nH 2 O (n=1-8) are calculated at B3LYP/6-311++G(d,p) level of theory and discussed in Chapter 2. Similarly various possible initial structures of CO •− 3 .nH 2 O (n=1-8) clusters are considered for global geometry optimization and a number of minimum energy structures (conformers) are obtained. Fully optimized global minimum energy structure of each size of hydrated cluster, CO •− 3 .nH 2 O (n=1-8) at B3LYP/6-311++G(d,p) level is displayed in Fig. 5.2. These structures of the hydrated cluster, CO • 3 ⎯.nH 2 O are very close to that discussed in Chapter 2. It is observed that CO • 3 ⎯.nH 2 O clusters are stabilized by double hydrogen bonding (DHB), single hydrogen bonding (SHB) as well as inter water hydrogen bonding (WHB). In each case, the distance between the C and O atoms of carbonate moiety (CO • 3 ⎯) is ~ 1.3 Å. The calculated distance between O (of CO • 3 ⎯) and H-bonded H atoms is 1.8-2.2 Å (SHB and DHB bond) and the distance between O and H atoms in inter water network is 1.9-2.1 Å (WHB bond). It is worth to mention that the globally optimized structures for both the cases are very close to that of most stable structure as discussed in Chapter 2. 5.3.2. UV-Vis Spectra Calculations are performed to find out a few low lying excited states for all the solvated clusters as well as for the isolated dimer radical anion (Cl •− 2 ) at both CIS and TDDFT level of theory to observe the shift in optical absorption wavelength (l) of the dimer radical anion (Cl •− 2 ) with addition of solvent water molecules. The absorption maxima (λ max ) for isolated dimer radical anion (Cl •− 2 ) is found to be at 437 nm at CIS/6- 89
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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
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Boyd proposed the use of Gaussian t
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eported experimental findings. Theo
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hydrated halide series, X¯.nH 2 O,
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anions (Cl •− 2 , Br •− 2 &
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geometrical parameters close to MP2
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symmetrical DHB, SHB or WHB arrange
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of I-I axis and having the least I-
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Br •− 2 .nH 2 O hydrated cluste
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VI-F VI-G VII-A VII-B VII-C VII-D V
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To see the effect of hydration on t
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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: most stable conformer for each size
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
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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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