CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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CO 3 2 ⎯) and H-bonded H atoms is 1.7-2.1 Å (SHB and DHB bond) and the distance between O and H atoms in inter water network is 1.7-2.1 Å (WHB bond). A B C D E F Fig.2.4. Fully optimized most stable structures at B3LYP/6-311++G(d,p) level of theory for (A) 2− 2− 2− 2− 2− CO 3 .H2 O, (B) CO 3 .2H2 O, (C) CO 3 .3H2 O, (D) CO 3 .4H2 O, (E) CO 3 .5H2 O, and (F) 2− CO 3 .6H2 O. C atoms are shown by the grey colour spheres, the smallest spheres refer to H atoms and the rest correspond 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. It is to be noted that the geometry of small size hydrated clusters, X. nH 2 O (n=1- 3; X= Cl 2 •− , Br 2 •− , I 2 •− , CO 3 •− , NO 3 − and CO 3 2− ) are also calculated incorporating correction due to basis set superposition error (BSSE) following counterpoise method. 45 48
However, these calculations do not lead to any significant change in the structural parameters of these hydrated clusters. 2.3.2. Solvent Stabilization and Interaction Energy where E I The stabilzation energy of I 2 •− .nH 2 O clusters can be expressed as solv E = E . − − ( nE E I nH O HO+ . −), . I . − 2 2 . nH O 2 2 2 2 , E HO 2 and E I2 .− refer to the total energy of the cluster I 2 •− .nH 2 O, the energy of a single H 2 O molecule and the energy of the bare I 2 •− system, respectively. Thus, E solv essentially refers to the total interaction energy of the solute with n solvent H 2 O units around it in the hydrated cluster of size n. A number of minimum energy configurations are obtained in these hydrated clusters and it is increasing with the size (n) of the cluster. It is understood that at a particular temperature there will be a statistical contribution of the conformers of a particular size to the overall property. So the weighted average solvent stabilization energy ( E w solv ) values are calculated and provided in Table 1. The plot for the variation of E w solv vs. n is shown in Fig. 2.5(a). The weight factor of a conformer within a particular size (n) of the cluster is calculated based on the Boltzmann statistical population of the conformer at 150 K. It is observed that E w solv varies linearly with n, the number of water molecules in the hydrated clusters and the variation of E w solv is best fitted as E w solv = -0.83 + 11.25 n, When, E w solv is expressed in kcal/mol and n is the number of water molecules. This linear fitted plot has correlation coefficient ~ 0.999 promising the power of prediction of 49
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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
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: clusters. Hydrated cluster having c
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 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
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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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