CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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D E F G H Fig.2.3. Fully optimized most stable 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 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. The structures of the various conformations of CO 3•¯.nH 2 O clusters are very similar to that of NO 3¯.nH 2 O clusters. So, only the most stable structures of CO 3•¯.nH 2 O clusters are displayed in Fig. 2.3. The 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). H-bonded water network having two, three, four or five H 2 O units are present in different conformers of these clusters. Surface structures are preferred upto tetra- hydrated cluster keeping the solute anion at the surface of the solute water 46
clusters. Hydrated cluster having cyclic water network units, is the most stable conformer for each size cluster (see Fig. 2.3). 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 the inter water network is 1.9-2.1 Å (WHB bond). 2.3.1.3. Structure of CO 2 3 ⎯.nH 2 O Clusters In the previous two sections, structures of singly anionic species are discussed. It is also interesting to study structure of microhydrated polyatomic species with doubly negative charge like carbonate anion (CO 2− 3 ). On full geometry optimization at B3LYP/6-311++G(d.p) level of theory, different minimum energy structures are obtained for each size of hydrated carbonate dianion cluster, CO 2− 3 .nH 2 O (n=1-6). It is observed that the structures of conformers of each size of CO 2− 3 .nH 2 O cluster are very close to those obtained for NO 3¯.nH 2 O and CO 3•¯.nH 2 O clusters. The most stable structure for each size of hydrated cluster, CO 2− 3 .nH 2 O is displayed in Fig. 2.4. It is clear from the figure that CO 2− 3 .nH 2 O clusters are stabilized by double hydrogen bonding (DHB), single hydrogen bonding (SHB) as well as inter water hydrogen bonding (WHB). H-bonded water network having two or three, H 2 O units are present in the different conformers of these clusters. But structures with cyclic water network is not the most stable structures for n=3-5 in contrast to the other hydrated clusters of Cl •− 2 , Br •− 2 , I •− 2 , CO •− 3 and NO − 3 . For n=6, the most stable structure has one cyclic water network. No structure with four of higher member water network is found. In each case, the distance between the C and O atoms of the carbonate moiety (CO 2 3 ⎯) is ~ 1.3 Å. The calculated distance between O (of 47
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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
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 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: VIII-K VIII-L Fig.2.2. Fully optimi
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 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
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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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