CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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cluster. Nine conformers are obtained with all real frequencies based on full geometry optimization followed by Hessian calculations. The optimized structures are displayed in Fig. 2.1-VIII(A-I). One can see from Fig. 2.1-VIIIA that the anion moiety is sandwiched between the two cyclic water tetramers in the most stable conformer. Structure VIII-B making one cyclic water tetramer is less stable than the most stable conformer by 0.67 kcal/mol. Structure VIII (A-C, E-F) has at least one cyclic water tetramer. The least stable conformer (~10 kcal/mol less stable compared to VIII-A), (see Fig. 2.1-VIII(I)) has two H 2 O cyclic trimers and two DHB arrangements. It is noticed that several minimum energy conformations with a small energy difference can exist for the hydrated cluster, I •− 2 .nH2O (n=3-8). It is clear from the figure that the I •− 2 .nH 2 O clusters are stabilized by double hydrogen bonding (DHB), single hydrogen bonding (SHB) and inter water hydrogen bonding (WHB). Conformation having H-bonded water network (WHB arrangements) are more stable over the other structures where H 2 O units are connected to the anion moiety independently either by SHB or DHB for a particular size of the cluster. H-bonded water network, having two, three or four H 2 O units, are present in different conformers of these clusters. Hydrated cluster having cyclic water network units is the most stable conformer for each size cluster. Hydrated I •− 2 .nH 2 O clusters of size n=4-8 contain at least one four member water ring (see Fig. 2.1). In each case, the distance between the two I atoms is ~ 3.3 Å, the distance between I and H-bonded H atoms is 2.3-2.8 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). Structures of microhydrated species, Cl •− 2 .nH 2 O and Br •− 2 .nH 2 O are also calculated. Similar minimum energy structures are also observed for Cl •− 2 .nH 2 O and 28
Br •− 2 .nH 2 O hydrated cluster. For Cl •− 2 .nH 2 O cluster, in each case, the distance between the two Cl atoms is ~ 2. 6 Å, the distance between Cl and H-bonded H atoms is 2.3-2.8 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). For Br •− 2 .nH 2 O cluster, in each case, the distance between the two Br atoms is ~ 2. 8 Å, the distance between Br and H-bonded H atoms is 2.3-2.8 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). I II-A II-B III-A III-B III-C III-D IV-A IV-B IV-C IV-D IV-E Fig. 2.1 (Contd.) 29
Page 1 and 2:
MICROSOLVATION OF CHARGED AND NEUTR
Page 3 and 4:
STATEMENT BY AUTHOR This dissertati
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Dedicated to my Daughter, Wife and
Page 7 and 8: CONTENTS Page No. SYNOPSIS LIST OF
Page 9 and 10: CHAPTER 4 Solubility of Halogen Gas
Page 11 and 12: 7.3.4. IR and Raman Spectra 117-121
Page 13 and 14: S Macroscopic Microscopic Dual leve
Page 15 and 16: molecular level interaction during
Page 17 and 18: Chapter 3: This chapter describes I
Page 19 and 20: In this system the conformers of a
Page 21 and 22: LIST OF FIGURES Page No. Fig. 1.1 2
Page 23 and 24: 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: of I-I axis and having the least I-
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 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
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stabilization energy does not follo
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80 Cl 2 .nH 2 O (n=1-8) 80 Br 2 .nH
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separated ion pair in presence of s
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adical ( • OH) reacts with HCO 3
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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
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molar extinction coefficient value
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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
Page 153 and 154:
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,
Page 161 and 162:
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.
Page 173 and 174:
LIST OF PUBLICATIONS *1. “σ/σ
Page 175 and 176:
13. “Vibrational analysis of I
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CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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