CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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adical anion (CO 3 • ⎯) is found to be at 580 nm at TDDFT (B3LYP)/6-311++G(d,p) level of theory. 10000 2000 8000 a 1500 a ε (M -1 cm -1 ) 6000 4000 2000 c b ε (M -1 cm -1 ) 1000 500 b 0 250 300 350 400 450 500 550 600 Wave length (nm) 0 450 500 550 600 650 700 Wavelength (nm) I II Fig. 5.3. (I) Optical absorption profile for (a) Cl 2•¯ and (b) Cl 2•¯.10H 2 O at CIS/6-311++G(d,p) level of theory. (c) Experimental absorption profile for Cl 2•¯ in aqueous solution. (II) Optical absorption profile for (a) the most stable structure of CO • 3 ⎯.8H 2 O at TDDFT/6-311++G(d,p) with B3LYP hybrid density functional and (b) experimental absorption profile for CO • 3 ⎯ in aqueous solution. The λ max values of the CO • 3 ⎯.nH 2 O clusters (n=1-8) calculated at the same level of theory are supplied in Table 5.1. Visualization of the appropriate molecular orbital (MO) indicates that the optical absorption is mainly due to an electronic transition from the highest doubly occupied bonding sigma MO to the lowest singly occupied antibonding sigma MO (σ→σ*) in all these hydrated clusters. The optical absorption profiles for each of the CO • 3 ⎯.nH 2 O systems (n=0-8) are generated based on ten low lying excited states and the UV-Vis spectra for CO •− 3 .8H 2 O systems is shown in Fig. 5.3-II(a). There is an excellent agreement between the experimental aqueous phase optical absorption spectrum (see Fig. 5.3-II(b)) and the present calculated one for the most stable structure of CO • 3 ⎯.8H 2 O cluster. 60 The calculated absorbance is scaled with the reported experimental 92
molar extinction coefficient value for CO • 3 ⎯(aq) following pulse radiolysis technique. It is to be noted that λ max values of the CO • 3 ⎯.nH 2 O clusters calculated by applying CIS (configuration interaction with single electron excitation) procedure is largely blue shifted (~ 350 nm) in all these hydrated clusters. 5.4. Conclusions Global minimum energy structures of Cl •− 2 and CO •− 3 hydrated clusters are obtained applying simulated annealing with Monte Carlo sampling procedure. Based on a few calculated low lying excited states applying CIS procedure, UV-Vis spectra of these hydrated clusters are simulated. UV-Vis spectra of Cl •− 2 .10H 2 O cluster is in excellent agreement with the measured aqueous phase spectra of Cl •− 2 system. Simulated UV-Vis spectra of CO •− 3 .8H 2 O cluster at B3LYP-TDDFT/6-311++G(d,p) level is in excellent agreement with the measured aqueous phase spectra of CO •− 3 system. In all the cases the strong absorption is due to an electronic transition from the highest doubly occupied MO to the lowest singly occupied MO (σ→σ*). 93
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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
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arrangements. In total, it has one
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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 and 118: most stable conformer for each size
Page 119 and 120: The structures of the hydrated clus
Page 121: Table 5.1. Calculated absorption ma
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
Page 169 and 170: 29. Turi, L.; Sheu, W.; Rossky,P.J.
Page 171 and 172: 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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