CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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Table 8.1. Bulk vertical detachment (∆E DE ∞) and adiabatic detachment (∆E DE ∞) energy for I − . nH 2 O, Br − . nH 2 O, Cl − . nH 2 O, NO 3 − . nH 2 O, SO 4 2− .nH 2 O and C 2 O 4 2− .nH 2 O systems. Systems Calculated ∆E DE ∞ Calculated ∆E DE ∞ Experimental or ∆E DE ∞in eV or ∆E DE ∞in eV ∆E DE ∞ or based on extrapolation based on extrapolation ∆E DE ∞ in eV a using new derived using Eq.1 a relations a I − . nH 2 O 7.08 b (4) 8.34 d (13) 7.40 f Br − . nH 2 O 7.56 c (7) 10.17 d (25) 8.15 f Cl − . nH 2 O 9.18 c (3) 12.47 (40) 8.90 f NO 3− . nH 2 O 7.28 c (2) 10.92 (46) 7.46 g 2− SO 4 .nH 2 O 8.07 c (7) 12.3 e (42) 8.65 g 2− C 2 O 4 .nH 2 O 6.83 c (7) 11.5 e (57) 7.32 g a ∆E DE ∞ values for I − . nH 2 O, Br − . nH 2 O and Cl − . nH 2 O systems and ∆E DE ∞ values for NO − 3 . nH 2 O, SO 2− 4 .nH 2 O and C 2 O 2− 4 .nH 2 O systems. Bold values in the parentheses refers to % of error with respect to the experimental value. b Calculated values are based on Eq. (12). c Calculated values are based on Eq. (16). d Ref. 35 (calculated based on Eq. 1). e Ref. 9 (calculated based on Eq. 1). f Ref. 87. g Ref. 88. 132
The calculated bulk detachment energy ∆E DE ∞ is shown in Table 8.1 along with the experimentally measured value. It is clear from Table1 that the results of ∆E DE ∞ obtained from the expression derived here based on microscopic theory are in very good agreement with experimental results in comparison to the calculated results obtained from the empirical law given by Eq(1). ∆E DE ∞ using Eq.(27) is also calculated and obtained the same value ∆E DE ∞ based on Eq.(16). This happens because is 3 and is not large enough in comparison to the average sizes (n) of the cluster. However, in the case of small size hydrated clusters 86,32 viz. . (n= 1 to 6), . (n=1 to 15), and . (n=1 to 5), it is found that the calculated results of ∆E DE ∞ based on Eq.(27) are in much better agreement than the same quantity calculated based on Eq.(16). The reason is very obvious, since values of . , . and . systems are 2, 2.5 and 2.5, respectively, and these values are significant in comparison to the sizes of the clusters. The calculated values of ∆E DE ∞ along with the same calculated values based on empirical relation given by Eq.(1) for these three systems, are shown in Table 8.1. Here also, the calculated results of ∆E DE ∞ based on Eq.(27) are found to be in much better agreement than the same calculated values based on the empirical Eq(1) (see Table 8.1). Now the doubly negatively charged ionic clusters viz. . and . are considered. The size of the hydrated clusters for these systems for which experimental data are available cover the range from n= 4 to 13 (for VDE) and from n= 4 to 40 (for ADE) for . clusters 9,30-31 and n= 4 to 40 for . clusters (ADE). 9 Since the sizes of the clusters are small here, ∆E VDE (n) is calculated and ∆E ADE (n) for . system and ∆E ADE (n) for . system 133
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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
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V-E V-F V-G V-H V-I VI-A VI-B VI-C
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VII-D VII-E VII-F VII-G VII-H VII-I
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VIII-K VIII-L Fig.2.2. Fully optimi
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clusters. Hydrated cluster having c
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However, these calculations do not
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Table 2.1. Weighted average energy
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Where, E[I •− 2 .nH 2 O] is the
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The variation of the weighted avera
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CHAPTER 3 IR Spectra of Water Embed
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ecome more meaningful. At present,
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I-A II-A II-B III-A III-B III-C III
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Cluster experiments are carried out
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3350-3500 cm -1 (scaling factor ~0.
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these systems, X. nH 2 O (X= Br 2
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CHAPTER 4 Solubility of Halogen Gas
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including polarized and diffuse fun
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and I 2 systems. The most stable st
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Cl Cl Br Br I I VA VB VC Cl Cl Br B
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(Br δ+ -Br δ- ) in the studied hy
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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
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Page 119 and 120: The structures of the hydrated clus
Page 121 and 122: Table 5.1. Calculated absorption ma
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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
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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: known. However, for most of the com
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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