CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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corresponds 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. Fig. 5.3 92 (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. Fig. 6.1 98-99 The fully optimized structures calculated at BHHLYP/6-311++G(2d,2p) level of theory for (I) K.NH 3 , (II) K.2NH 3 , (III) K.3NH 3 , (IV) K.4NH 3 , (V) K.5NH 3 , and (VI) K.6NH 3 clusters. K atoms are shown by the largest yellow colour spheres, the smallest white spheres refer to H atoms and the rest (pink colour) corresponds to N atoms in each structure shown in the figure. Marked alphabets in upper case are used to refer different minimum energy conformers for each hydrated cluster size arranged in order of stability showing ‘A’ as the most stable one. Fig. 6.2 102 solv Plot of calculated weighted average (A) solvent stabilization energy ( E w ) in kcal/mol and (B) vertical ionization potential (VIP w ) in eV vs. number of ammonia molecules (n) in K.nNH 3 (n=1-6) cluster at BHHLYP/6-311++G(2d,2p) level of theory. To estimate solv E w and VIP w the weight factor is calculated based on the statistical population of all the minimum energy structures of each size cluster at 150 K. xxvi
Fig. 6.3 104-105 Calculated scaled IR spectra at BHHLYP/6-311++G(2d,2p) level of theory for (A) free NH 3 molecule, and for the ammoniated cluster, K.nNH 3 (n=1-3), (B) K.NH 3 ; (C) K.2NH 3 ; (D) K.3NH 3 . Calculated scaled weighted average IR spectra at same level for the ammoniated cluster, K.nNH 3 (n=4-6), (E) K.4NH 3 ; (F) K.5NH 3 ; (G) K.6NH 3 . The scaling factor is taken as 0.93 to account the anharmonic nature of vibrations. The weight factor is calculated based on statistical population of individual conformer at 150 K. Lorentzian line shape has been considered with peak half-width of 20 cm -1 for all the IR plots. Fig. 7.1 111 Fully optimized global minimum energy structures calculated at BHHLYP/6-311+G(d) level of theory for (A) I 2•¯.CO 2 , (B) I 2•¯.2CO 2 , (C) I 2•¯.3CO 2 , (D) I 2•¯.4CO 2 , (E) I 2•¯.5CO 2 , (F) I 2•¯.6CO 2 , (G) I 2•¯.7CO 2 , (H) I 2•¯.8CO 2 , (I) I 2•¯.9CO 2 and (J) I 2•¯.10CO 2 clusters (I atom is treated by 6-311G(d) basis set). I atoms are shown by the largest violet spheres, the grey spheres correspond to C atoms and the red spheres refer to O atoms of solvent CO 2 units in each structure of the solvated cluster. In each case, the distance between the two I atoms is ~ 3.3 –3.0 Å, the distance between C and I atoms is ~ 3.9- 4.9Å. Fig. 7.2 117 (I) Variation of calculated (a) solvent stabilization energy (E solv ), (b) ion-solvent interaction energy ( E int− is ) and (c) solvent-solvent interaction energy ( E int− ss ) in kcal/mol with the number of solvent CO 2 molecules (n) in I 2•¯.nCO 2 cluster at MP2/6-311+G(d) level of theory .(II) Plot of vertical detachment energy, ( VDE n ) in eV vs. number of CO2 xxvii
Page 1 and 2: MICROSOLVATION OF CHARGED AND NEUTR
Page 3 and 4: STATEMENT BY AUTHOR This dissertati
Page 5 and 6: 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: (IIIA) Cl 2 .3H 2 O; (IIIB) Br 2 .3
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 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
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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
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separated ion pair in presence of s
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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
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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-
Page 131 and 132:
6.3.3. Vertical Ionization Potentia
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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
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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
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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
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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