CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

More documents

Recommendations

Info

espectively. The interaction energy for the hepta- and the octa- hydrated clusters of Cl 2 systems is smaller than that of the hexa- hydrated cluster. This may be due to the specific geometry of the hydrated clusters where seven solvent water molecules form H-bonded cluster and remains far away from Cl 2 moiety. For Br 2 .nH 2 O clusters, the calculated interaction energy profile shows saturation at n=7. In case of I 2 .nH 2 O clusters, the calculated interaction energy profile shows a stepwise saturation nature at n=6 and 8. Table 4.1: Calculated solvent stabilization and interaction energy in kcal/mol for X 2 .nH 2 O systems (X=Cl, Br & I; n=1-8) at MP2/6-311++G(d,p) level of theory. 6-311 basis set is applied for I atom. Species X 2 .nH 2 O Solvent stabilization energy of X 2 .nH 2 O clusters (kcal/mol) Interaction energy of X 2 .nH 2 O clusters (kcal/mol) X=Cl X=Br X=I X=Cl X=Br X=I n = 1 2.85 3.86 4.57 3.07 4.11 4.88 n = 2 9.85 5.52 8.42 4.36 5.76 3.00 n = 3 9.88 13.53 16.31 3.91 7.74 10.80 n = 4 25.82 27.68 32.18 7.42 9.58 14.59 n = 5 28.24 30.23 33.69 8.49 11.02 15.76 n = 6 45.66 47.87 52.70 9.31 11.66 16.48 n = 7 65.00 60.03 67.40 4.55 11.32 23.40 n = 8 73.25 71.26 76.71 6.57 13.73 23.11 80
80 Cl 2 .nH 2 O (n=1-8) 80 Br 2 .nH 2 O (n=1-8) Energy (kcal/mol) 60 40 20 E solv E int Energy (kcal/mol) 60 40 20 E solv E int 0 0 2 4 6 8 n 0 0 2 4 6 8 n A B Energy (kcal/mol) 80 60 40 20 I 2 .nH 2 O (n=1-8) E solv E int 0 0 2 4 6 8 n C Fig. 4.2. Plot of calculated interaction energy, E int and solvent stabilization energy, E solv at MP2/6- 311++G(d,p) level in kcal/mol vs. n, number of water molecules for (A) Cl 2 .nH 2 O, (B) Br 2 .nH 2 O and (C) I 2 .nH 2 O clusters. The interaction energy (E int ) is the measure of the interaction between the halogen moiety and water units. Thus, a large value of E int indicates the presence of a large number of water molecules in close surrounding of the halogen moiety. For the present systems, calculated E int is small and does show only a small increase with the addition of water molecules. That explains the presence of only a few water molecules (2–3) in the 81
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 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 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: stabilization energy does not follo
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
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
show all

CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

Create successful ePaper yourself

Delete template?

Save as template?