CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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check the nature of the equilibrium geometry and to generate the IR spectrum. Geometry of small size hydrated clusters are also calculated incorporating correction due to basis set superposition error (BSSE) following counterpoise method. 45 Population (P i ) of the conformers of each size clusters has been calculated based on free energy change (ΔG i ) at 150 K (T) following Boltzmann distribution i. e. P i = Exp(-ΔG i /kT). The weighted average properties (A w ) is constructed as A w = PiA . All electronic structure i ∑ i calculations have been carried out adopting GAMESS program system on a LINUX cluster platform. 46 MOLDEN program systems have been used for visualization of molecular geometry. 47 Triple split Gaussian type basis sets for Br and I atoms are obtained from the Extensible Computational Chemistry Environment Basis Set Database, Pacific Northwest Laboratory. 2.3. Results and Discussion 2.3.1.1. Structure of X.nH 2 O (X= Cl •− 2 , Br •− 2 & I •− 2 ) Clusters To choose a suitable level of theoretical method for these calculations, geometrical parameters of mono-, di and tri-hydrated clusters of Cl •− 2 , Br •− 2 & I •− 2 are carried out following 30 correlated density functionals (hybrid, pure and meta generalized gradient approximation density functionals). The calculated geometrical parameters are compared to that of at second-order Moller–Plesset perturbation (MP2) theory adopting 6-311++G(d,p) basis functions (I atom treated by 6-311 basis set). It is observed that Becke’s half-and-half (BHH) non-local exchange and Lee–Yang–Parr (LYP) non-local correlation functionals (BHHLYP) perform well to describe these clusters producing 22
geometrical parameters close to MP2 values. So, BHHLYP functional is used for geometry search throughout. Several minimum energy structures are obtained for I •− 2 .nH 2 O (n=1-8) clusters, on full geometry optimization. All the stable conformers for each size hydrated cluster are displayed in Fig. 2.1. Fig. 2.1-I shows the structure of monohydrate cluster (I •− 2 .H 2 O) consisting symmetrical double hydrogen bonding (DHB) arrangement where two I atoms and two H-atoms of the H 2 O molecule are connected by H-bonding of distance ~2 Å. It is worthmentioning that all possible combinations of initial geometry for optimization converged on the same structure. Two minimum energy structures are obtained for the dihydrate (I •− 2 .2H 2 O) cluster. Structure II-A having one DHB, one single hydrogen bonding (SHB) and one inter water H-bonding (WHB) arrangements is calculated to be more stable compared to the structure II-B having two symmetrical DHB arrangements by 1.42 kcal/mol. It appears that structure II-A is formed when H-bonded water dimer is connected to two I atoms of I •− 2 system by three free H atoms via H-bonding. But the initial guess structure of II-A is the one where two water molecules are connected via one WHB arrangement and two SHB arrangements. II-B is obtained from the initial guess where a water molecule is added to the structure I from opposite side of H 2 O making another DHB arrangement. It is worth mentioning that structure II-B is also obtained from a initial guess where two water molecules approach the I •− 2 moiety from two sides of I-I axis. Structure II-B is planar having the dihedral angle, O-I-I-O as 180 o . The energy for a WHB and SHB in such system is calculated to be 7.0 and 6.6 kcal/mol, respectively whereas the H-bonding energy in neutral water dimer is ~6.0 kcal/mol. Thus, a particular minimum energy structure is obtained on compromise between the formation of inter 23
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: anions (Cl •− 2 , Br •− 2 &
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 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 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
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CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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