CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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comparison to the onebased on empirical expression (Eq.(1)). These derived new relations are tested for hydrated cluster of simple spherical anions ( , and to complex non-spherical anions ( , and . The maximum error in bulk values based on present theoretical calculation is 7% with respect to experimentally measured values compared to 57% based on the previous model. More importantly, the robust scheme proposed here provide a route to obtain ∆E DE ∞ and ∆E DE ∞ from the knowledge of ∆E VDE (n) and ∆E ADE (n) for finite and complex systems whose inter particle potentials are unknown. 136
References 1. Ohtaki, H.; Radani, T. Chem. Rev. 1993, 93, 1157. 2. Delahay, P. Acc. Chem. Res. 1982, 15, 40. 3. Nagarajan, V.; Fessenden, R. W. J. Phys. Chem.1985, 89, 2330. 4. Onsager, L. J. Am. Chem. Soc.1936, 58, 1486. 5. Kirkwood, J. G. J. Chem. Phys. 1939, 7, 911. 6. Cramer, C. J.; Truhlar, D. G. Chem. Rev. 1999, 99, 2161. 7. Ayotte, P. G.; Weddle, H.; Kim, J.; Johnson, M. A. J. Am. Chem. Soc. 1998, 120, 12361. 8. Robertson, W. H.; Diken, E. G.; Price, E. A.; Shin, J. W.; Johnson, M. A. Science 2003, 299, 1367. 9. Wang, X. B.; Yang, X.; Nicholas, J. B.; Wang, L. S. Science, 2001, 294, 1322. 10. (a) Lehr, L.; Zannai, M. T.; Frischkorn,C.; Weinkauf, R.; Neumark, D. M. Science, 1999, 284, 635. (b) Ehrler, O. T.; Neumark, D. M. Acc. Chem. Res. 2009, 42, 769. 11. Ignaczak, A.; Gomes, J.A. N. F.; Cordeiro, M. N. D. S. Eletrochimica Acta. 1999, 45, 659. 12. Vaughn, S. J.; Akhmatskaya, E. V.; Vincent, M. A.; Masters, A. J.; Hillier, I. H. J. Chem. Phys. 1999, 110, 4338. 13. Faeder, J.; Parson, R. J. Chem. Phys. 1998, 108, 3909. 14. (a) Chen, H-Y.; Shew, W-S. J. Am. Chem. Soc.2000, 122, 7534. (b) Masamura, M. J. Chem. Phys. 2003, 118, 6336. (c) Majumdar, D.; Kim, J.; Kim, K. S. J. Chem. Phys. 2000, 112, 101. 137
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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
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80 Cl 2 .nH 2 O (n=1-8) 80 Br 2 .nH
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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
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: espect to experimentally measured v
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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