CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

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7.3.3. Vertical Detachment Energy Vertical detachment energy (VDE) of I •− 2 .nCO 2 (n=1-8) clusters are reported by Neumark and co-workers. 48 Vertical detachment energy (VDE) is the energy required to remove an electron from the anionic solvated clusters. VDE of the solvated clusters, I •− 2 .nCO 2 can be defined by the relation: VDE n = E[I •− 2 .nCO 2 ] - E s [I 2 .nCO 2 ], where E[I •− 2 .nCO 2 ] is the energy of the optimized I •− 2 .nCO 2 cluster and E s [I 2 .nCO 2 ] is the single point energy of the I 2 .nCO 2 obtained by removing the extra electron from the optimized I •− 2 .nCO 2 cluster. The VDE for the minimum energy structures (most stable structure) of the cluster, I •− 2 .nCO 2 (n=1-8) is calculated following post Hartree-Fock second order Moller-Plesset (MP2) perturbation theory with 6-311+G(d) set of basis functions (for I 6-311G(d) basis set is taken). The VDE values calculated without and with spin-orbit coupling are tabulated in Table 7.1. The variation of VDE with the size of the cluster (n) is shown in Fig. 7.2-II (a) and II (b), respectively without and with spinorbit coupling (SOC) with relativistic corrections. 80 It is clearly seen that the VDE values is blue-shifted with increasing cluster size and this is consistent with the previous report (the experimental data is also shown in Fig. 7.2-II-c). 48 Increasing VDE with size signifies that the stability of the neutral cluster decreases with size. The calculated values of VDE and the variation of present theoretical values on VDE of solvated clusters with size is in excellent agreement with the VDE value corresponding to the X band measured by Neumark and coworker (see Table 7.1). 48 The X band is only surviving band for highest cluster (n=8) in their study. It is worth to mention that the weighted average VDE is also calculated for the I •− 2 .8CO 2 cluster (taking 6 minimum energy structures) and no 116
change in VDE is observed. This is due to the fact that all the minimum energy structure are very close in energy and all having nearly same VDE. As calculation of VDE at CCSD(T) level for higher cluster is beyond our scope at present so VDE for the two lower cluster are calculated at CCSD(T) level of theory with same basis set and are systematically lower than the MP2 values by 0.27 eV (see Table 7.1). Energy (x 10 3 eV) 3.0 2.5 2.0 1.5 1.0 0.5 0.0 I 2 .- .nCO 2 a b c VDE n (eV) 4.2 4.0 3.8 3.6 3.4 I 2 .- .nCO 2 a b c 0 2 4 6 8 10 n 0 2 4 6 8 n I II Fig. 7.2. (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 CO 2 molecules (n) of I 2•¯.nCO 2 cluster (n=1-8) (a) at MP2/6- 311+G(d) level without SOC corrections , (b) at MP2/6-311+G(d) level with SOC corrections and (c) at experimental level. (I is treated by 6-311G(d) basis set). 7.3.4. IR and Raman Spectra As discussed in the earlier section, I •− 2 .nCO 2 (n=1-10) clusters are stabilized by the interaction between I •− 2 -CO 2 (solute-solvent) as well as CO 2 -CO 2 (solvent-solvent) interactions. Due to these interactions, it is expected that the normal modes of solute and 117
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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
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: Table 7.1. Various energy parameter
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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