5. Lehr, L.; Zannai, M. T.; Frischkorn,C.; Weinkauf, R.; Neumark, D. M. Science, 1999, 284, 635. 6. Wang, X. B.; Yang, X.; Nicholas, J. B.; Wang, L. S. Science, 2001, 294, 1322. 7. Ayotte, P. G.; Weddle, H.; Kim, J.; Johnson, M. A. J. Am. Chem. Soc. 1998, 120, 12361. 8. Xantheas, S. S. J. Am. Chem. Soc. 1995, 117, 10373. 9. Chen, H-. Y.; Shew, W-S. J. Am. Chem. Soc.2000, 122, 7534. 10. Masamura, M. J. Chem. Phys. 2003, 118, 6336 11. Majumdar, D.; Kim, J.; Kim, K. S. J. Chem. Phys. 2000, 112, 101. 12. Hertel, I. V., Huglin, C. N.; Psculz, C. P. Phys. Rev. Lett. 1991, 67, 1767. 13. Hashimoto, K.; Morokuma, K. J. Am. Chem. Soc. 1995, 117, 4151. 14. H. Gomez, T. R. Taylor, and D. M. Neumark, J. Chem. Phys. 2002, 116, 6111. 15. Greenblatt, B. J.; Zanni, M. T.; Neumark, D. M. Science 1997, 276, 1675. 16. Robertson, W. H.; Diken, E. G.; Price, E. A.; Shin, J. W.; Johnson, M. A. Science 2003, 299, 1367. 17. Weber, J. M.; Kelley, J. A.; Nielson, S. B.; Ayotte, P.; Johnson, M. A. Science 2000, 287, 2461. 18. Price, E. A.; Hammeer, N. I.; Johnson, M. A. J. Phys. Chem. A 2004, 108, 3910. 19. Barnett, R. N.; Landman, U.; Clevelend, C. L.; Jortnar, J. J. Chem. Phys. 1988, 88, 4429. 20. Zhan, C. G.; Zheng, F.; Dixon, D. A. J. Chem. Phys. 2003, 119, 781. xx
LIST OF FIGURES Page No. Fig. 1.1 2 Different models of solvations are displayed pictorially. In case of macroscopic solvation the solute ‘S’ is kept in solvent continuum. In microsolvation, the solute is encapsulated by a finite number of solvent molecules. In dual level solvation the microsolvated species is kept in the solvent continuum. In case of microscopic and dual level solvation, the central indigo colour ball refers to the solute and remaining balls refer to the solvent network (here, water is considered as solvent). Fig. 2.1 29-32 Fully optimized minimum energy structures at BHHLYP/6-311++G(d,p) level of theory for (I) I 2•¯.H 2 O, (II) I 2•¯.2H 2 O, (III) I 2•¯.3H 2 O, (IV) I 2•¯.4H 2 O, (V) I 2•¯.5H 2 O, (VI) I 2•¯.6H 2 O, (VII) I 2•¯.7H 2 O, and (VIII) I 2•¯.8H 2 O clusters. I atoms are shown by the largest green colour spheres, the smallest spheres refer to H atoms and the rest (red in colour) corresponds to O 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. 2.2 39-45 Fully optimized minimum energy structures at B3LYP/6-311++G(d,p) level of theory for (I) NO 3¯.H 2 O, (II) NO 3¯.2H 2 O, (III) NO 3¯.3H 2 O, (IV) NO 3¯.4H 2 O, (V) NO 3¯.5H 2 O, (VI) NO 3¯.6H 2 O, (VII) NO 3¯.7H 2 O and (VIII) NO 3¯.8H 2 O. N atoms are shown by the yellow colour spheres, the smallest spheres refer to H atoms and the rest corresponds to O atoms in each structure shown in the figure. Pink colour spheres refer to the nitrate O atoms and rest (red in colour) for water O atoms. Marked alphabets in upper case are xxi
- 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: In this system the conformers of a
- 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
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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
- Page 85 and 86:
The variation of the weighted avera
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CHAPTER 3 IR Spectra of Water Embed
- Page 89 and 90:
ecome more meaningful. At present,
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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
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(Br δ+ -Br δ- ) in the studied hy
- Page 109 and 110:
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
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adical ( • OH) reacts with HCO 3
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most stable conformer for each size
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The structures of the hydrated clus
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Table 5.1. Calculated absorption ma
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molar extinction coefficient value
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ammonia. 61-62 Hydrogen bonded wate
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stable minimum energy structure is
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IV-A IV-B V-A V-B V-C VI-A VI-B VI-
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6.3.3. Vertical Ionization Potentia
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311++G(2d,2p) level, the scaling fa
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K(NH 3 ) 4 K(NH 3 ) 5 IR Intensity
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CHAPTER 7 Structure, Energetics and
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Thus Monte Carlo based simulated an
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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
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Table 7.1. Various energy parameter
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change in VDE is observed. This is
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symmetric C-O stretching mode of CO
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to the maximum charge transfer of t
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CHAPTER 8 A Generalized Microscopic
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possible breakdown of these laws ma
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P 7 P , , P , ,, 1 ∂ 2
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M DE = (r, ω)C DE , (r,
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known. However, for most of the com
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The calculated bulk detachment ener
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espect to experimentally measured v
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References 1. Ohtaki, H.; Radani, T
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29. Turi, L.; Sheu, W.; Rossky,P.J.
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61. (a) Ehrler, O. T.; Neumark, D.
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LIST OF PUBLICATIONS *1. “σ/σ
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13. “Vibrational analysis of I
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