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| - Vibrational Analysis of I2•−.nCO2 Clusters (n = 1−10): A First Principle Study on Microsolvation
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| Abstract
| - Structure, stability, and vibrational IR and Raman spectra of I2•−.nCO2 clusters (n = 1−10) are reported based on first-principle electronic structure calculations. Several close-lying minimum energy structures are predicted for these solvated clusters following the quasi Newton−Raphson procedure of geometry optimization. Search strategy based on Monte−Carlo simulated annealing is also applied to find out the global minimum energy structures of these clusters. Successive addition of solvent CO2 molecules to the negatively charged diatomic solute, I2•−, is fairly symmetrical. Energy parameters of these solvated clusters are calculated following second-order Moller−Plesset perturbation (MP2) as well as coupled cluster theory with 6−311+G(d) set of basis function (I atom is treated with 6−311G(d) set of basis function). The excess electron in these solvated clusters is observed to be localized mainly over the two I atoms. Average interaction energy between the anionic solute, I2•−, and a solvent CO2 molecule is ∼129 meV in I2•−.nCO2 clusters, and the average interaction energy between two solvent CO2 molecules is ∼85 meV in the case of neutral (CO2)n clusters at MP2 level of theory. IR spectra show similar features in all these solvated clusters, depicting a strong band at ∼2330 cm−1 for C−O stretching and a weak band at ∼650 cm−1 for CO2 bending modes. Degeneracy of the bending mode of a free solvent CO2 unit gets lifted when it interacts with the charged solute I2•− to form a molecular cluster because of the change in structure of solvent CO2 units. The vibrational band at the bending region of CO2 in the Raman spectra of these anionic clusters shows a characteristic feature for the formation of I2•−.nCO2 clusters showing a Raman band at ∼650 cm−1.
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| - Vibrational Analysis of I2•−.nCO2 Clusters
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