Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 114, Issue 6, Pages 2250-2258Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp909397z
Keywords
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Funding
- Board of Research in Nuclear Sciences (BRNS) Mumbai, India
- Council of Scientific and Industrial Research, New Delhi, India
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The gas-phase geometries, binding energies (BEs), vibrational spectra, and electron density topological features of methanol (M), water (W), and methanol-water mixed clusters (MmWn, where m = 0-4 and n = 0-4; m + n <= 4) have been calculated using Hartree-Fock, second-order Moller-Plesset perturbation, and density functional theory with Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional methods. Bader's atoms in molecules theory has been used to analyze the hydrogen bonding network. To understand the effect of cooperativity, we have performed natural bond orbital analysis and reduced variational space decomposition analysis. The results show that BEs of methanol and mixed clusters are higher than those of water clusters due to the electron-donating nature of the methyl group. These findings are in accordance with the role of cooperative polarization and cooperative charge transfer in the methanol and mixed clusters. As the size of the cluster increases, the contribution from the cooperative effects also increases. The cooperativity contributes similar to 14 and 24% of stabilization in trimers and tetramers, respectively. The calculated nu(OH) frequencies at MP2/6-311++G(d,p) are in close agreement with the corresponding experimental values.
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