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Methyl hydrogen peroxide dimer: A structural study |
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| Authors: | Anant D Kulkarni Dhurba Rai Libero J Bartolotti Rajeev K Pathak |
| Institution: | aDepartment of Chemistry, University of Pune, Pune 411 007, India bDepartment of Physics, University of Pune, Pune 411 007, India cDepartment of Chemistry, East Carolina University, Science and Technology Building, Suite 300, Greenville, NC 27858-4353, USA dDepartment of Physics, P. Stern Hall, Tulane University, New Orleans, LA 70118, USA |
| Abstract: | Methyl hydrogen peroxide (MHP) exhibits a tendency to form a stable dimer by hydrogen-bonding. Ab initio theoretical investigations on methyl hydrogen peroxide dimer (MHPD) carried out herein lead to several energetically stable structures that have a direct bearing on the reactivity of the monomer in terms of its molecular electrostatic potential (MESP). To gauge the role played by the electron-correlation in lending stability to MHP and its dimer, we employ the density functional theory (DFT) (as implemented by B3LYP-functional), and subsequently second order Møller-Plesset (MP2) perturbation theory, using the basis sets 6-31G(d, p) and 6-311++G(2d, 2p). Simulated infra-red vibrational spectra lead to spectral intensity redistribution upon dimerization. Energetically the lowest MHPD is endowed with inversion symmetry and has two hydrogen bonds, while three other structures emerge: one energetically very close with two H-bonds, and the two others, with three H-bonds each, yet higher by about 2 kcal mol?1. |
| Keywords: | Methyl hydrogen peroxide Density functional theory Hydrogen bonding MP2 Molecular electrostatic potential Vibrational frequencies |
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