Biomedical subjects

Anant D Kulkarni

Publications and source records attributed to Anant D Kulkarni.

4 recordsLinked to original sources

PubMed2006

Interaction of peroxyformic acid with water molecules: a first-principles study.

The present article comprises a theoretical study of structures and energetics of the lowest energy conformers of peroxyformic acid (PFA) and its hydrated variants, viz. PFA...(H2O)n (n = 1-4), at the molecular level. We have employed two different ab initio quantum chemical methods, viz. restricted Hartree-Fock (RHF) and the second-order Møller-Plesset (MP2) perturbation theory with the basis sets 6-31G(d,p) and 6-311++G(2d,2p). Modifications in the structure as well as vibrational frequencies of PFA brought about by successive addition of H2O molecules are also discussed. Cooperativity of hydrogen bonding in these clusters can be gauged through a detailed many body interaction energy analysis.

Journal Article↗

PubMed2006

Effect of additional hydrogen peroxide to H2O2...(H2O)n, n=1 and 2 complexes: quantum chemical study.

Hydrogen peroxide, H2O2, acts as a particularly strong reactant in aqueous environment. It has been demonstrated earlier that agglomerates with a single peroxide interacting with one and two water molecules manifest in several stable conformers within a narrow energy range. In the present study we seek structural changes brought out by adding an extra H2O2 to these systems at molecular level employing ab initio quantum chemical methods, viz., restricted Hartree-Fock and the second order Moller-Plesset perturbation theory. These clusters exhibit consistent trends in energy hierarchy at both the levels. Further, a many body interaction energy analysis quantifies the strength and cooperativity of hydrogen bonding in the (H2O2)2...(H2O)n, (n=1 and 2) clusters, bringing out structuring/destructuring effects attributed to attachment of water and hydrogen peroxide molecules.

Chemistry, Physical↗

PubMed2005

Structures, energetics, and vibrational spectra of H2O2...(H2O)n, n = 1-6 clusters: Ab initio quantum chemical investigations.

Hydrogen-bonded heteroclusters of H(2)O(2)...(H(2)O)(n)(), with n varying from 1 through 6, have been investigated herein employing ab initio quantum chemical methods. For a given n, several energetically comparable conformers emerge as local minima on the potential energy surface (PES). All of the conformers obtained at restricted Hartree-Fock (RHF) and Møller-Plesset second-order perturbation (MP2) levels of theory exhibit parallel trends in energy hierarchy. The effect of clustering by water on the modification in the vibrational frequencies has also been investigated and further, a many-body interaction-energy analysis is carried out providing insights into cooperativity in H(2)O(2)...(H(2)O)(n)() clusters.

Journal Article↗

PubMed2004

Many-body interaction analysis: algorithm development and application to large molecular clusters.

A completely automated algorithm for performing many-body interaction energy analysis of clusters (MBAC) [M. J. Elrodt and R. J. Saykally, Chem. Rev. 94, 1975 (1994); S. S. Xantheas, J. Chem. Phys. 104, 8821 (1996)] at restricted Hartree-Fock (RHF)/MA Plesset 2nd order perturbation theory (MP2)/density functional theory (DFT) level of theory is reported. Use of superior guess density matrices (DM's) for smaller fragments generated from DM of the parent system and elimination of energetically insignificant higher-body combinations, leads to a more efficient performance (speed-up up to 2) compared to the conventional procedure. MBAC approach has been tested out on several large-sized weakly bound molecular clusters such as (H(2)O)(n), n=8, 12, 16, 20 and hydrated clusters of amides and aldehydes. The MBAC results indicate that the amides interact more strongly with water than aldehydes in these clusters. It also reconfirms minimization of the basis set superposition error for large cluster on using superior quality basis set. In case of larger weakly bound clusters, the contributions higher than four body are found to be repulsive in nature and smaller in magnitude. The reason for this may be attributed to the increased random orientations of the interacting molecules separated from each other by large distances.

Journal Article↗