• Anuja P Rahalkar

      Articles written in Journal of Chemical Sciences

    • Molecular tailoring approach for exploring structures, energetics and properties of clusters

      Shridhar R Gadre K V Jovan Jose Anuja P Rahalkar

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      Molecular Tailoring Approach (MTA) is a method developed for enabling ab initio calculations on prohibitively large molecules or atomic/molecular clusters. A brief review of MTA, a linear scaling technique based on set inclusion and exclusion principle, is provided. The Molecular Electrostatic Potential (MESP) of smaller clusters is exploited for building initial geometries for the larger ones, followed by MTA geometry optimization. The applications of MTA are illustrated with a few test cases such as (CO2)$_n$ and Li$_n$ clusters employing Density Functional theory (DFT) and a nanocluster of orthoboric acid at the Hartree-Fock (HF) level. Further, a discussion on the geometries and energetics of benzene tetramers and pentamers, treated at the Møller-Plesset second order (MP2) perturbation theory, is given. MTA model is employed for evaluating some cluster properties viz. adiabatic ionization potential, MESP, polarizability, Hessian matrix and infrared frequencies. These property evaluations are carried out on a series of test cases and are seen to offer quite good agreement with those computed by an actual calculation. These case studies highlight the advantages of MTA model calculations vis-à-vis the actual ones with reference to the CPU-time, memory requirements and accuracy.

    • Tailoring approach for obtaining molecular orbitals of large systems

      Anuja P Rahalkar Shridhar R Gadre

      More Details Abstract Fulltext PDF

      Molecular orbitals (MO’s) within Hartree-Fock (HF) theory are of vital importance as they provide preliminary information of bonding and features such as electron localization and chemical reactivity. The contemporary literature treats the Kohn-Sham orbitals within density functional theory (DFT) equivalently to the MO's obtained within HF framework. The high scaling order of ab initio methods is the main hurdle in obtaining the MO's for large molecular systems. With this view, an attempt is made in the present work to employ molecular tailoring approach (MTA) for obtaining the complete set of MO's including occupied and virtual orbitals, for large molecules at HF and B3LYP levels of theory. The energies of highest occupied and lowest unoccupied molecular orbitals, and hence the band gaps, are accurately estimated by MTA for most of the test cases benchmarked in this study, which include 𝜋-conjugated molecules. Typically, the root mean square errors of valence MO's are in range of 0.001 to 0.010 a.u. for all the test cases examined. MTA shows a time advantage factor of 2 to 3 over the corresponding actual calculation, for many of the systems reported.

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