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

Abstract

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.