Density functional studies on reactivity of first row transition metal oxide clusters in their ground and higher spin states

Abstract

This thesis is the culmination of our efforts to investigate the exciting chemistry of TMOs by using their clusters as computational models with the purpose to exploit them in catalysis. With the advent of supersonic expansion, molecular beam techniques coupled with the state-of-the art computing technology and highly efficient algorithms, extensive and intensive studies by experimentalists and theoreticians have established cluster science as a major domain of research with immense scope. The distinct chemical properties of clusters emerge from a variety of factors, including their very high surface-to-volume ratio, quantum confinement at reduced sizes, and unique geometric and electronic structures. In this context, present work makes significant contributions to the understanding of structure, property and reactivity of TMO clusters. The core of designing a TMO cluster based catalyst lies in understanding the structure-property relationship and unambiguous identification of active sites and mechanisms that govern the reactions. Model systems of size selected clusters in gas phase provide clear perception of these issues. Rigorous and reliable density functional calculations performed in the course of this thesis work provide detailed understanding of the structure, properties and reactivity of first row TMO clusters. It is hoped that these fingerprint calculations will guide the experimentalists to tap the full potential of these materials and synergistic interplay between their experimental studies and computations will be witnessed in near future. newline