Electronic structure codes are computationally intensive scientic applications used to probe and elucidate chemical processes at an atomic level. Maximizing the performance of these applications on any given hardware platform is vital in order to facilitate larger and more accurate computations. An important part of this endeavor is the development of protocols for measuring performance, and models to describe that performance as a function of system architecture. This thesis makes contributions in both areas, with a focus on shared memory parallel computer architectures and the Gaussian electronic structure code. Shared memory parallel computer systems are increasingly important as hardware man- ufacturers are unable to extract performance improvements by increasing clock frequencies. Instead the emphasis is on using multi-core processors to provide higher performance. These processor chips generally have complex cache hierarchies, and may be coupled together in multi-socket systems which exhibit highly non-uniform memory access (NUMA) characteristics. This work seeks to understand how cache characteristics and memory/thread placement affects the performance of electronic structure codes, and to develop performance models that can be used to describe and predict code performance by accounting for these effects. A protocol for performing memory and thread placement experiments on NUMA systems is presented and its implementation under both the Solaris and Linux operating systems is discussed. A placement distribution model is proposed and subsequently used to guide both memory/thread placement experiments and as an aid in the analysis of results obtained from experiments. In order to describe single threaded performance as a function of cache blocking a simple linear performance model is investigated for use when computing the electron repulsion integrals that lie at the heart of virtually all electronic structure methods. A parametric cache variation study is performed. This is achieved by combining parameters obtained for the linear performance model on existing hardware, with instruction and cache miss counts obtained by simulation, and predictions are made of performance as a function of cache architecture. Extension of the linear performance model to describe multi-threaded performance on complex NUMA architectures is discussed and investigated experimentally. Use of dynamic page migration to improve locality is also considered. Finally the use of large scale electronic structure calculations is demonstrated in a series of calculations aiming to study the charge distribution for a single positive ion solvated within a shell of water molecules of increasing size
