Oceanic freak waves, optical spikes and extreme events in numerous contexts can arguably be modelled by modulationally unstable solutions within nonlinear systems. In particular, the fundamental nonlinear Schroedinger equation (NLSE) hosts a high-amplitude spatiotemporally localised solution on a plane-wave background, called the Peregrine breather, which is generally considered to be the base-case prototype of a rogue wave. Nonetheless, until very recently, little was known about what to expect when observing or engineering entire clusters of extreme events. Accordingly, this thesis aims to elucidate this matter by investigating complicated structures formed from collections of Peregrine breathers. Many novel NLSE solutions are discovered, all systematically classifiable by their geometry. The methodology employed here is based on the well-established concept of Darboux transformations, by which individual component solutions of an integrable system are nonlinearly superimposed to form a compound wavefunction. It is primarily implemented in a numerical manner within this study, operating on periodically modulating NLSE solutions called breathers. Rogue wave structures can only be extracted at the end of this process, when a limit of zero modulation frequency is applied to all components. Consequently, a requirement for breather asymmetry ensures that a multi-rogue wavefunction must be formed from a triangular number of individual Peregrine breathers (e.g. 1, 3, 6, 10, ...), whether fused or separated. Furthermore, the arrangements of these are restricted by a maximum phase-shift allowable along an evolution trajectory through the relevant wave field. Ultimately, all fundamental high-order rogue wave solutions can be constructed via polynomial relations between origin-translating component shifts and squared modulation frequency ratios. They are simultaneously categorisable by both these mathematical existence conditions and the corresponding visual symmetries, appearing spatiotemporally as triangular cascades, pentagrams, heptagrams, and so on. These parametric relations do not conflict with each other, meaning that any arbitrary NLSE rogue wave solution can be considered a hybridisation of this elementary set. Moreover, this hierarchy of structures is significantly general, with complicated arrangements persisting even on a cnoidal background
