The primary motivation for systematic bases in first principles electronic structure simulations is to derive physical and chemical properties of molecules and solids with predetermined accuracy. This requires a detailed understanding of the asymptotic behaviour of many-particle Coulomb systems near coalescence points of particles. Singular analysis provides a convenient framework to study the asymptotic behaviour of wavefunctions near these singularities. In the present work, we want to introduce the mathematical framework of singular analysis and discuss a novel asymptotic parametrix construction for Hamiltonians of many-particle Coulomb systems. This corresponds to the construction of an approximate inverse of a Hamiltonian operator with remainder given by a so-called Green operator. The Green operator encodes essential asymptotic information and we present as our main result an explicit asymptotic formula for this operator. First applications to many-particle models in quantum chemistry are presented in order to demonstrate the feasibility of our approach. The focus is on the asymptotic behaviour of ladder diagrams, which provide the dominant contribution to short-range correlation in coupled cluster theory. Furthermore, we discuss possible consequences of our asymptotic analysis with respect to adaptive wavelet approximation.

Boundary value problems on a manifold with smooth boundary are closely related to the edge calculus where the boundary plays the role of an edge. The problem of expressing parametrices of Shapiro-Lopatinskij elliptic boundary value problems for differential operators gives rise to pseudo-differential operators with the transmission property at the boundary. However, there are interesting pseudo-differential operators without the transmission property, for instance, the Dirichlet-to-Neumann operator. In this case the symbols become edge-degenerate under a suitable quantisation, cf. Chang et al. (J Pseudo-Differ Oper Appl 5(2014):69-155, 2014). If the boundary itself has singularities, e.g., conical points or edges, then the symbols are corner-degenerate. In the present paper we study elements of the corresponding corner pseudo-differential calculus.

We study spaces on manifolds with double weights and iterated discrete and continuous asymptotics, and their relationship with corner pseudo-differential operators.

We establish a quantisation of corner-degenerate symbols, here called Mellin-edge quantisation, on a manifold with second order singularities. The typical ingredients come from the "most singular" stratum of which is a second order edge where the infinite transversal cone has a base that is itself a manifold with smooth edge. The resulting operator-valued amplitude functions on the second order edge are formulated purely in terms of Mellin symbols taking values in the edge algebra over . In this respect our result is formally analogous to a quantisation rule of (Osaka J. Math. 37:221-260, 2000) for the simpler case of edge-degenerate symbols that corresponds to the singularity order 1. However, from the singularity order 2 on there appear new substantial difficulties for the first time, partly caused by the edge singularities of the cone over that tend to infinity.

We study a new approach to determine the asymptotic behaviour of quantum many-particle systems near coalescence points of particles which interact via singular Coulomb potentials. This problem is of fundamental interest in electronic structure theory in order to establish accurate and efficient models for numerical simulations. Within our approach, coalescence points of particles are treated as embedded geometric singularities in the configuration space of electrons. Based on a general singular pseudo-differential calculus, we provide a recursive scheme for the calculation of the parametrix and corresponding Green operator of a nonrelativistic Hamiltonian. In our singular calculus, the Green operator encodes all the asymptotic information of the eigenfunctions. Explicit calculations and an asymptotic representation for the Green operator of the hydrogen atom and isoelectronic ions are presented.