Understanding many-electron phenomena with competing near-degenerate electronic states is of fundamental importance to chemistry and condensed matter physics. One of the most significant challenges for exploring such many-electron phenomena is the necessity for large system sizes in order to realize competing states, far beyond those practical for first-principles methods. Here, we show how allowing non-integer nuclear charges expands the space of computationally tractable electron systems that host competing electronic states. The emergence of competing electronic states from non-integer nuclear charges is exemplified in the simple 2electron H 2 molecule and used to examine the microscopic structure of doped quasi-1D cuprate chains, showing how non-integer nuclear charges can open a window for first-principles calculations of difficult many-electron phenomena.Complex materials are those exhibiting many-electron physics emerging from competition between intertwined charge, spin, orbital, and lattice degrees of freedom [1]. While scientifically interesting in their own right, such materials present enormous technological potential as high-temperature superconductors and materials with charge-density wave orders. Understanding the competition between intertwined states remains a key step in controlling these desirable properties and their evolution under external controls like doping, temperature, pressure, and electromagnetic field.Effective Hamiltonian models such as the Hubbard model [2] have been important tools in these studies, e.g., for cuprate superconductors [3,4]. These effective Hamiltonian models provide a generic description of competing electronic states that can be extended to better model specific classes of systems. For example, the 1D Hubbard model with the on-site Coulomb repulsion can be extended to include a near-neighbor attraction to better match