With a scanning tunneling microscope (STM), it is possible to study single atoms, the building blocks of all materials.
For STM measurements, these atoms, though, must in general always reside on a conducting surface, which affects them.
This thesis concerns the influence of a metal surface on measurements of three specific atomic systems.

The first system is chains of classical spins on a superconductor giving rise to Yu-Shiba-Rusinov in-gap band dispersion. We present a short junction surface scattering theory to evaluate the effective Hamiltonian of this dispersion, requiring only the unperturbed chain Hamiltonian and the Fermi self-energy of the surface.

The second system is field-emission resonances, which behave like artificial atoms when confined by chlorine vacancies on copper nitride and the STM tip. We use density function theory (DFT) to get increased insight into their lifetimes.

The final system is titanium atomic magnets, which can be coherently driven by electron spin resonance (ESR). We model these systems using open system dynamics to find what coherent operations are possible given the quantum coherence. Specific operations studied are a coherent flip-flop interaction between an electron and a nuclear spin, a proposal to create and detect entanglement, and, in the outlook, coherent spin evolution in spin chains.

Nuclear spins owe their long-lived magnetic states to their excellent isolation from the environment. At the same time, a finite degree of interaction with their surroundings is necessary for reading and writing the spin state. Therefore, detailed knowledge of and control over the atomic environment of a nuclear spin is key to optimizing conditions for quantum information applications. While various platforms enabled single-shot readout of nuclear spins, their direct environments were either unknown or impossible to controllably modify on the atomic scale. Scanning tunneling microscopy (STM), combined with electron spin resonance (ESR), provides atomic-scale information of individual nuclear spins via the hyperfine interaction. Here, we demonstrate single-shot readout of an individual ⁴⁹Ti nuclear spin with an STM. Employing a pulsed measurement scheme, we find its lifetime to be in the order of seconds. Furthermore, we shed light on the pumping and relaxation mechanisms of the nuclear spin by investigating its response to both ESR driving and tunneling current, which is supported by model calculations. These findings give an atomic-scale insight into the nature of nuclear spin relaxation and are relevant for the development of atomically assembled qubit platforms.

The nuclear spin, being much more isolated from the environment than its electronic counterpart, presents opportunities for quantum experiments with prolonged coherence times. Electron spin resonance (ESR) combined with scanning tunnelling microscopy (STM) provides a bottom-up platform to study the fundamental properties of nuclear spins of single atoms on a surface. However, access to the time evolution of nuclear spins remained a challenge. Here, we present an experiment resolving the nanosecond coherent dynamics of a hyperfine-driven flip-flop interaction between the spin of an individual nucleus and that of an orbiting electron. We use the unique local controllability of the magnetic field emanating from the STM probe tip to bring the electron and nuclear spins in tune, as evidenced by a set of avoided level crossings in ESR-STM. Subsequently, we polarize both spins through scattering of tunnelling electrons and measure the resulting free evolution of the coupled spin system using a DC pump-probe scheme. The latter reveals a complex pattern of multiple interfering coherent oscillations, providing unique insight into hyperfine physics on a single atom level.

Certifying quantum entanglement is a critical step toward realizing quantum-coherent applications. In this work, we show that entanglement of spins can be unambiguously evidenced in a scanning tunneling microscope with electron spin resonance by exploiting the fact that entangled states undergo a free time evolution with a distinct characteristic time constant that clearly distinguishes it from the time evolution of non-entangled states. By implementing a phase control scheme, the phase of this time evolution can be mapped back onto the population of one entangled spin, which can then be read out reliably using a weakly coupled sensor spin in the junction of the scanning tunneling microscope. We demonstrate through open quantum system simulations with currently available spin coherence times of T2 ≈ 300 ns, that a signal directly correlated with the degree of entanglement can be measured at temperatures of 100–400 mK accessible in sub-Kelvin scanning tunneling microscopes.

Atomically engineered artificial lattices are a useful tool for simulating complex quantum phenomena, but have so far been limited to the study of Hamiltonians where electron-electron interactions do not play a role. However, it is precisely the regime in which these interactions do matter where computational times lend simulations a critical advantage over numerical methods. Here, we propose a platform for constructing artificial matter that relies on the confinement of field-emission resonances, a class of vacuum-localized discretized electronic states. We use atom manipulation of surface vacancies in a chlorine-terminated Cu(100) surface to reveal square patches of the underlying metal, thereby creating atomically precise potential wells that host particle-in-a-box modes. By adjusting the dimensions of the confining potential, we can access states with different quantum numbers, making these patches attractive candidates as quantum dots or artificial atoms. We demonstrate that the lifetime of electrons in these engineered states can be extended and tuned through modification of the confining potential, either via atomic assembly or by changing the tip-sample distance. We also demonstrate control over a finite range of state filling, a parameter which plays a key role in the evolution of quantum many-body states. We model the transport through the localized state to disentangle and quantify the lifetime-limiting processes, illustrating the critical dependence of the electron lifetime on the properties of the underlying bulk band structure. The interplay with the bulk bands gives rise to negative differential resistance, leading to possible applications in engineering custom atomic-scale resonant tunnelling diodes, which exhibit similar current-voltage characteristics.

Full insight into the dynamics of a coupled quantum system depends on the ability to follow the effect of a local excitation in real-time. Here, we trace the free coherent evolution of a pair of coupled atomic spins by means of scanning tunneling microscopy. Rather than using microwave pulses, we use a direct-current pump-probe scheme to detect the local magnetization after a current-induced excitation performed on one of the spins. By making use of magnetic interaction with the probe tip, we are able to tune the relative precession of the spins. We show that only if their Larmor frequencies match, the two spins can entangle, causing angular momentum to be swapped back and forth. These results provide insight into the locality of electron spin scattering and set the stage for controlled migration of a quantum state through an extended spin lattice.