Quantum/classical simulation of molecular excited state dynamics and spectroscopy

The ability of modern quantum chemistry to answer ever more complex questions rises steadily. In this thesis, a comprehensive exploration of molecular photochemistry using high-level electronic structure methods for quantum-classical dynamics is presented. The first chapter introduces theoretical methods for simulating photodynamical processes, focussing on the relaxation of molecules in explicit atomistic environments. These approaches include nuclear wavepacket dynamics embedded within classical molecular dynamics. The presented Ehrenfest and multi-configurational Ehrenfest approaches are applied to small molecules surrounded by noble gas atoms. Furthermore, trajectory surface hopping is discussed, as, in later chapters, the program SHARC is used to perform such simulations. During this thesis, adaptive time-stepping and two new interfaces to electronic structure codes were implemented. These methods facilitate efficient and accurate dynamics calculations on a variety of photochemically relevant systems ranging from simulations in the gas phase with high-level XMS-CASPT2 electronic structure (including spin-orbit couplings) to QM/MM simulations in the condensed phase. The second chapter focuses on the energy transfer between an infrared laser and solvated molecules, combining the traditional harmonic approximation to calculate infrared spectra with methods based on \textit{ab initio} molecular dynamics. This methodology is used to elucidate the coherent energy transfer dynamics from the field to the molecule in field-resolved spectroscopic measurements. The third chapter of this thesis surveys the intricate world of 2-enone photochemistry. By exploring $\pi\pi^*$ and $n\pi^*$ reactivity using high-level electronic structure methods, insights are gained into the \textit{Z}/\textit{E} isomerization of cyclohept-2-enone and the photoinduced rearrangement of 5,5-dimethylcyclopent-2-enone to a ketene. In the final chapter, mechanistic investigations are extended to Lewis acid\hyp coordinated enones, uncovering the impact of coordination on the electronic states, UV-Vis spectra, and reactivity. Trajectory surface hopping calculations are used in combination with ultrafast transient absorption spectroscopy to uncover the dynamics of the relaxation of cyclohex-2-enone-BF$_3$ to the reactive triplet states and the photo-induced B\textendash Cl bond dissociation in benzaldehyde-BCl$_3$. Collectively, this work exemplifies the potent synergy of computational and spectroscopic techniques in unraveling photochemical mechanisms. From explicit solvent relaxation to multi-step organic reactions and from spectroscopic signatures to intricate electronic transitions, this thesis advances our understanding of photochemical processes across a spectrum of molecular examples. The findings have implications for the design and understanding of photochemical reactions and spectroscopic studies in complex environments

The role of azacitidine in the management of myelodysplastic syndromes (MDS)

Myelodysplastic syndromes (MDS) are a group of common bone marrow disorders characterized by ineffective hematopoiesis, peripheral cytopenias, and a propensity for transformation to acute myeloid leukemia (AML). For many years, the main treatment option for MDS was best supportive care which alleviates symptoms but has no effect on the natural course of the disease. The recent approval of the demethylating agent azacitidine represents a significant advance in the treatment of MDS. The results of two randomized trials with azacitidine have shown an overall response rate between 40% and 60%, an improved quality of life, a reduced risk of transformation to AML and a definite survival advantage compared to best supportive care or low-dose chemotherapy. Current data on azacitidine and its place in the treatment of MDS are reviewed

Spectral Density of the Two-Impurity Anderson Model

We investigate static and dynamical ground-state properties of the two-impurity Anderson model at half filling in the limit of vanishing impurity separation using the dynamical density-matrix renormalization group method. In the weak-coupling regime, we find a quantum phase transition as function of inter-impurity hopping driven by the charge degrees of freedom. For large values of the local Coulomb repulsion, the transition is driven instead by a competition between local and non-local magnetic correlations. We find evidence that, in contrast to the usual phenomenological picture, it seems to be the bare effective exchange interactions which trigger the observed transition.Comment: 18 pages, 6 figures, submitted to J. Phys.:Condens. Matte

Photonic Bloch oscillations and Zener tunneling in two-dimensional optical lattices

We report on the first experimental observation of photonic Bloch oscillations and Zener tunneling in two-dimensional periodic systems. We study the propagation of an optical beam in a square photonic lattice superimposed on a refractive index ramp, and demonstrate the tunneling of light from the first to the higher-order transmission bands of the lattice bandgap spectrum, associated with the spectral dynamics inside the first Brillouin zone and corresponding oscillations of the primary beam.Comment: 4 pages, 4 figure

Experimental evidence of spontaneous symmetry breaking in intracavity type-II second harmonic generation with triple resonance

We describe an experiment showing a spontaneous symmetry breaking phenomenon between the intensities of the ordinary and extraordinary components of the fundamental field in intracavity type-II harmonic generation. It is based on a triply resonant dual cavity containing a type II phase matched $\chi^{(2)}$ crystal pumped at the fundamental frequency $\omega_0$. The pump beam generates in the cavity a second harmonic mode at frequency $2\omega_0$ which acts as a pump for frequency degenerate type II parametric down conversion. Under operating conditions which are precisely symmetric with respect to the ordinary and extraordinary components of the fundamental wave, we have observed a breaking of the symmetry on the intensities of these two waves in agreement with the theoretical predictions.Comment: submitte

Lasing modes in ZnO nanowires coupled to planar metals

Semiconductor nanowire lasers can be subject to modifications of their lasing threshold resulting from a variation of their environment. A promising choice is to use metallic substrates to gain access to low-volume Surface-Plasmon-Polariton (SPP) modes. We introduce a simple, yet quantitatively precise model that can serve to describe mode competition in nanowire lasers on metallic substrates. We show that an aluminum substrate can decrease the lasing threshold for ZnO nanowire lasers while for a silver substrate, the threshold increases compared with a dielectric substrate. Generalizing from these findings, we make predictions describing the interaction between planar metals and semiconductor nanowires, which allow to guide future improvements of highly-integrated laser sources

Design of an imaging spectrometer for Earth observation using freeform mirrors

Design of an imaging spectrometer for earth observation using freeform mirrors Thomas Peschel1, Christoph Damm1, Matthias Beier1, Andreas Gebhard1, Stefan Risse1, Ingo Walter2, Ilse Sebastian2, David Krutz2 1 Fraunhofer Institut für Angewandte Optik und Feinwerktechnik, Jena 2 DLR, Institut für Optische Sensorsysteme, Berlin In 2017 the new hyperspectral DLR Earth Sensing Imaging Spectrometer (DESIS) will be integrated in the Multi-User-System for Earth Sensing (MUSES) platform /1/ installed on the International Space Station (ISS). The DESIS instrument is developed under the responsibility of the DLR. It will deliver images of the earth with a spatial resolution of 30 m on ground in 235 spectral channels in the wavelength range from 400 nm to 1 µm. As partner of the development team Fraunhofer IOF is responsible for the optical system of the imaging spectrometer.The optical system is made of two primary components: A compact Three-Mirror-Anastigmat (TMA) telescope images the ground strip under observation onto a slit. The following spectrometer reimages the slit onto the detector and performs the spectral separation using a reflective grating. The whole optical system is realized using metal-based mirrors the surfaces of which are made by Single-Point-Diamond Turning (SPDT). Since the spectral range is in the visible, a post-processing of the surfaces by Nickel plating is necessary. The final surface shape and roughness are realized by a second SPDT step and subsequent Magneto-Rheological Finishing. The TMA provides a focal length of 320 mm and an aperture of F/2.8. Its mechanical design relies on the Duolith-technology of IOF as well as optical and mechanical reference structures on the mirrors /2/ manufactured in the same SPDT run. This strategy allows for a significantly simplified adjustment of the optical system /3/. The spectrometer was designed on the basis of the so-called Offner scheme. Because of the high aperture of the system a freeform mirror had to be introduced in order to provide a good imaging quality over the whole spectral range. The above optical design requires a grating on a curved surface. Technologies are developed in order to fabricate the grating either by SPDT or, alternatively, by laser lithography. The mechanical design uses light-weight housing elements which wrap the optical path to suppress stray light. An athermal design is provided by using the same metal for mirrors and housing. To provide high adjustment precision, the housing elements carry reference and mounting features made by SPDT as well. This approach allows for a stiff mechanical set-up of the system, which is compatible with the harsh requirements of a space flight. References: 1 N. Humphrey, “A View From Above: Imaging from the ISS”, Teledyne DALSA 2014, http://possibility.teledynedalsa.com/a-view-from-above/ 2 S. Scheiding, e.a., “Ultra-precisely manufactured mirror assemblies with well-defined reference structures“, Proc. SPIE 7739, 2010. 3 T. Peschel, e.a., “Anamorphotic telescope for earth observation in the mid-infrared range”, ICSO 201

Entanglement and boundary critical phenomena

We investigate boundary critical phenomena from a quantum information perspective. Bipartite entanglement in the ground state of one-dimensional quantum systems is quantified using the Renyi entropy S_alpha, which includes the von Neumann entropy (alpha=1) and the single-copy entanglement (alpha=infinity) as special cases. We identify the contribution from the boundary entropy to the Renyi entropy, and show that there is an entanglement loss along boundary renormalization group (RG) flows. This property, which is intimately related to the Affleck-Ludwig g-theorem, can be regarded as a consequence of majorization relations between the spectra of the reduced density matrix along the boundary RG flows. We also point out that the bulk contribution to the single-copy entanglement is half of that to the von Neumann entropy, whereas the boundary contribution is the same.Comment: 4 pages, 2 figure

A Bosonic Model of Hole Pairs

We numerically investigate a bosonic representation for hole pairs on a two-leg t-J ladder where hard core bosons on a chain represent the hole pairs on the ladder. The interaction between hole pairs is obtained by fitting the density profile obtained with the effective model to the one obtained with the \tj model, taking into account the inner structure of the hole pair given by the hole-hole correlation function. For these interactions we calculate the Luttinger liquid parameter, which takes the universal value $K_{\rho}=1$ as half filling is approached, for values of the rung exchange $J'$ between strong coupling and the isotropic case. The long distance behavior of the hole-hole correlation function is also investigated. Starting from large $J'$, the correlation length first increases as expected, but diminishes significantly as $J'$ is reduced and bound holes sit mainly on adjacent rungs. As the isotropic case is approached, the correlation length increases again. This effect is related to the different kind of bonds in the region between the two holes of a hole pair when they move apart.Comment: 11 page