Quantum effects and dynamics in hydrogen-bonded systems: a first-principles approach to spectroscopic experiments

Computer simulations have become an important tool in physics. Especially systems in the solid state have been investigated extensively with the help of modern computational methods. This thesis focuses on the simulation of hydrogen-bonded systems, using quantum chemical methods combined with molecular dynamics (MD) simulations. MD simulations are carried out for investigating the energetics and structure of a system under conditions that include physical parameters such as temperature and pressure. Ab initio quantum chemical methods have proven to be capable of predicting spectroscopic quantities. The combination of these two features still represents a methodological challenge. Furthermore, conventional MD simulations consider the nuclei as classical particles. Not only motional effects, but also the quantum nature of the nuclei are expected to influence the properties of a molecular system. This work aims at a more realistic description of properties that are accessible via NMR experiments. With the help of the path integral formalism the quantum nature of the nuclei has been incorporated and its influence on the NMR parameters explored. The effect on both the NMR chemical shift and the Nuclear Quadrupole Coupling Constants (NQCC) is presented for intra- and intermolecular hydrogen bonds. The second part of this thesis presents the computation of electric field gradients within the Gaussian and Augmented Plane Waves (GAPW) framework, that allows for all-electron calculations in periodic systems. This recent development improves the accuracy of many calculations compared to the pseudopotential approximation, which treats the core electrons as part of an effective potential. In combination with MD simulations of water, the NMR longitudinal relaxation times for 17O and 2H have been obtained. The results show a considerable agreement with the experiment. Finally, an implementation of the calculation of the stress tensor into the quantum chemical program suite CP2K is presented. This enables MD simulations under constant pressure conditions, which is demonstrated with a series of liquid water simulations, that sheds light on the influence of the exchange-correlation functional used on the density of the simulated liquid.

On the renormalization flow representation of field theory and some applications

In this thesis we discuss a representation of quantum mechanics and quantum and statistical field theory based on a functional renormalization flow equation for the one-particle-irreducible average effective action, and we employ it to get information on some specific systems.

Superfluid and antiferromagnetic phases in ultracold fermionic quantum gases

In this thesis several models are treated, which are relevant for ultracold fermionic quantum gases loaded onto optical lattices. In particular, imbalanced superfluid Fermi mixtures, which are considered as the best way to realize Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) states experimentally, and antiferromagnetic states, whose experimental realization is one of the next major goals, are examined analytically and numerically with the use of appropriate versions of the Hubbard model.rnrnThe usual Bardeen-Cooper-Schrieffer (BCS) superconductor is known to break down in a magnetic field with a strength exceeding the size of the superfluid gap. A spatially inhomogeneous spin-imbalanced superconductor with a complex order parameter known as FFLO-state is predicted to occur in translationally invariant systems. Since in ultracold quantum gases the experimental setups have a limited size and a trapping potential, we analyze the realistic situation of a non-translationally invariant finite sized Hubbard model for this purpose. We first argue analytically, why the order parameter should be real in a system with continuous coordinates, and map our statements onto the Hubbard model with discrete coordinates defined on a lattice. The relevant Hubbard model is then treated numerically within mean field theory. We show that the numerical results agree with our analytically derived statements and we simulate various experimentally relevant systems in this thesis.rnrnAnalogous calculations are presented for the situation at repulsive interaction strength where the N'eel state is expected to be realized experimentally in the near future. We map our analytical results obtained for the attractive model onto corresponding results for the repulsive model. We obtain a spatially invariant unit vector defining the direction of the order parameter as a consequence of the trapping potential, which is affirmed by our mean field numerical results for the repulsive case. Furthermore, we observe domain wall formation, antiferromagnetically induced density shifts, and we show the relevant role of spin-imbalance for antiferromagnetic states.rnrnSince the first step for understanding the physics of the examined models was the application of a mean field approximation, we analyze the effect of including the second order terms of the weak coupling perturbation expansion for the repulsive model. We show that our results survive the influence of quantum fluctuations and show that the renormalization factors for order parameters and critical temperatures lead to a weaker influence of the fluctuations on the results in finite sized systems than on the results in the thermodynamical limit. Furthermore, in the context of second order theory we address the question whether results obtained in the dynamical mean field theory (DMFT), which is meanwhile a frequently used method for describing trapped systems, survive the effect of the non-local Feynman diagrams neglected in DMFT.

New developments in state-specific multireference coupled-cluster theory

Coupled-cluster theory in its single-reference formulation represents one of the most successful approaches in quantum chemistry for the description of atoms and molecules. To extend the applicability of single-reference coupled-cluster theory to systems with degenerate or near-degenerate electronic configurations, multireference coupled-cluster methods have been suggested. One of the most promising formulations of multireference coupled cluster theory is the state-specific variant suggested by Mukherjee and co-workers (Mk-MRCC). Unlike other multireference coupled-cluster approaches, Mk-MRCC is a size-extensive theory and results obtained so far indicate that it has the potential to develop to a standard tool for high-accuracy quantum-chemical treatments. This work deals with developments to overcome the limitations in the applicability of the Mk-MRCC method. Therefore, an efficient Mk-MRCC algorithm has been implemented in the CFOUR program package to perform energy calculations within the singles and doubles (Mk-MRCCSD) and singles, doubles, and triples (Mk-MRCCSDT) approximations. This implementation exploits the special structure of the Mk-MRCC working equations that allows to adapt existing efficient single-reference coupled-cluster codes. The algorithm has the correct computational scaling of d*N^6 for Mk-MRCCSD and d*N^8 for Mk-MRCCSDT, where N denotes the system size and d the number of reference determinants. For the determination of molecular properties as the equilibrium geometry, the theory of analytic first derivatives of the energy for the Mk-MRCC method has been developed using a Lagrange formalism. The Mk-MRCC gradients within the CCSD and CCSDT approximation have been implemented and their applicability has been demonstrated for various compounds such as 2,6-pyridyne, the 2,6-pyridyne cation, m-benzyne, ozone and cyclobutadiene. The development of analytic gradients for Mk-MRCC offers the possibility of routinely locating minima and transition states on the potential energy surface. It can be considered as a key step towards routine investigation of multireference systems and calculation of their properties. As the full inclusion of triple excitations in Mk-MRCC energy calculations is computational demanding, a parallel implementation is presented in order to circumvent limitations due to the required execution time. The proposed scheme is based on the adaption of a highly efficient serial Mk-MRCCSDT code by parallelizing the time-determining steps. A first application to 2,6-pyridyne is presented to demonstrate the efficiency of the current implementation.

Quantum Integrability in Non-Linear Sigma Models related to Gauge/String Correspondences

The Thermodynamic Bethe Ansatz analysis is carried out for the extended-CP^N class of integrable 2-dimensional Non-Linear Sigma Models related to the low energy limit of the AdS_4xCP^3 type IIA superstring theory. The principal aim of this program is to obtain further non-perturbative consistency check to the S-matrix proposed to describe the scattering processes between the fundamental excitations of the theory by analyzing the structure of the Renormalization Group flow. As a noteworthy byproduct we eventually obtain a novel class of TBA models which fits in the known classification but with several important differences. The TBA framework allows the evaluation of some exact quantities related to the conformal UV limit of the model: effective central charge, conformal dimension of the perturbing operator and field content of the underlying CFT. The knowledge of this physical quantities has led to the possibility of conjecturing a perturbed CFT realization of the integrable models in terms of coset Kac-Moody CFT. The set of numerical tools and programs developed ad hoc to solve the problem at hand is also discussed in some detail with references to the code.

Ab initio quantum mechanical investigation of structural and chemical-physical properties of selected minerals for minero-petrological, structural ceramic and biomaterial applications

The purpose of this thesis is the atomic-scale simulation of the crystal-chemical and physical (phonon, energetic) properties of some strategically important minerals for structural ceramics, biomedical and petrological applications. These properties affect the thermodynamic stability and rule the mineral-environment interface phenomena, with important economical, (bio)technological, petrological and environmental implications. The minerals of interest belong to the family of phyllosilicates (talc, pyrophyllite and muscovite) and apatite (OHAp), chosen for their importance in industrial and biomedical applications (structural ceramics) and petrophysics. In this thesis work we have applicated quantum mechanics methods, formulas and knowledge to the resolution of mineralogical problems ("Quantum Mineralogy”). The chosen theoretical approach is the Density Functional Theory (DFT), along with periodic boundary conditions to limit the portion of the mineral in analysis to the crystallographic cell and the hybrid functional B3LYP. The crystalline orbitals were simulated by linear combination of Gaussian functions (GTO). The dispersive forces, which are important for the structural determination of phyllosilicates and not properly con-sidered in pure DFT method, have been included by means of a semi-empirical correction. The phonon and the mechanical properties were also calculated. The equation of state, both in athermal conditions and in a wide temperature range, has been obtained by means of variations in the volume of the cell and quasi-harmonic approximation. Some thermo-chemical properties of the minerals (isochoric and isobaric thermal capacity) were calculated, because of their considerable applicative importance. For the first time three-dimensional charts related to these properties at different pressures and temperatures were provided. The hydroxylapatite has been studied from the standpoint of structural and phonon properties for its biotechnological role. In fact, biological apatite represents the inorganic phase of vertebrate hard tissues. Numerous carbonated (hydroxyl)apatite structures were modelled by QM to cover the broadest spectrum of possible biological structural variations to fulfil bioceramics applications.

The g-factor of the electron bound in 28 Si 13+ : the most stringent test of bound-state quantum electrodynamics

This thesis describes the ultra-precise determination of the g-factor of the electron bound to hydrogenlike 28Si13+. The experiment is based on the simultaneous determination of the cyclotron- and Larmor frequency of a single ion, which is stored in a triple Penning-trap setup. The continuous Stern-Gerlach effect is used to couple the spin of the bound electron to the motional frequencies of the ion via a magnetic bottle, which allows the non-destructive determination of the spin state. To this end, a highly sensitive, cryogenic detection system was developed, which allowed the direct, non-destructive detection of the eigenfrequencies with the required precision.rnThe development of a novel, phase sensitive detection technique finally allowed the determination of the g-factor with a relative accuracy of 40 ppt, which was previously inconceivable. The comparison of the hereby determined value with the value predicted by quantumelectrodynamics (QED) allows the verification of the validity of this fundamental theory under the extreme conditions of the strong binding potential of a highly charged ion. The exact agreement of theory and experiment is an impressive demonstration of the exactness of QED. The experimental possibilities created in this work will allow in the near future not only further tests of theory, but also the determination of the mass of the electron with a precision that exceeds the current literature value by more than an order of magnitude.

Highly accurate quantum chemistry : spin-orbit splittings via multireference coupled-cluster methods and applications in heavy-atom main-group chemistry

Diese Dissertation demonstriert und verbessert die Vorhersagekraft der Coupled-Cluster-Theorie im Hinblick auf die hochgenaue Berechnung von Moleküleigenschaften. Die Demonstration erfolgt mittels Extrapolations- und Additivitätstechniken in der Single-Referenz-Coupled-Cluster-Theorie, mit deren Hilfe die Existenz und Struktur von bisher unbekannten Molekülen mit schweren Hauptgruppenelementen vorhergesagt wird. Vor allem am Beispiel von cyclischem SiS_2, einem dreiatomigen Molekül mit 16 Valenzelektronen, wird deutlich, dass die Vorhersagekraft der Theorie sich heutzutage auf Augenhöhe mit dem Experiment befindet: Theoretische Überlegungen initiierten eine experimentelle Suche nach diesem Molekül, was schließlich zu dessen Detektion und Charakterisierung mittels Rotationsspektroskopie führte. Die Vorhersagekraft der Coupled-Cluster-Theorie wird verbessert, indem eine Multireferenz-Coupled-Cluster-Methode für die Berechnung von Spin-Bahn-Aufspaltungen erster Ordnung in 2^Pi-Zuständen entwickelt wird. Der Fokus hierbei liegt auf Mukherjee's Variante der Multireferenz-Coupled-Cluster-Theorie, aber prinzipiell ist das vorgeschlagene Berechnungsschema auf alle Varianten anwendbar. Die erwünschte Genauigkeit beträgt 10 cm^-1. Sie wird mit der neuen Methode erreicht, wenn Ein- und Zweielektroneneffekte und bei schweren Elementen auch skalarrelativistische Effekte berücksichtigt werden. Die Methode eignet sich daher in Kombination mit Coupled-Cluster-basierten Extrapolations-und Additivitätsschemata dafür, hochgenaue thermochemische Daten zu berechnen.

Higher-order molecular properties and excitation energies in single-reference and multireference coupled-cluster theory

Coupled-cluster (CC) theory is one of the most successful approaches in high-accuracy quantum chemistry. The present thesis makes a number of contributions to the determination of molecular properties and excitation energies within the CC framework. The multireference CC (MRCC) method proposed by Mukherjee and coworkers (Mk-MRCC) has been benchmarked within the singles and doubles approximation (Mk-MRCCSD) for molecular equilibrium structures. It is demonstrated that Mk-MRCCSD yields reliable results for multireference cases where single-reference CC methods fail. At the same time, the present work also illustrates that Mk-MRCC still suffers from a number of theoretical problems and sometimes gives rise to results of unsatisfactory accuracy. To determine polarizability tensors and excitation spectra in the MRCC framework, the Mk-MRCC linear-response function has been derived together with the corresponding linear-response equations. Pilot applications show that Mk-MRCC linear-response theory suffers from a severe problem when applied to the calculation of dynamic properties and excitation energies: The Mk-MRCC sufficiency conditions give rise to a redundancy in the Mk-MRCC Jacobian matrix, which entails an artificial splitting of certain excited states. This finding has established a new paradigm in MRCC theory, namely that a convincing method should not only yield accurate energies, but ought to allow for the reliable calculation of dynamic properties as well. In the context of single-reference CC theory, an analytic expression for the dipole Hessian matrix, a third-order quantity relevant to infrared spectroscopy, has been derived and implemented within the CC singles and doubles approximation. The advantages of analytic derivatives over numerical differentiation schemes are demonstrated in some pilot applications.

Entanglement entropy in 1-d quantum spin chains

In questa tesi abbiamo studiato il comportamento delle entropie di Entanglement e dello spettro di Entanglement nel modello XYZ attraverso delle simulazioni numeriche. Le formule per le entropie di Von Neumann e di Renyi nel caso di una catena bipartita infinita esistevano già, ma mancavano ancora dei test numerici dettagliati. Inoltre, rispetto alla formula per l'Entropia di Entanglement di J. Cardy e P. Calabrese per sistemi non critici, tali relazioni presentano delle correzioni che non hanno ancora una spiegazione analitica: i risultati delle simulazioni numeriche ne hanno confermato la presenza. Abbiamo inoltre testato l'ipotesi che lo Schmidt Gap sia proporzionale a uno dei parametri d'ordine della teoria, e infine abbiamo simulato numericamente l'andamento delle Entropie e dello spettro di Entanglement in funzione della lunghezza della catena di spin. Ciò è stato possibile solo introducendo dei campi magnetici ''ad hoc'' nella catena, con la proprietà che l'andamento delle suddette quantità varia a seconda di come vengono disposti tali campi. Abbiamo quindi discusso i vari risultati ottenuti.

Spectral theory of differential operators on finite metric graphs and on bounded domains

Die vorliegende Arbeit widmet sich der Spektraltheorie von Differentialoperatoren auf metrischen Graphen und von indefiniten Differentialoperatoren auf beschränkten Gebieten. Sie besteht aus zwei Teilen. Im Ersten werden endliche, nicht notwendigerweise kompakte, metrische Graphen und die Hilberträume von quadratintegrierbaren Funktionen auf diesen betrachtet. Alle quasi-m-akkretiven Laplaceoperatoren auf solchen Graphen werden charakterisiert, und Abschätzungen an die negativen Eigenwerte selbstadjungierter Laplaceoperatoren werden hergeleitet. Weiterhin wird die Wohlgestelltheit eines gemischten Diffusions- und Transportproblems auf kompakten Graphen durch die Anwendung von Halbgruppenmethoden untersucht. Eine Verallgemeinerung des indefiniten Operators $-tfrac{d}{dx}sgn(x)tfrac{d}{dx}$ von Intervallen auf metrische Graphen wird eingeführt. Die Spektral- und Streutheorie der selbstadjungierten Realisierungen wird detailliert besprochen. Im zweiten Teil der Arbeit werden Operatoren untersucht, die mit indefiniten Formen der Art $langlegrad v, A(cdot)grad urangle$ mit $u,vin H_0^1(Omega)subset L^2(Omega)$ und $OmegasubsetR^d$ beschränkt, assoziiert sind. Das Eigenwertverhalten entspricht in Dimension $d=1$ einer verallgemeinerten Weylschen Asymptotik und für $dgeq 2$ werden Abschätzungen an die Eigenwerte bewiesen. Die Frage, wann indefinite Formmethoden für Dimensionen $dgeq 2$ anwendbar sind, bleibt offen und wird diskutiert.

Probing quantum chromodynamics with the ATLAS detector : charged-particle event shape variables and the dijet cross-section

Die Quantenchromodynamik ist die zugrundeliegende Theorie der starken Wechselwirkung und kann in zwei Bereiche aufgeteilt werden. Harte Streuprozesse, wie zum Beispiel die Zwei-Jet-Produktion bei hohen invarianten Massen, können störungstheoretisch behandelt und berechnet werden. Bei Streuprozessen mit niedrigen Impulsüberträgen hingegen ist die Störungstheorie nicht mehr anwendbar und phänemenologische Modelle werden für Vorhersagen benutzt. Das ATLAS Experiment am Large Hadron Collider am CERN ermöglicht es, QCD Prozesse bei hohen sowie niedrigen Impulsüberträgen zu untersuchen. In dieser Arbeit werden zwei Analysen vorgestellt, die jeweils ihren Schwerpunkt auf einen der beiden Regime der QCD legen:rnDie Messung von Ereignisformvariablen bei inelastischen Proton--Proton Ereignissen bei einer Schwerpunktsenergie von $sqrt{s} = unit{7}{TeV}$ misst den transversalen Energiefluss in hadronischen Ereignissen. rnDie Messung des zweifachdifferentiellen Zwei-Jet-Wirkungsquerschnittes als Funktion der invarianten Masse sowie der Rapiditätsdifferenz der beiden Jets mit den höchsten Transversalimpulsen kann genutzt werden um Theorievorhersagen zu überprüfen. Proton--Proton Kollisionen bei $sqrt{s} = unit{8}{TeV}$, welche während der Datennahme im Jahr 2012 aufgezeichnet wurden, entsprechend einer integrierten Luminosität von $unit{20.3}{fb^{-1}}$, wurden analysiert.rn

Exact quantum Monte Carlo methods for correlated electron systems

Thema dieser Arbeit ist die Entwicklung und Kombination verschiedener numerischer Methoden, sowie deren Anwendung auf Probleme stark korrelierter Elektronensysteme. Solche Materialien zeigen viele interessante physikalische Eigenschaften, wie z.B. Supraleitung und magnetische Ordnung und spielen eine bedeutende Rolle in technischen Anwendungen. Es werden zwei verschiedene Modelle behandelt: das Hubbard-Modell und das Kondo-Gitter-Modell (KLM). In den letzten Jahrzehnten konnten bereits viele Erkenntnisse durch die numerische Lösung dieser Modelle gewonnen werden. Dennoch bleibt der physikalische Ursprung vieler Effekte verborgen. Grund dafür ist die Beschränkung aktueller Methoden auf bestimmte Parameterbereiche. Eine der stärksten Einschränkungen ist das Fehlen effizienter Algorithmen für tiefe Temperaturen.rnrnBasierend auf dem Blankenbecler-Scalapino-Sugar Quanten-Monte-Carlo (BSS-QMC) Algorithmus präsentieren wir eine numerisch exakte Methode, die das Hubbard-Modell und das KLM effizient bei sehr tiefen Temperaturen löst. Diese Methode wird auf den Mott-Übergang im zweidimensionalen Hubbard-Modell angewendet. Im Gegensatz zu früheren Studien können wir einen Mott-Übergang bei endlichen Temperaturen und endlichen Wechselwirkungen klar ausschließen.rnrnAuf der Basis dieses exakten BSS-QMC Algorithmus, haben wir einen Störstellenlöser für die dynamische Molekularfeld Theorie (DMFT) sowie ihre Cluster Erweiterungen (CDMFT) entwickelt. Die DMFT ist die vorherrschende Theorie stark korrelierter Systeme, bei denen übliche Bandstrukturrechnungen versagen. Eine Hauptlimitation ist dabei die Verfügbarkeit effizienter Störstellenlöser für das intrinsische Quantenproblem. Der in dieser Arbeit entwickelte Algorithmus hat das gleiche überlegene Skalierungsverhalten mit der inversen Temperatur wie BSS-QMC. Wir untersuchen den Mott-Übergang im Rahmen der DMFT und analysieren den Einfluss von systematischen Fehlern auf diesen Übergang.rnrnEin weiteres prominentes Thema ist die Vernachlässigung von nicht-lokalen Wechselwirkungen in der DMFT. Hierzu kombinieren wir direkte BSS-QMC Gitterrechnungen mit CDMFT für das halb gefüllte zweidimensionale anisotrope Hubbard Modell, das dotierte Hubbard Modell und das KLM. Die Ergebnisse für die verschiedenen Modelle unterscheiden sich stark: während nicht-lokale Korrelationen eine wichtige Rolle im zweidimensionalen (anisotropen) Modell spielen, ist in der paramagnetischen Phase die Impulsabhängigkeit der Selbstenergie für stark dotierte Systeme und für das KLM deutlich schwächer. Eine bemerkenswerte Erkenntnis ist, dass die Selbstenergie sich durch die nicht-wechselwirkende Dispersion parametrisieren lässt. Die spezielle Struktur der Selbstenergie im Impulsraum kann sehr nützlich für die Klassifizierung von elektronischen Korrelationseffekten sein und öffnet den Weg für die Entwicklung neuer Schemata über die Grenzen der DMFT hinaus.

Planck stars: theory and phenomenology

General Relativity (GR) is one of the greatest scientific achievements of the 20th century along with quantum theory. Despite the elegance and the accordance with experimental tests, these two theories appear to be utterly incompatible at fundamental level. Black holes provide a perfect stage to point out these difficulties. Indeed, classical GR fails to describe Nature at small radii, because nothing prevents quantum mechanics from affecting the high curvature zone, and because classical GR becomes ill-defined at r = 0 anyway. Rovelli and Haggard have recently proposed a scenario where a negative quantum pressure at the Planck scales stops and reverts the gravitational collapse, leading to an effective “bounce” and explosion, thus resolving the central singularity. This scenario, called Black Hole Fireworks, has been proposed in a semiclassical framework. The purpose of this thesis is twofold: - Compute the bouncing time by means of a pure quantum computation based on Loop Quantum Gravity; - Extend the known theory to a more realistic scenario, in which the rotation is taken into account by means of the Newman-Janis Algorithm.