Entanglement is one of the most technologically important quantum phenomena and its con-trolled creation brings us a step closer to the realisation of a quantum computer. Hybrid electron and nuclear spin systems which combine long nuclear decoherence times with the high polarisation and rapid processing times of electron spins are considered reliable candidates for the representation of the fundamental building block of a quantum computer, the qubit. In the literature electron spins quite often play the role of a mediator which can access, manipulate and couple states with long coherence times, beneficial for storing quantum information. Despite the fact that an electron spin can be a useful resource for nuclear spin systems, its permanent presence can be a source of decoherence. The use of transient photoexcited electron spins provide an additional advantage and once the operations which involve the electron spin are completed, the electron spin can decay and not interfere further with the evolution of the system. In this thesis we report magnetic resonance experiments and density functional theory calculations for the demonstration of nuclear - nuclear entanglement using photoexcited triplet states. We study homonuclear and heteronuclear fullerene derivatives and we identify in each case the relevant parameters that can lead to high fidelity entangling operations. The hyperfine interaction in a homonuclear system is the key parameter which determines the degree of entanglement between the nucelar spins according to a recent theoretical proposal. We measure and calculate the hyperfine interaction in homonuclear systems with ¹³C nuclear spins in order to prove the feasibility of this scheme. Further experiments on a fullerene system with two nuclear spins a ³¹P and a ¹H show that entangling operations of high fidelity which involve the demonstration of CNOT gates, are possible within the lifetime of the triplet state.

This thesis aims at the methodological developments in Nuclear Magnetic Resonance (NMR). The methodological developments in NMR has a long and successful history. The present thesis attempts to contribute some novel methods in this direction. This thesis restricts itself to two methodological developments, namely, (1) effects of cross-correlations between the chemical shift anisotropy (CSA) and dipole-dipole interactions in the relaxation of various nuclei and experiments which utilize spatial encoding. The cross-correlation has been successfully utilized to investigate the anisotropic motions of liquid crystals, and to understand the chemical shift anisotropy of fluorine atoms of Fluorine substituted ring compounds. Spatial encoding schemes have been developed to facilitate single scan measurements of longitudinal spin lattice relaxation times and implementations of parallel search algorithms.

The vicinity of continuous quantum phase transitions displays unique properties such as scaling behavior and incoherent excitation spectra which are not found in any stable phase of matter. This fascinating quantum critical regime is crucial for progress on key problems of modern condensed matter physics. The three research projects of this thesis challenge and refine our understanding of quantum criticality in different ways. Part I concerns unexpected quantum critical behavior near the Mott transition. The bandwidth-controlled Mott transition in the half-filled one-band Hubbard model is one of the most paradigmatic phenomena of strongly correlated physics. Within the approximation of dynamical mean-field theory (DMFT) this metal-insulator transition is of first order at low temperatures, with the transition line ending at a critical temperature. Surprisingly, numerical calculations with DMFT and experiments in organic salts consistently found quantum critical scaling of the resistivity above the critical temperature. The aim of this project is to explain this unexpected scaling in the absence of a quantum critical point in the phase diagram. To this end, we perform extensive DMFT simulations with the numerical renormalization group as a state-of-the-art impurity solver. We find that the quantum critical scaling can be traced back to the metastable insulator at the boundary of the coexistence region at T = 0 which exhibits previously unknown scale-invariance on the frequency axis. In Part II we study how magnetic quantum criticality is affected by the coupling to additional non-critical degrees of freedom. Considering typical electronic energy scales the study of quantum critical phenomena in magnets requires very low temperatures in the sub-100mK range. In this regime additional effects which are typically neglected in the theoretical modeling may become important. Here we focus on one particular example, which is the hyperfine coupling to nuclear spins. We investigate the fate of the quantum critical behavior at lowest temperatures and determine crossover scales below which a purely electronic description is no longer sufficient. Explicit calculations for paradigmatic models on the level of mean-field theory plus Gaussian fluctuations reveal that the quantum phase transition can be shifted or smeared in the presence of nuclear spins. More exotic effects of nuclear spins, e.g. in spin liquids, are discussed on a qualitative level. Part III is devoted to the discussion of domain-driven phase transitions in easy-axis ferromagnets.This work is motivated by an experimental study of LiHoF4, a dipolar easy-axis ferromagnet that displays a well-studied quantum phase transition from a ferromagnetic to a paramagnetic phase as function of a transverse field. Measurements of the ac susceptibility found a well-defined phase transition even in tilted fields where the Ising symmetry is explicitly broken and Landau theory of the microscopic order parameter predicts a crossover. We are able to explain and model the transition in tilted fields by the inclusion of domain effects, i.e., by taking into account the spontaneous breaking of translational symmetry by mesoscale pattern formation in the ferromagnetic phase. The modeling of stray-field energies as effective antiferromagnetic couplings between magnetization components in different domains is in excellent quantitative agreement with the experimental results.:1 Phases and their transitions . . . . . . . . . . . . . . . . . . . . 4 1.1 Thermal and quantum phase transitions . . . . . . . . . . . . . . . . . . . . 4 1.2 Theoretical description of phase transitions . . . . . . . . . . . . . . . . . . 8 1.3 Project overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 I Mott quantum criticality in the one-band Hubbard model . . . . . . . . . . .15 2 Introduction to the Mott transition . . . . . . . . . . . . . . . . . . . . 16 2.1 Metal-insulator transitions and the Hubbard model . . . . . . . . . . . . . . 16 2.2 A local perspective: the idea of dynamical mean-field theory . . . . . . . . . 19 2.3 Quantum critical scaling near the Mott transition . . . . . . . . . . . . . . . 21 3 Dynamical mean-field theory (DMFT) . . . . . . . . . . . . . . . . . . . . 25 3.1 Single-impurity Anderson model . . . . . . . . . . . . . . . . . . . . . . . . 25 3.2 Theoretical foundations of DMFT . . . . . . . . . . . . . . . . . . . . . . . 28 3.3 Wilson's numerical renormalization group . . . . . . . . . . . . . . . . . . . 32 3.4 Implementation and choice of parameters . . . . . . . . . . . . . . . . . . . 36 4 Power-law spectra and quantum critical scaling . . . . . . . . . . . . . . . . . . 38 4.1 Scale-invariant solutions of DMFT . . . . . . . . . . . . . . . . . . . . . . . 38 4.2 Spectral power laws at T=0 in the metastable insulator . . . . . . . . . . . 40 4.3 Finite-temperature crossovers in the spectral function . . . . . . . . . . . . 47 4.4 Resistivity scaling driven by spectral power laws . . . . . . . . . . . . . . . 50 4.5 Scaling analysis of the dynamic susceptibility . . . . . . . . . . . . . . . . . 58 4.6 Ideas and obstacles towards an analytical understanding . . . . . . . . . . . 62 4.7 Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63 II Limits on magnetic quantum criticality from nuclear spins . . . . . . . . . . . . .65 5 Stability of magnetic transitions to hyperfine coupling . . . . . . . . . . . . . . . .66 5.1 Nuclear spins near quantum criticality . . . . . . . . . . . . . . . . . . . . . 66 5.2 Introduction to nuclear spins and hyperfine coupling . . . . . . . . . . . . . 67 5.3 Magnetic phases in the presence of nuclear spins . . . . . . . . . . . . . . . 69 5.4 Two scenarios for magnetic quantum criticality plus nuclear spins . . . . . . 70 6 Paradigmatic models for magnetic quantum phase transitions . . . . . . . . . 73 6.1 Transverse-field Ising model . . . . . . . . . . . . . . . . . . . . . . . . . . . 73 6.2 Coupled-dimer model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76 6.3 Frustrated spin models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 7 Crossover scales introduced by nuclear spins . . . . . . . . . . . . . . . . . . .83 7.1 Shifted transitions: transverse-field Ising magnets . . . . . . . . . . . . . . . 83 7.2 Smeared transitions: coupled-dimer magnets . . . . . . . . . . . . . . . . . . 90 7.3 Additional transitions due to nuclear spins . . . . . . . . . . . . . . . . . . . 98 7.4 Exotic magnetic quantum phase transitions plus nuclear spins . . . . . . . . 101 7.5 Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102 III Domain-driven phase transitions in easy-axis ferromagnets . . . . . . . . 105 8 Easy-axis ferromagnet LiHoF4 . . . . . . . . . . . . . . . . . . . . 106 8.1 Easy-axis ferromagnets in tilted fields . . . . . . . . . . . . . . . . . . . . . 106 8.2 LiHoF4 and its phase transitions . . . . . . . . . . . . . . . . . . . . . . . . 109 9 Modeling of microscopic degrees of freedom in LiHoF4 . . . . . . . . . . . . 112 9.1 Landau theory in tilted fields . . . . . . . . . . . . . . . . . . . . . . . . . . 112 9.2 Crystal field effects and microscopic Hamiltonian . . . . . . . . . . . . . . . 113 9.3 Crossovers in the microscopic model . . . . . . . . . . . . . . . . . . . . . . 118 10 Modeling of mesoscopic degrees of freedom in LiHoF4 . . . . . . . . . . . . . . .123 10.1 Domains in ferromagnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 10.2 Modeling of domain effects as effective interactions . . . . . . . . . . . . . . 127 10.3 Combined mean-field Hamiltonian and domain optimization . . . . . . . . . 130 10.4 Nature of the phase transition in tilted fields . . . . . . . . . . . . . . . . . 132 10.5 Domain-driven phase transition at T = 0 . . . . . . . . . . . . . . . . . . . . 135 10.6 Domain-driven phase transition at finite temperatures . . . . . . . . . . . . 141 10.7 Comparison with experimental results . . . . . . . . . . . . . . . . . . . . . 146 10.8 Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 IV Summary & Outlook . . . . . . . . . . . . . . . . . . . . 151 V Appendices . . . . . . . . . . . . . . . . . . . . 155 A Part I: NRG level spectra . . . . . . . . . . . . . . . . . . . . 156 B Part I: Analytical properties of scale-invariant DMFT solutions . . . . . . . . . . .159 B.1 Kondo perturbation theory as an impurity solver . . . . . . . . . . . . . . . 159 B.2 Analytical properties of a power-law self-energy . . . . . . . . . . . . . . . . 166 C Part I: Scaling analysis of the resistivity . . . . . . . . . . . . . . . . . . 168 D Part II: Solution of the transverse-field Ising model with nuclear spins . . . . . . 172 D.1 Holstein-Primakoff representation of the electronic and nuclear spins . . . . 172 D.2 Determination of the classical reference state . . . . . . . . . . . . . . . . . 174 D.3 Excitation spectrum of the coupled nuclear-electronic model . . . . . . . . . 175 D.4 Magnetization, susceptibility, and heat capacity . . . . . . . . . . . . . . . . 177 E Part II: Solution of the coupled-dimer model with nuclear spins . . . . . . . . . . . 181 E.1 Bond-operator description of the electronic spins . . . . . . . . . . . . . . . 181 E.2 Determination to the electronic ground state . . . . . . . . . . . . . . . . . 185 E.3 Holstein-Primakoff representation of the nuclear spins . . . . . . . . . . . . 188 E.4 Excitation spectrum of the coupled nuclear-electronic model . . . . . . . . . 189 E.5 Staggered magnetization and susceptibility . . . . . . . . . . . . . . . . . . 192 F Part III: Calculation of domain-induced effective interactions . . . . . . . . . . . . . 198 Bibliography . . . . . . . . . . . . . . . . . . . . 203

Ressonância magnética nuclear é particularmente útil na caracterização de síntese molecular. Quase todos os compostos moleculares de interesse contêm átomos de nitrogênio e oxigênio em sua estrutura. Como esses elementos químicos costumam desempenhar funções estratégicas em reações e interações intra e intermoleculares, seus espectros NMR têm particular interesse. Com foco na blindagem magnética nuclear e no acoplamento entre spins nucleares, investigamos a dependência dessas constantes magnéticas com relação ao meio. A polarização eletrônica e relaxação geométrica do soluto, devido à presença do solvente, foram sistematicamente consideradas utilizando um tratamento sequencial QM/MM. Nossas observações gerais mostram que efeitos de relaxação de geometria mediados pelo meio têm pouca influência sobre o mecanismo da blindagem magnética nuclear, pelo menos quanto aos sistemas aqui investigados. Em contrapartida, os efeitos da polarização eletrônica são cruciais sobre essa propriedade molecular. Para o nitrogênio em piridina, amônia e formamida, por exemplo, as contribuições isoladas provenientes da relaxação geométrica são da ordem de 1,2 ppm. Note-se que este efeito é muito pequeno se considerarmos que com frequência são observados desvios gás-líquido da ordem de -26 ppm para o nitrogênio. Sobre o oxigênio, esses efeitos podem chegar até 100 ppm. Assim, é crucial entender as origens desses efeitos se desejamos utilizar corretamente espectroscopia RMN em caracterização molecular. Relevantes contribuições para a blindagem magnética têm origens em interações específicas entre soluto e solvente, como ligações de hidrogênio, as quais apenas podem ser isoladas e quantificadas através de modelagem molecular. Sistematicamente constatamos que a blindagem magnética é drasticamente afetada pelo caráter doador ou aceitador do sítio atômico envolvido em ligações de hidrogênio. Com respeito ao nitrogênio, nossos resultados indicam que o comportamento aceitador de hidrogênio de um elemento é responsável por um desvio gás-líquido positivo, enquanto que o caráter doador causa um desvio negativo. Nossas investigações também mostram que a blindagem magnética nuclear é independente com relação à hibridização do nitrogênio e oxigênio, indicando que as contribuições principais têm origens em interações específicas soluto-solvente, as quais devem ser corretamente modeladas. Investigamos sistematicamente os efeitos do solvente sobre o acoplamento indireto entre spins nucleares em amônia líquida. Embora a polarização do soluto seja realmente importante, para essa propriedade há outras contribuições fundamentais. Sem considerar efeitos de geometria, calculamos o acoplamento ANTPOT. 1 J(N-H) como -67,8 Hz. Após incluir esses efeitos, conseguimos uma descrição teórica mais apurada, obtendo um acoplamento de -63,9 Hz. Esses resultados mostram que efeitos de relaxação geométrica mediado pelo meio têm grande influência sobre o acoplamento indireto entre spins nucleares. / Nuclear magnetic resonance is helpful on molecular characterization. Most organic molecular compounds of interest contain nitrogen or oxygen atoms which play strategic functions in chemical reactions and molecular interactions. The NMR technique provides local atomic scale information on molecular properties, thus the study of nuclear magnetic properties of these elements in molecules is of particular interest. Focusing on nuclear magnetic shielding and spin-spin coupling constants we investigated the dependence of these magnetic constants with respect to the medium. Electronic polarization and geometry relaxation effects due to solvent were systematically studied. Our general findings indicate that geometry contributions are negligible in understanding the variation of shielding constants of the investigated systems, but polarization effects are crucial for this molecular property. On nitrogen in pyridine, ammonia and formamide, for instance, isolated contributions from geometry relaxation to shielding constants are around 1,2 ppm. Nitrogen shielding constants are very sensitive to the medium, where solvent effects around -26 ppm are often observed. On oxygen-17 magnetic shielding, the solvent effects can easily reach 100 ppm. It is crucial to understand the origins of these effects if one desires to correctly use NMR spectroscopy for molecular characterization. Our investigations also show that magnetic shielding constants are totally independent of the nitrogen or oxygen hybridization, which indicated that the main contributions arise from solute-solvent interactions. Relevant contributions to shielding constants come from specific solute-solvent interactions like hydrogen-bonds, which can only be quantified by explicit molecular modeling, and we observed that this property has a very strong dependence on the donor or acceptor character of the atomic site involved in hydrogen-bonding interactions. On nitrogen, the acceptor behavior is responsible by the positive gas-liquid shift in shielding constants, while the donor character causes positive shift. We systematically investigated the solvent effects on indirect spin-spin coupling constants of liquid ammonia. Solute polarization is very important, but there are other fundamental contributions to this property. Without including geometry effects we calculated the 1J (N-H) coupling to be -67,8 Hz. After accounting for the solute geometry relaxation we improved the theoretical prediction obtaining the coupling constant value of -63,9 Hz. These results show that geometry relaxation has drastic influence on indirect spin-spin coupling constants.

The progess in NMRQIP can be outlined in to four parts.1) Implementation of theoretical protocols on small number of qubits. 2) Demonstration of QIP on various NMR systems. 3) Designing and implementing the algorithms for mixed initial states. 4) Developing the techniques for coherent and decoherent control on higher number(up to 15) of qubits. This thesis contains some efforts in the direction of first three points. Quantum-state discrimination has important applications in the context of quantum communication and quantum cryptography. One of the characteristic features of quantum mechanics is that it is impossible to devise a measurement that can distinguish nonorthogonal states perfectly. However, one can distinguish them with a finite probability by an appropriate measurement strategy. In Chapter 2, we describe the implementation of a theoretical protocol of programmable quantum-state discriminator, on a two-qubit NMR System. The projective measurement is simulated by adding two experiments. This device does the unambiguous discrimination of a pair of states of the data qubit that are symmetrically located about a fixed state. The device is used to discriminate both linearly polarized states and eillipitically polarized states. The maximum probability of successful discrimination is achieved by suitably preparing the ancilla quubit. The last step of any QIP protocol is the readout. In NMR-QIP the readout is done by using density matrix tomography. It was first proposed by Ernst and co-workers that a two-dimensional method can be used to correlate input and output states. This method uses an extra (aniclla) qubit, whose transitions indicate the quantum states of the remaining qubits. The 2D spectrum of ancilla qubit represent the input and output states along F1 and F2 dimensions respectively. However the 2D method requires several t1 increments to achieve the required spectral width and resolution in the indirect dimension, hence leads to large experimental time. In chapter 3, the conventional 2D NMRQIP method is speeded-up by using Hadamard spectroscopy. The Hadamard method is used to implement various two-, three-qubit gates and qutrit gates. We also use Hadamard spectroscopy for information storage under spatial encoding and to implement a parallel search algorithm. Various slices of water sample can be spatially encoded by using a multi-frequency pulse under the field gradient. Thus the information of each slice is projected to the frequency space. Each slice represents a classical bit, where excitation and no excitation corresponds to the binary values 0 and 1 respectively. However one has to do the experiment for each binary information, by synthesizing a suitable multi-frequency pulse. In this work we show that by recording the data obtained by various Hadamard encoded multi-frequency pulses, one can suitably decode it to obtain any birnary information, without doing further experiments. Geometric phases depend only on the geometry of the path executed in the projective Hilbert space, and are therefore resilient to certain types of errors. This leads to the possibility of an intrinsically fault-tolerant quantum computation. In liquid state NMRQIP. Controlled phase shift gates are achieved by using qubit selective pulses and J evolutions, and also by using geometir phases. In order to achieve higher number of qubits in NMR, one explores dipolar couplings which are larger in magnitude, yielding strongly coupled spectra. In such systems since the Hamiltonian consists of terms, it is difficult to apply qubit selective pulses. However such systems have been used for NMRQIP by considering 2n eigen states as basis states of an n-qubit system. In chapter 4, it is shown that non-adiabatic geometric phases can be used to implement controlled phase shift gates in strongly dipolar coupled systems. A detailed theoretical explanation of non-adiabatic geometric phases in NMR is given, by using single transition operators. Using such controlled phase shift gates, the implementation of Deutsch-Jozsa and parity algorithms are demonstrated. Search algorithms play an important role in the filed of information processing. Grovers quantum search algorithm achieves polynomial speed-up over the classical search algorithm. Bruschweiler proposed a Liouville space search algorithm which achieve polymonial speed-up. This algorithm requires a weakly coupled system with a mixed initial state. In chapter 5 we modified the Bruschweiler’s algorithm, so that it can be implemented on a weakly as well as strongly coupled system. The experiments are performed on a strongly dipolar coupled four-qubit system. The experiments from four spin-1/2 nuclei of a molecule oriented in a liquid crystal matrix. Chapter 6 describes the implementation of controlled phase shift gates on a quadrupolar spin-7/2 nucleus, using non-adiabatic geometric phases. The eight energy levels of spin-7/2 nucleus, form a three qubit system. A general procedure is given, for implementing a controlled phase shift gate on a system consisting of any number of energy levels. Finally Collin’s version of three-qubit DJ algorithm using multi-frequency pulses, is implemented in the spin-7/2 system.

Ressonância magnética nuclear é particularmente útil na caracterização de síntese molecular. Quase todos os compostos moleculares de interesse contêm átomos de nitrogênio e oxigênio em sua estrutura. Como esses elementos químicos costumam desempenhar funções estratégicas em reações e interações intra e intermoleculares, seus espectros NMR têm particular interesse. Com foco na blindagem magnética nuclear e no acoplamento entre spins nucleares, investigamos a dependência dessas constantes magnéticas com relação ao meio. A polarização eletrônica e relaxação geométrica do soluto, devido à presença do solvente, foram sistematicamente consideradas utilizando um tratamento sequencial QM/MM. Nossas observações gerais mostram que efeitos de relaxação de geometria mediados pelo meio têm pouca influência sobre o mecanismo da blindagem magnética nuclear, pelo menos quanto aos sistemas aqui investigados. Em contrapartida, os efeitos da polarização eletrônica são cruciais sobre essa propriedade molecular. Para o nitrogênio em piridina, amônia e formamida, por exemplo, as contribuições isoladas provenientes da relaxação geométrica são da ordem de 1,2 ppm. Note-se que este efeito é muito pequeno se considerarmos que com frequência são observados desvios gás-líquido da ordem de -26 ppm para o nitrogênio. Sobre o oxigênio, esses efeitos podem chegar até 100 ppm. Assim, é crucial entender as origens desses efeitos se desejamos utilizar corretamente espectroscopia RMN em caracterização molecular. Relevantes contribuições para a blindagem magnética têm origens em interações específicas entre soluto e solvente, como ligações de hidrogênio, as quais apenas podem ser isoladas e quantificadas através de modelagem molecular. Sistematicamente constatamos que a blindagem magnética é drasticamente afetada pelo caráter doador ou aceitador do sítio atômico envolvido em ligações de hidrogênio. Com respeito ao nitrogênio, nossos resultados indicam que o comportamento aceitador de hidrogênio de um elemento é responsável por um desvio gás-líquido positivo, enquanto que o caráter doador causa um desvio negativo. Nossas investigações também mostram que a blindagem magnética nuclear é independente com relação à hibridização do nitrogênio e oxigênio, indicando que as contribuições principais têm origens em interações específicas soluto-solvente, as quais devem ser corretamente modeladas. Investigamos sistematicamente os efeitos do solvente sobre o acoplamento indireto entre spins nucleares em amônia líquida. Embora a polarização do soluto seja realmente importante, para essa propriedade há outras contribuições fundamentais. Sem considerar efeitos de geometria, calculamos o acoplamento ANTPOT. 1 J(N-H) como -67,8 Hz. Após incluir esses efeitos, conseguimos uma descrição teórica mais apurada, obtendo um acoplamento de -63,9 Hz. Esses resultados mostram que efeitos de relaxação geométrica mediado pelo meio têm grande influência sobre o acoplamento indireto entre spins nucleares. / Nuclear magnetic resonance is helpful on molecular characterization. Most organic molecular compounds of interest contain nitrogen or oxygen atoms which play strategic functions in chemical reactions and molecular interactions. The NMR technique provides local atomic scale information on molecular properties, thus the study of nuclear magnetic properties of these elements in molecules is of particular interest. Focusing on nuclear magnetic shielding and spin-spin coupling constants we investigated the dependence of these magnetic constants with respect to the medium. Electronic polarization and geometry relaxation effects due to solvent were systematically studied. Our general findings indicate that geometry contributions are negligible in understanding the variation of shielding constants of the investigated systems, but polarization effects are crucial for this molecular property. On nitrogen in pyridine, ammonia and formamide, for instance, isolated contributions from geometry relaxation to shielding constants are around 1,2 ppm. Nitrogen shielding constants are very sensitive to the medium, where solvent effects around -26 ppm are often observed. On oxygen-17 magnetic shielding, the solvent effects can easily reach 100 ppm. It is crucial to understand the origins of these effects if one desires to correctly use NMR spectroscopy for molecular characterization. Our investigations also show that magnetic shielding constants are totally independent of the nitrogen or oxygen hybridization, which indicated that the main contributions arise from solute-solvent interactions. Relevant contributions to shielding constants come from specific solute-solvent interactions like hydrogen-bonds, which can only be quantified by explicit molecular modeling, and we observed that this property has a very strong dependence on the donor or acceptor character of the atomic site involved in hydrogen-bonding interactions. On nitrogen, the acceptor behavior is responsible by the positive gas-liquid shift in shielding constants, while the donor character causes positive shift. We systematically investigated the solvent effects on indirect spin-spin coupling constants of liquid ammonia. Solute polarization is very important, but there are other fundamental contributions to this property. Without including geometry effects we calculated the 1J (N-H) coupling to be -67,8 Hz. After accounting for the solute geometry relaxation we improved the theoretical prediction obtaining the coupling constant value of -63,9 Hz. These results show that geometry relaxation has drastic influence on indirect spin-spin coupling constants.