In this thesis we are investigating a different formalism of non-relativistic quantum mechanics called the path integral formalism. It is a generalization of the classical least action principle. The introduction to this subject begins with the construction of the path integral in terms of the idea of probability amplitudes whose absolute square gives the probability of finding a system in a particular state. Then we show that if the Lagrangian is a quadratic form one needs only to calculate the classical action besides from a time-dependent normalization constant to find the explicit expression of the path integral. We look in to the subject of two kinds of slit-experiments: The square slit, the single- and the double-Gaussian slit. Also, the propagator for constrained paths is calculated and applied to the Aharonov-Bohm effect, which shows that the vector potential defined in classical electrodynamics have a physical meaning in quantum mechanics. It is also shown that the path integral formulation is equivalent to the Schrödinger description of quantum mechanics, by deriving the Schrödinger equation from the path integral. Further applications of the path integral are discussed. / I detta fördjupningsarbete undersöker vi en annan formalism av icke-relativistisk kvantmekanik kallad banintegral formalismen. Det är en generalisering av den klassiska verkansprincipen. Introduktionen till detta ämne börjar med konstruktionen av banintegralen i termer av sannolikhetsamplituder vars absolutbelopp i kvadrat ger sannolikheten av att finna ett system i ett särskilt tillstånd. Sedan visar vi att om Lagrangianen är av kvadratisk form så krävs endast en beräkning av den klassiska verkan förutom en tidsberoende normaliseringskonstant för att finna ett uttryck för banintegralen. Vi ser på två olika typer av spaltproblem: Den kantinga spalten, enkel- och dubbel Gaussisk spalt. Vi beräknar dessutom propagatorn för banor med restriktioner och applicerar detta på Aharonov-Bohm effekten, som visar att den klassiska vektorpotentialen som definierad i klassisk elektrodynamik har en fysikalisk mening i kvantmekaniken. Vi visar också ekvivalensen av banintegralformalismen med Schrödingerekvationen genom att härleda Schrödingerekvationen från banintegralen. Andra applikationer av banintegralen diskuteras.

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This thesis presents an implementation of path integral molecular dynamics (PIMD) for sampling equilibrium and dynamical properties within the molecular modelling toolkit (MMTK) [J. Comp. Chem. 21, 79 (2000)], an open source Python package. Rigorous simulation using this code serves to benchmark this implementation as well as the robust- ness of the path integral Langevin equation as a thermostat [J. Chem. Phys. 133, 124104 (2010)]. PIMD is used to calculate equilibrium properties for clusters of HeN-CO2 at low- temperatures, with comparison to experimental and exact results. We characterize the convergence of structural and energetic properties as a function of path-integral discretiza- tion error. The radial and angular distribution of these clusters is studied as a function of size in the absence of rotation and bosonic exchange. These distributions are subsequently used to calculate vibrational shifts of CO2. This result is compared to high-accuracy path integral Monte Carlo simulations which include rotational and exchange effects. These sim- ulations indicate that the neglect of rotational degrees of freedom leads to an unphysical localization of helium atoms and incorrect vibrational shifts when compared to experiment. Approximate real-time quantum dynamics is presented for doped helium clusters using the ring-polymer molecular dynamics (RPMD) method. The accuracy of RPMD is tested iii for low-temperature simulations and compared to exact results. Preliminary calculation of the dynamics of the helium solvated CO2 dopant with respect to the center of mass of the cluster is presented. The effect of a cartesian integrator versus a normal-mode integrator for quantum dynamics is addressed. The path integral ground-state method is applied in order to calculate T = 0 properties. A convergence study of the ground-state energy of the quantum harmonic oscillator with respect to sampling time and path discretization is shown. As a final application of this implementation, a sugar in a periodic water box is simulated at T = 300K. The calculation of rotamer populations and a dipole autocorrelation indicate negligible change with the inclusion of quantum effects. This work offers a comprehensive foundation from which to base future PIMD centered research.

This thesis presents an implementation of path integral molecular dynamics (PIMD) for sampling equilibrium and dynamical properties within the molecular modelling toolkit (MMTK) [J. Comp. Chem. 21, 79 (2000)], an open source Python package. Rigorous simulation using this code serves to benchmark this implementation as well as the robust- ness of the path integral Langevin equation as a thermostat [J. Chem. Phys. 133, 124104 (2010)]. PIMD is used to calculate equilibrium properties for clusters of HeN-CO2 at low- temperatures, with comparison to experimental and exact results. We characterize the convergence of structural and energetic properties as a function of path-integral discretiza- tion error. The radial and angular distribution of these clusters is studied as a function of size in the absence of rotation and bosonic exchange. These distributions are subsequently used to calculate vibrational shifts of CO2. This result is compared to high-accuracy path integral Monte Carlo simulations which include rotational and exchange effects. These sim- ulations indicate that the neglect of rotational degrees of freedom leads to an unphysical localization of helium atoms and incorrect vibrational shifts when compared to experiment. Approximate real-time quantum dynamics is presented for doped helium clusters using the ring-polymer molecular dynamics (RPMD) method. The accuracy of RPMD is tested iii for low-temperature simulations and compared to exact results. Preliminary calculation of the dynamics of the helium solvated CO2 dopant with respect to the center of mass of the cluster is presented. The effect of a cartesian integrator versus a normal-mode integrator for quantum dynamics is addressed. The path integral ground-state method is applied in order to calculate T = 0 properties. A convergence study of the ground-state energy of the quantum harmonic oscillator with respect to sampling time and path discretization is shown. As a final application of this implementation, a sugar in a periodic water box is simulated at T = 300K. The calculation of rotamer populations and a dipole autocorrelation indicate negligible change with the inclusion of quantum effects. This work offers a comprehensive foundation from which to base future PIMD centered research.

The Casimir effect refers to the primarily attractive force between material bodies due to quantum fluctuations in the electromagnetic field. The Casimir effect is difficult to calculate in general, since it is sensitive to the exact shapes of the bodies and involves contributions from all frequencies. As a result, calculating the Casimir effect between general bodies usually requires a numerical approach. The worldline method computes Casimir energies by creating an ensemble of space-time paths corresponding to a virtual particle interacting with the bodies. This method was originally developed for a scalar fields coupled to an idealized background potential, rather than the vector electromagnetic field interacting with media. This thesis presents work on extending the worldline method to account for the material properties of the interacting bodies, and the polarizations of electromagnetism. This thesis starts by covering background material on path integrals, and quantizing the electromagnetic field in media. The electromagnetic field is decomposed in terms of two scalar fields for planar bodies, where these scalar fields correspond to the transverse-electric and transverse-magnetic polarizations of the electromagnetic field. The worldline path integrals are developed for both polarizations, and solved analytically. Next, numerical methods are developed and tested in the context of planar bodies. The starting positions, and scale of the paths, and shape of the paths are sampled via Monte Carlo methods. The transverse-magnetic path integral also requires specialized methods for estimating derivatives, and path construction. The analytical and numerical results for both worldline path integrals are in agreement with known solutions. Finally, specialized methods are developed for computing derivatives of the worldline Casimir-energy path integrals, allowing for efficient numerical computations of Casimir forces and torques.

A fundamental understanding of ultrafast nonequilibrium dynamical processes in molecular aggregates is crucially important for the design of nanodevices that utilize quantum mechanical effects. However, understanding the coupled electron-phonon dynamics of such high-dimensional systems remains a challenging issue. As a result of the ever-growing computational power that is available, realistic parameterization of model Hamiltonians and implementation of sophisticated quantum dynamics algorithms have become indispensable tools for gaining insight into these processes. The focus of this dissertation is the development and implementation of approximate path integral-based methods to compute the time-evolution as well as linear and nonlinear spectroscopic signals of molecular aggregates following photo-excitation. The developments and applications presented here are geared toward gaining a better understanding of the role that electron-phonon coupling plays in framing ultrafast excitation energy transfer networks in photosynthetic light-harvesting complexes. The ultrafast excitation energy transfer dynamics that occurs upon photo-excitation of a network of electronically coupled chromophores is remarkably sensitive to the strength of electronic coupling as well as the frequencies and coupling strengths that characterize electron-phonon interactions. Based on approximations to the diabatic representation of molecular Hamiltonians, energetic models of condensed phase molecular aggregates can be parameterized from a first principles description. Often times, computational parameterization of these models reveals comparable magnitudes for intermolecular electronic couplings and electron-phonon couplings, negating the applicability of popular perturbative algorithms (such as those based on Forster or Redfield theory) for describing their time-evolution. Moreover, non-perturbative exact methods (e.g. stochastic Schrodinger equations and the Hierarchical Equations of Motion) are generally inefficient for all but a few specific limiting forms of electron-phonon coupling, or make assumptions about autocorrelation timescales of the vibrational environment. Because of the failure of the energetic parameters determined through recent ab initio studies of natural molecular aggregates to abide by the rather restrictive requirements for efficient application of the above-mentioned methods, the development of approximate non-perturbative algorithms for predicting nonequilibrium dynamical properties of such systems is a central theme in this dissertation. Following a general introductory section describing the basic concepts that are fundamental to the remainder of the thesis, the derivation of path integral dynamics methods is presented. These include a cartesian phase space path integral derivation of the truncated Wigner approximation as applied to the Meyer-Miller-Stock-Thoss mapping model for describing vibronic systems as well as a novel derivation of the Partially Linearized Density Matrix algorithm, highlighting its emergence as a leading order approximation to an, in principle, exact expression for the density matrix. An algorithm for computing the nonlinear response function for higher-order optical spectroscopy signals is presented within the framework of the partially linearized density matrix formalism. Time-resolved two-dimensional electronic spectra are computed and compared with exact results as well as standard perturbation theory-based results, highlighting the accuracy and efficiency of the developed method. Additionally, the recently popularized symmetrical quasi-classical method for computing the reduced density matrix dynamics is extended for computing linear optical spectroscopy signals, and compared with results from the partially linearized density matrix treatment. A generalization of the model Hamiltonian form utilized in recent ab initio studies is presented, allowing for direct vibrational energy relaxation due to coupling between intramolecular normal modes and their environment. The consequences of including these interactions within a model Hamiltonian that is inspired by energetic parameters found in studies of a photosynthetic light-harvesting complex are highlighted in the context of density matrix dynamics and time-resolved two-dimensional electronic spectroscopy. The results indicate that this physical process can be utilized as a means of optimizing the efficiency of excitation energy transfer and localization. Inspired by ab initio characterization of model Hamiltonians for molecular aggregates, a new approximate semiclassical propagator for describing the time-evolution of a system consisting of discrete electronic states in the presence of both high-frequency harmonic vibrational modes as well as slow environmental DOFs with arbitrary potentials is presented. Results indicate that this algorithm provides a more accurate description in this parameter regime than standard linearized path integral methods such as the partially linearized density matrix algorithm and the truncated Wigner approximation. Finally, preliminary results of dynamics involving non-perturbative field-matter interactions is presented with emphasis on strategically shaped pulses, field design through optimal control, and non-perturbative pump-probe spectroscopy.

The path integral formulation of quantum mechanics generalizes the action principle of classical mechanics. The Feynman path integral is, roughly speaking, a sum over all possible paths that a particle can take between fixed endpoints, where each path contributes to the sum by a phase factor involving the action for the path. The resulting sum gives the probability amplitude of propagation between the two endpoints, a quantity called the propagator. Solutions of the Feynman path integral formula exist, however, only for a small number of simple systems, and modifications need to be made when dealing with more complicated systems involving singular potentials, including the Coulomb potential. We derive a generalized path integral formula, that can be used in these cases, for a quantity called the pseudo-propagator from which we obtain the fixed-energy amplitude, related to the propagator by a Fourier transform. The new path integral formula is then successfully solved for the Hydrogen atom in two and three dimensions, and we obtain integral representations for the fixed-energy amplitude. / Vägintegral-formuleringen av kvantmekanik generaliserar minsta-verkanprincipen från klassisk mekanik. Feynmans vägintegral kan ses som en summa över alla möjliga vägar en partikel kan ta mellan två givna ändpunkter A och B, där varje väg bidrar till summan med en fasfaktor innehållande den klassiska verkan för vägen. Den resulterande summan ger propagatorn, sannolikhetsamplituden att partikeln går från A till B. Feynmans vägintegral är dock bara lösbar för ett fåtal simpla system, och modifikationer behöver göras när det gäller mer komplexa system vars potentialer innehåller singulariteter, såsom Coulomb--potentialen. Vi härleder en generaliserad vägintegral-formel som kan användas i dessa fall, för en pseudo-propagator, från vilken vi erhåller fix-energi-amplituden som är relaterad till propagatorn via en Fourier-transform. Den nya vägintegral-formeln löses sedan med framgång för väteatomen i två och tre dimensioner, och vi erhåller integral-representationer för fix-energi-amplituden.

<p>This thesis presents and develops the path integral simulation techniques in application to small quantum systems at finite temperatures. The first goal is to obtain exact thermodynamic expressions for systems of noninteracting</p><p>The rest and the major part of the thesis is dedicated to the development and testing of Bead-Fourier path integral molecular dynamics. Although, path integral molecular dynamics as well as path integral Monte Carlo are well</p><p>First, molecular dynamics under Bead-Fourier scheme was developed and tested on the examples of quantum harmonic oscillator and Hydrogen atom. The main attention was paid to ergodicity problems. Then we addressed the question,</p><p>Later, the formalism for identical particles was developed.</p><p>Finally, the question of molecular dynamics efficacy was raised. It was shown, that formalisms for identical and distinguishable particles, both, can be reformulated into a more efficient ones, providing all dynamical variables</p>

This thesis presents and develops the path integral simulation techniques in application to small quantum systems at finite temperatures. The first goal is to obtain exact thermodynamic expressions for systems of noninteracting The rest and the major part of the thesis is dedicated to the development and testing of Bead-Fourier path integral molecular dynamics. Although, path integral molecular dynamics as well as path integral Monte Carlo are well First, molecular dynamics under Bead-Fourier scheme was developed and tested on the examples of quantum harmonic oscillator and Hydrogen atom. The main attention was paid to ergodicity problems. Then we addressed the question, Later, the formalism for identical particles was developed. Finally, the question of molecular dynamics efficacy was raised. It was shown, that formalisms for identical and distinguishable particles, both, can be reformulated into a more efficient ones, providing all dynamical variables