The focus of this dissertation is the study of the photodissociation dynamics of halogen oxide species (XO, X = Cl, Br, I). These radical species are known to be important in stratospheric and tropospheric ozone depletion cycles. They are also useful benchmark systems for the comparison to current theoretical methods where they provide insight into the dynamics occurring beyond the Franck-Condon region. These systems are studied using velocity map ion imaging, a technique that measures velocity and angular information simultaneously. Photofragment species are state-selectively ionized for detection using 2+1 REMPI (Resonance Enhanced Multi-Photon Ionization). The instrumentation employs a molecular beam of the XO radicals formed using pyrolitic and photolytic methods. The current work involves the measurement of fundamental physical constants of the XO species. The bond dissociation energy of IO is measured. Vibrational level dependent correlated final state branching ratios of the predissociation of the A(^2 II_3/2) state of ClO and BrO are reported, and comparison to theoretical methods is discussed.

As the hydrodynamic theory breaks down with the local density ap- proximation in the fermionic superfluid with spin-polarization, we develop a general formalism of the adiabatic dynamics for the low-lying collective modes in the BEC-BCS crossover, which is exact in the adiabatic limit. This adi- abatic dynamic theory is based on a static density functional theory of the spin-polarized superfluid system, which we derive as a generalization of the conventional density functional theory of superfluid for current experimental interests. A special case where the system is uniform and analytically solv- able is studied in detail. We show that our adiabatic equations of motion are reduced to the hydrodynamic equations of motion within local density approx- imation, which provides a solid microscopic foundation for the well-publicized phenomenological hydrodynamic theory. / text

The specialized pigment-protein complexes involved in the first process of photosynthesis are light-harvesting structures that are composed of networks of chromophores in protein scaffolds. Though light-harvesting complexes vary in chromophore composition and protein structure, they are capable of transferring the absorbed energy as molecular excitation energy from chromophore to chromophore with maximal efficiency. Thus, numerous interdisciplinary studies focus on elucidating energy transfer mechanisms in these biological complexes and how the same principles can be applied to artificial photosynthetic and photovoltaic machines. From advanced spectroscopic measurements and theoretical models, the interaction between the excited electronic states and the nuclear vibrational degrees of freedom is now established to be crucial for efficient energy transfer. In light-harvesting complexes of plants and bacteria, it is now understood that the classical-like vibrational modes of the protein and solvent environment drive energy transfer between the energetically close electronic states of the chromophores. On the other hand, recent spectroscopic measurements on algae light-harvesting complexes discovered signatures of quantized, high frequency vibrational modes of the chromophore. Unfortunately, a deterministic interpretation of the data and the underlying Hamiltonian is hindered due to significant inhomogeneous spectral line-broadening. Though numerous model Hamiltonians have been proposed from theoretical work, various computational approximations employed in these studies necessitate empirical parameter tuning in order to obtain agreement with benchmark linear optical spectra. Thus in this work, we present a simple, but improved, computational prescription to compute the ensemble of Hamiltonians for four closely-related algae light-harvesting complexes. We verify the reliability of our proposed models by comparing simulated optical spectra with experimental measurements. We show that static disorder and inhomogeneous broadening are significant for phycobiliproteins due to large site energy fluctuations. We also show that the nuclear environment plays an important role in defining the trapping state, or the final energy acceptor. Finally, our work for the first time suggests that EET dynamics can be tuned by varying the titration states of the chromophores.

Molecules are traditionally treated quantum mechanically using the Born-Oppenheimer formalism. In this formalism, different electronic states of the molecule are treated independently. However, most photo-initiated phenomena occurring in nature are driven by the couplings between different electronic states in both isolated molecules and molecular aggregates, and therefore occur beyond the Born-Oppenheimer formalism. These couplings are relevant in reactions relating to the perception of vision in the human eye, the oxidative damage and repair of DNA, the harvesting of light in photosynthesis, and the transfer of charge across large chains of molecules. While these reaction dynamics have traditionally been studied with visible and ultraviolet spectroscopy, attosecond XUV pulses formed through the process of high harmonic generation form a perfect tool for probing coupled electronic dynamics in molecules. In this thesis, I will present our work in using ultrafast, XUV spectroscopy to study these dynamics in molecules of increasing complexity. We begin by probing the relaxation dynamics of superexcited states in diatomic O₂. These states can relax via two types of electronic couplings, either through autoionization or neutral dissociation. We find that our pump-probe scheme can disentangle the two relaxation mechanisms and independently measure their contributing lifetimes. Next, we present our work in observing a coherent electron hole wavepacket initiated by the ionization of polyatomic CO₂ near a conical intersection. The electron-nuclear couplings near the conical intersection drive the electron hole between different orbital configurations. We find that we can not only measure the lifetime of quantum coherence in the electron hole wavepacket, but also control its evolution with a strong, infrared probing field. Finally, we propose an experiment to observe the migration of an electron hole across iodobenzene on the few-femtosecond timescale. We present experimental modifications made to the high harmonic generation set-up in order to probe this ultrafast and elusive charge migration. These results demonstrate the potential of ultrafast, XUV spectroscopy in probing the inner-workings of electronic couplings occurring in nature.

This thesis presents a joint experimental and theoretical study of vector correlations in the electronically, vibrationally, and rotationally inelastic collisions of simple molecules with rare-gas atoms. In the first instance, empirical and calculated data are presented for rotationally inelastic scattering in the NO(X)+Ar and ND₃(X̃)+Ar systems at collision energies in the range 405-2210 cm^-1. These experiments - the first to be conducted on a newly commissioned crossed-molecular beam machine - measured the k-k' correlation, i.e. that between the vectors describing the relative velocities before and after collision, respectively. The empirical data were subjected to rigorous comparison with both quantum-mechanical and quasi-classical trajectory (QCT) calculations. For both the NO(X)+Ar and ND₃(X̃)+Ar systems, there is generally good agreement between experiment and theory at all four collision energies investigated. Two chapters of this thesis focus on the development of trajectory surface-hopping (TSH) QCT models of the OH(A, v = 0)+Kr and OH(A, v = 0)+Xe systems. Experimental data relating to scalar quantities (rotational energy transfer (RET) and electronic quenching) and to the j-j' correlation (which quantifies the depolarisation of the angular momentum of the OH(A) radical) are compared to variable-collision-energy TSH QCT calculations in which the length of the OH bond is fixed. The algorithms involve all three PESs of the OH(A/X)+Kr system, and the full range of electrostatic and roto-electronic mechanisms that couple them, for the first time. The most complete model succeeded in accounting for 93% of experimentally observed quenching. For the OH(A/X)+Xe system, coupling matrix elements were estimated from those of OH(A/X)+Kr, and the most complete model recovered 63% of experimentally observed quenching. This thesis also presents a novel theoretical study of rotationally inelastic dynamics in the OH(A, v = 1)+Kr system. Provisional results from adiabatic calculations in which the OH bond length is allowed to vary over the course of a trajectory are presented alongside experimental data that were reported previously. To date, these calculations continue to underestimate the extent of empirical RET data. Reasons for the observed discrepancy, and suggestions to resolve it, are outlined in detail.

Very short lifetimes of excited states of isolated bases in nucleic acids, on the picosec- ond order, are believed to contribute to photostability of the genetic code. When embedded in DNA this behavior becomes more complex, mainly due to their inter- actions via stacking and hydrogen bonding. The DNA photophysiscs is not fully understood yet. It depends e.g. on the conformation and the character of excited states. The studies on smaller systems can help to improve the understanding of these phenomena. The aim of this work was to examine the dynamics of the excited states of the n → π∗ character of the complex of N-methylformamide dimer and two waters. The study was performed using non-adiabatic dynamics simulations with on-the-fly Surface Hopping algorithm based on the potential energy surfaces and non-adiabatic couplings obtained with multi-reference approach. The results show that after the vertical excitation into delocalized S2 state the system relaxes into S1 state within several tens femtoseconds. For majority of the population, the charac- ter of the state then oscillates between localized and delocalized during the whole course of the dynamics. Comparison with calculations with the waters removed in- dicates that the delocalization is caused by waters serving as a bridge between the two chromophores. 1

The surface and interface of the metal nanoclusters and semiconducting nanomaterials play a key role in determining the electronic structure and overall photophysical properties. A single strand DNA stabilizes the metal nanoclusters, but it also influences the structural change, solvation free energy, and photophysical properties. On the other hand, surface and interface states in Pb and Cd chalcogenide nanomaterials affect the phonon mediated hot carrier relaxation. We applied DFT and DFT based non-adiabatic dynamics methods to study the surface and interface?s effects on the photoexcited processes. In the first part, we have studied the Ag nanoclusters' photophysical properties that are affected by the structural isomers, redox potential, nucleobase passivation, and cluster size. Ag nanoclusters are shown alternative reduction potential, which makes nanoclusters of singlet spin multiplicity thermodynamically favorable. Besides, the optically bright transition in the range of 2.5-3.5 eV is shown metal to ligand charge transfer. It is modulated by the s+p+d orbital mixing in the hole and electron states. We also simulate the charge transfer from the photoexcited PbS QD to organic dye (PDI) attached to the QD surface. Depending on the linker group and the dipole moment of neighboring passivating ligands, the PDI-QD conformations are varies. In response to structural change, the total dipole moment is modulated, changing its electronic structure and hence the photoexcited electron transfer rate from the PbS QD to PDI. We also investigate the inorganic-inorganic interactions in the PbCl2 bridged PbSe NPL and PbSe|CdSe Janus heterostructure. The energy dissipation rate of hot electrons is slower in NPL than the hot hole, while hot e-h relaxed to the band-edge by ?1.0ps in the QD. The slower relaxation rate is rationalized by a large average intraband energy difference and smaller coupling term. Besides, the hot carriers in the NPL are spatially separated by ?1.00 ps, which is a favorable condition for the carrier multiplication process. In Janus QD, (100) interfacial layer creates a structural mismatch in the CdSe part. Besides, the energy offset between the valance localized on PbSe and CdSe part is minimum in the PbSe Janus QD of an interface of (111) facet.

Light or photons can excite electrons in a molecule, leading to creation of electronically excited states. Such processes are ubiquitous in nature, such as, vision, photo-protection of DNA/RNA nucleobases, light harvesting, energy and charger transfer etc. This photoexcitation induces nuclear motion on the excited states, leading the excess energy to dissipate either non-radiatively via internal conversion back down to the ground state, isomerization, and dissociation, or radiatively via fluorescence and phosphorescence. In this dissertation, we investigate the non-radiative processes in organic chromophores that ensue in an ultrafast manner, mediated via conical intersections (CoIn). Description of such excited state processes generally require multi-reference treatment because of quasi-degeneracy near CoIns. Hence, most insight about these processes is typically gained by constructing potential energy surface (PES) using multi-reference electronic structure methods along important reaction coordinates. Nonetheless, the aforementioned static treatment fails to provide any dynamical information, such as, excited state lifetime, state populations, branching ratio, quantum yield etc. In this dissertation, we have gone beyond the static treatment by undertaking computationally expensive non-adiabatic excited state molecular dynamics simulations employing trajectory surface hopping (TSH) methodology on PESs created on-the-fly using multi-reference electronic structure methods. This allows us to compare theoretical results to experimental observables, when possible, strengthening the explanations underlying those processes. Our goal is to examine the effect of structure, and of electronic structure methods on the excited state dynamics. We have examined the non-adiabatic excited state dynamics of cis,cis-1,3-cyclooctadiene (cc-COD), a cyclic diene, in an effort to systematically compare and contrast the dynamics of cc-COD to that of other well studied conjugated molecules. Such exploration is very significant, since the majority of the molecules involved in natural photoexcited processes, include an ethylenic double bond or alternating double bonds creating conjugation. Our calculations have revealed ultrafast sub-ps decay for cc-COD, and have illustrated that the internal conversion dynamics is facilitated by CoIns, dominated by twisting of one of the double bonds and pyramidalization of one of the carbons of that double bond, similar to trans-1,3-butadiene and unlike 1,3-cyclohexadiene (CHD). Our high-level electronic structure calculations have also explained the features in the experimental time-resolved photoelectron spectrum of cc-COD. Another molecule of biological importance, uracil, was also investigated using TSH simulations, by systematically increasing dynamical correlation. We have found that the inclusion of dynamical correlation for uracil leads to an almost barrierless PES on S2, leading to a faster decay and no population trap on this state. Uracil also contains a double bond and the simulations have revealed that the ultrafast relaxation is dominated by an ethylenic twist and pyramidalization of a carbon of that bond, increasing importance of such nuclear motion in photoexcited molecular dynamics. A comparison of the molecules studied have illustrated that the rigid molecules, such as uracil, CHD, have a very local CoIn seam space, whereas cc-COD, which is flexible having many low frequency degrees of freedom, has a non-local or extended CoIn seam space. Overall, the work performed in this dissertation, elucidates the significance of structure and conjugation, in the photoinduced coupled electron-nuclear dynamics in organic molecules. / Chemistry

The broad range of applications for photochemical reactions is the result of light-matter interaction at the electronic level. The diverse application of photochemistry in various fields, including photovoltaic materials, molecular switches, and biological systems are due to electronic and structural transformations induced by photoexcitation as well as molecular alteration due to electron and charge transfer. An improved understanding of these photochemical events is dependent on the fundamental theoretical evaluation, to model and analyze the ultrafast processes. The studies discussed in this thesis explore such theoretical implementation in two different frontiers. In the first study, dynamic simulations are performed to model the light-induced bond dissociation of phenyl azide. The surface hopping formalism, implemented under the semiclassical molecular dynamics approach helped in tracing the time evolution of the electronic and structural levels, involved in the photodissociation. In the second study, the time-dependent density functional theory has been applied to generate XA spectra of imidazole solutions. The theoretical assessments support experimental measurements and provide more insight into the core excitations and structural influence on the absorption spectra. / Fotokemiska reaktioner styrs av växelverkan mellan ljus of materia på en elektronisk nivå. I olika fält finns det vitt skilda tillämpningarna av fotokemi. Dessa inkluderar ljusinducerade processer i solceller, molekylära strömbrytare, och biologiska system. Reaktionerna beror av elektroniska och strukturella transformationer som induceras av fotoexcitationen, och kan ge upphov till energi- och laddningsöverföring. För att få utökad förståelse av fotokemiska reaktioner behövs grundläggande teoretiska studier där ultrasnabba processer modelleras och analyseras i jämförelse med experiment. Undersökningar som presenteras i denna avhandling använder sig att teoretiska modeller i två olika områden av fotokemi. I den första studien har vi genomfört dynamiska simuleringar för att modellera ljusinducerad dissociation av fenylazid. Vi have använt en semi-klassisk approximation med hopp mellan olika elektroniska tillstånd vilket gör det möjligt att följa utvecklingen i elektroniska och geometriska frihetsgrader under fotodissociationen. I den andra studien har tidsberoende täthetsfunktionalteori använts för att simulera röntgenabsorptionsspektrum för imidazol i lösning. Genom att utvärdera olika geometriska modeller med teoretiska beräkningar kan vi berika tolkningen av experimentella mätningar, och även få detaljerat insikt i innerskalsexcitationer och hur geometrin påverka röntgenspektrum.

Dans cette thèse, nous avons répondu à certaines questions ouverts dans le domaine de la dynamique hors équilibre des systèmes quantiques unidimensionnels fermés. Durant ces dernières années, les avancées dans les techniques expérimentales ont revitalisé la recherche théorique en physique de la matière condensée et dans l'optique quantique. Nous avons traité trois sujets différents et en utilisant des techniques à la fois numériques et analytiques. Dans le cadre des techniques numériques, nous avons utilisé des méthodes de diagonalisation exacte, l'algorithme du groupe de renormalisation de la matrice densité en fonction du temps (t-DMRG) et l'algorithme de Lanczos. Au début, nous avons étudié la dynamique quantique adiabatique d'un système quantique près d'un point critique. Nous avons démontré que la présence d'un potentiel de confinement modifie fortement les propriétés d'échelle de la dynamique des observables en proximité du point critique quantique. La densité d'excitations moyenne et l'excès d'énergie, après le croisement du point critique, suivent une loi algébrique en fonction de la vitesse de la trempe avec un exposant qui dépend des propriétés spatio-temporelles du potentiel. Ensuite, nous avons étudié le comportement de bosons ultra-froids dans un réseau optique incliné. En commençant par l'hamiltonien de Bose-Hubbard, dans la limite de Hard-Core bosons, nous avons développé une théorie hydrodynamique qui reproduit exactement l'évolution temporelle d'une partie des observables du système. En particulier, nous avons observé qu'une partie de bosons reste piégée, et oscille avec une fréquence qui dépend de la pente du potentiel, au contraire, une autre partie est expulsée hors de la rampe. Nous avons également analysé la dynamique du modèle de Bose-Hubbard en utilisant l'algorithme t-DMRG et l'algorithme de Lanczos. De cette façon, nous avons mis en évidence le rôle de la non-intégrabilité du modèle dans son comportement dynamique. Enfin, nous avons abordé le problème de la thermalisation dans un système quantique étendu. À partir de considérations générales, nous avons introduit la notion de profil de température hors équilibre dans une chaîne des bosons à coeur dure. Nous avons analysé la dynamique du profil de temperature et, notamment, ses propriétés d'échelle / In this thesis we have addressed some open questions on the out-of-equilibrium dynamics of closed one-dimensional quantum systems. In recent years, advances in experimental techniques have revitalized the theoretical research in condensed matter physics and quantum optics. We have treated three different subjects using both numerical and analytical techniques. As far as the numerical techniques are concerned, we have used essentially exact diagonalization methods, the adaptive time-dependent density-matrix renormalization-group algorithm (t-DMRG) and the Lanczos algorithm. At first, we studied the adiabatic quantum dynamics of a quantum system close to a critical point. We have demonstrated that the presence of a confining potential strongly affects the scaling properties of the dynamical observables near the quantum critical point. The mean excitation density and the energy excess, after the crossing of the critical point, follow an algebraic law as a function of the sweeping rate with an exponent that depends on the space-time properties of the potential. After that, we have studied the behavior of ultra-cold bosons in a tilted optical lattice. Starting with the Bose-Hubbard Hamiltonian, in the limit of Hard-Core bosons, we have developed a hydrodynamic theory that exactly reproduces the temporal evolution of some of the observables of the system. In particular, it was observed that part of the boson density remains trapped, and oscillates with a frequency that depends on the slope of the potential, whereas the remaining packet part is expelled out of the ramp. We have also analyzed the dynamics of the Bose-Hubbard model using the tDMRG algorithm and the Lanczos algorithm. In this way we have highlighted the role of the non-integrability of the model on its dynamical behavior. Finally, we have addressed the issue of thermalization in an extended quantum system. Starting from quite general considerations, we have introduced the notion of out-of-equilibrium temperature profile in a chain of Hard-Core bosons. We have analyzed the dynamics of the temperature profile and especially its scaling properties