Coupled nuclear and electron dynamics in molecules

The interaction of light with a molecular system is the fundamental step of various chemical, physical and biological phenomena. Investigating the nuclear and electron dynamics initiated by light-matter interaction is important to understand, optimize and control the underlying processes. In this thesis two theoretical methods describing the coupled nuclear and electron dynamics in molecular systems are addressed. In the presented studies the coupled dynamics induced by photoexcitation, the subsequent relaxation processes and the possibility to control the dynamics in the vicinity of conical intersections (CoIns) are investigated for different molecular systems. In the first part of this work the photorelaxation pathways of a group of molecules commonly used in organic-based optoelectronic devices are characterized with the help of semiclassical ab intio molecular dynamics simulations. The relaxation pathways starting from the first excited singlet state of thiophene and of small oligothiophenes containing up to three rings is characterized by the interplay of internal conversion (IC) and intersystem crossing (ISC). Especially the ISC is mediated by ring-opening via a carbon-sulfur bond cleavage. The resulting entropically favored open-ring structures trap the molecules in a complex equilibrium between singlet and triplet states and a fast ring closure in the ground state is hindered. The extension of the π-system going from the monomer to the trimer weakens and slows down the ring opening process. Consequently the ISC is reduced for longer thiophene chains. The following two chapters are centered around the topics of controlling the molecular dynamics near a CoIn and monitoring the coherent electron dynamics induced by CoIns and laser interactions in the nucleobase uracil and the symmetric molecule NO2. In order to investigate the coherent electron dynamics, the ansatz used in this work allows a full-quantum description of the electron and nuclear motion and is called nuclear and electron dynamics in molecular systems (NEMol). As part of this work NEMol was extended to capture the coupled dynamics in complex high dimensional molecular systems. The observed electron dynamics both in NO2 and uracil reflects coherence, decoherence and reappearance which are all determined by the associated nuclear dynamics. The control of the molecular dynamics at a CoIn is realized with the help of a few-cycle infrared (IR) pulse. The applied control schema utilizes the carrierenvelope phase (CEP) of the pulse and allows to control the population distribution after the CoIn, the nuclear dynamics as well as the coherent electron dynamics. Depending on the chosen laser parameters and the molecular properties around the CoIn given by nature, two different mechanisms enable the control of the system. Both depend on the CEP but one is based on interference, which is generated by the interaction with the CoIn, and the other one is solely due to the few-cycle waveform of the pulse. As demonstrated for NO2 and uracil, the CEP control scheme even works for quite challenging boundary conditions. Therefore, it seems to be a general concept which can be used also in different molecules

Asymptotic dynamics of three-dimensional bipolar ultrashort electromagnetic pulses in an array of semiconductor carbon nanotubes

We study the propagation of three-dimensional bipolar ultrashort electromagnetic pulses in an array of semiconductor carbon nanotubes at times much longer than the pulse duration, yet still shorter than the relaxation time in the system. The interaction of the electromagnetic field with the electronic subsystem of the medium is described by means of Maxwell’s equations, taking into account the field inhomogeneity along the nanotube axis beyond the approximation of slowly varying amplitudes and phases. A model is proposed for the analysis of the dynamics of an electromagnetic pulse in the form of an effective equation for the vector potential of the field. Our numerical analysis demonstrates the possibility of a satisfactory description of the evolution of the pulse field at large times by means of a three-dimensional generalization of the sine-Gordon and double sine-Gordon equations

Ultrafast Excited State Dynamics in DNA and other Nanomaterials

Thesis advisor: Torsten FiebigThesis advisor: Mary RobertsUnderstanding the electronic nature of DNA is profound and has been attempted for decades. Photoexcitation of DNA with UV light deposits electronic energy in the base stack and prepares highly reactive excited states. These states are precursors for photoinduced damage reactions which can lead to mutations and ultimately to cell death. While many DNA photo products have been isolated and characterized, the primary events immediately after photon absorption are not yet understood. Recent studies with ultrafast lasers have revealed that the majority of excess energy gained by DNA with light absorbance is dissipated on the femtosecond and picosecond time scales. In this study double-stranded oligonucleotides with different base sequences, content and lengths were systematically examined using femtosecond pump-probe spectroscopy. The results indicate that excitations in DNA are delocalized over more than two bases and the extent of the delocalization depends strongly on the structure of the investigated systems. Exciton delocalization domains in the longer duplexes are larger than in the shorter ones. Also, single-stranded oligonucleotides show smaller extent of exciton delocalization than duplexes with the same length. In addition to the fundamental studies on DNA photophysics, the properties and the structure of new molecular beacons based on thiazole orange dimers were studied. A full account of the optical and structural properties of the dimers in different base environments and orientations is presented here. Currently, the development of efficient ways to utilizing solar energy is at the forefront of the scientific community due to the ever rising demand for energy. Both, colloidal semiconductor nanocrystals and single-walled carbon nanotubes are potential alternatives to conventional inorganic and organic materials in photovoltaic devices Thorough understanding of the charge transfer and related photophysical phenomena in these systems will answer the question whether these nanomaterials can be applied in future generations of solar cells. The photoinduced electron transfer in donor-acceptor CdSe/CdTe heterostructured nanorods, in which CdTe is grown on top of CdSe in a single rod structure, was studied. The electron transfer between the two nanocrystals occurs on the subpicosecond time scale, competing with the ultrafast relaxation mechanisms in the quantum confined nanocrystals. Furthermore, investigations on how quantum confinement influences the phonon wavepackets in semiconductor nanocrystals were carried out. Quantum beats corresponding to longitudinal optical phonon modes were observed in the femtosecond pump-probe spectra of colloidal CdTe nanocrystals. Size-dependent experiments revealed that the optical phonon frequencies and the exciton-phonon coupling strength do not depend on the crystal's size. Only the wavepacket dephasing time was influenced by the diameter of the particles which was correlated with the hole relaxation to the exciton band edge. Electron donor-acceptor constructs, based on single-walled carbon nanotubes (SWNT), can be attained by noncovalent functionalization of the nanotubes with pyrene derivatives. However, charge transfer does not take place in the simplest pyrene-SWNT constructs. For the first time the pure SWNT-pyrene construct was isolated and investigated. Our results revealed that the optical properties of pyrene are drastically altered due to strong electronic interactions with the SWNT surface. In other words, aromatic molecules lose their electronic (and chemical) signature when non-covalently attached to carbon nanotubes.Thesis (PhD) — Boston College, 2010.Submitted to: Boston College. Graduate School of Arts and Sciences.Discipline: Chemistry

Transporting and manipulating single electrons in surface-acoustic-wave minima

A surface acoustic wave (SAW) can produce a moving potential wave that can trap and drag electrons along with it. We review work on using a SAW to create moving quantum dots containing single electrons, with the aims of developing a current standard, emitting single photons, transferring single electrons between static quantum dots, and investigating non-adiabatic effects

Optics in Our Time

Optics, Lasers, Photonics, Optical Devices; Quantum Optics; Popular Science in Physics; History and Philosophical Foundations of Physic

SPIG2018

This Special Issue covers a wide range of topics from fundamental studies to applications of ionized gases. It is dedicated to four topics of interest: 1. ATOMIC COLLISION PROCESSES (electron and photon interactions with atomic particles, heavy particle collisions, swarms, and transport phenomena); 2. PARTICLE AND LASER BEAM INTERACTION WITH SOLIDS (atomic collisions in solids, sputtering and deposition, and laser and plasma interactions with surfaces); 3. LOW TEMPERATURE PLASMAS (plasma spectroscopy and other diagnostic methods, gas discharges, and plasma applications and devices); 4. GENERAL PLASMAS (fusion plasmas, astrophysical plasmas, and collective phenomena). This Special Issue of Atoms will highlight the need for continued research on ionized gas physics in different topics ranging from fundamental studies to applications, and will review current investigations

Investigating Electrostatics and Dynamics in Confinement and Constructs Using Two-Dimensional Infrared Spectroscopy and Molecular Simulations.

Understanding the ultrafast dynamics of enzymes is required to fully explain what makes them such efficient catalysts. Two-dimensional infrared (2D-IR) spectroscopy along with molecular modeling helps provide a more complete description of the environment of enzyme active sites and other related systems. A carbonyl-labeled copper site in a de novo peptide exhibits vibrationally driven nonequilibrium dynamics when characterized using 2D-IR spectroscopy. The source of the dynamics is found to be the coupling of the CO stretching mode to the CuCO bending mode, enhanced by distortions to the histidine side chains binding the copper. QM/MM calculations show the source of the distortions to be primarily from electrostatic interactions with the peptide. Using similar calculations, but with a refined sampling of starting structures, other de novo peptides are modeled to identify a candidate that will show different nonequilibrium dynamics from the original metalloenzyme. The selected enzyme is more catalytically active, and calculations predict a smaller coupling between the CO stretching and CuCO bending modes. This prediction is confirmed using 2D-IR, where the nonequilibrium dynamics have a smaller amplitude, but occur on the same time scale. Several thiocyanate salts in the Hofmeister series are studied in neat D2O and with alpha-cyclodextrin (a-CD). In neat D2O, 2D-IR shows slightly faster spectral diffusion for kosmotropes and slower spectral diffusion for chaotropes. When a-CD is introduced to the system, an additional slowly decaying component of the FFCF is found. The presence of the slower dynamics indicates the nitrogen in thiocyanate is not solvent exposed, but embedded in the interior of the a-CD. A combination of 2D-IR and molecular modeling was also needed to characterize the structure of a labeled crown either with a nearby sodium thiocyanate contact ion pair. The spectral diffusion of the metal carbonyl label shows dynamics occurring on a slower time scale than the vibrational lifetime of the probe. DFT calculations show that two different conformations of the thiocyanate ion around the crown ether have similar energies, but produce different CO frequencies. The time to sample these states is longer than the vibrational lifetime of the metal carbonyl.PHDChemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/120712/1/amwhi_1.pd