On Ultrafast Time-Domain TeraHertz Spectroscopy in the Condensed Phase: Linear Spectroscopic Measurements of Hydrogen-Bond Dynamics of Astrochemical Ice Analogs and Nonlinear TeraHertz Kerr Effect Measurements of Vibrational Quantum Beats

Much of the chemistry that affects life on planet Earth occurs in the condensed phase. The TeraHertz (THz) or far-infrared (far-IR) region of the electromagnetic spectrum (from 0.1 THz to 10 THz, 3 cm^-1 to 300 cm^-1, or 3000 μm to 30 μm) has been shown to provide unique possibilities in the study of condensed-phase processes. The goal of this work is to expand the possibilities available in the THz region and undertake new investigations of fundamental interest to chemistry. Since we are fundamentally interested in condensed-phase processes, this thesis focuses on two areas where THz spectroscopy can provide new understanding: astrochemistry and solvation science. To advance these fields, we had to develop new instrumentation that would enable the experiments necessary to answer new questions in either astrochemistry or solvation science. We first developed a new experimental setup capable of studying astrochemical ice analogs in both the TeraHertz (THz), or far-Infrared (far-IR), region (0.3 - 7.5 THz; 10 - 250 cm^-1) and the mid-IR (400 - 4000 cm^-1). The importance of astrochemical ices lies in their key role in the formation of complex organic molecules, such as amino acids and sugars in space. Thus, the instruments are capable of performing variety of spectroscopic studies that can provide especially relevant laboratory data to support astronomical observations from telescopes such as the Herschel Space Telescope, the Stratospheric Observatory for Infrared Astronomy (SOFIA), and the Atacama Large Millimeter Array (ALMA). The experimental apparatus uses a THz time-domain spectrometer, with a 1750/875 nm plasma source and a GaP detector crystal, to cover the bandwidth mentioned above with ~10 GHz (~0.3 cm^-1) resolution.

Using the above instrumentation, experimental spectra of astrochemical ice analogs of water and carbon dioxide in pure, mixed, and layered ices were collected at different temperatures under high vacuum conditions with the goal of investigating the structure of the ice. We tentatively observe a new feature in both amorphous solid water and crystalline water at 33 cm^-1 (1 THz). In addition, our studies of mixed and layered ices show how it is possible to identify the location of carbon dioxide as it segregates within the ice by observing its effect on the THz spectrum of water ice. The THz spectra of mixed and layered ices are further analyzed by fitting their spectra features to those of pure amorphous solid water and crystalline water ice to quantify the effects of temperature changes on structure. From the results of this work, it appears that THz spectroscopy is potentially well suited to study thermal transformations within the ice.

To advance the study of liquids with THz spectroscopy, we developed a new ultrafast nonlinear THz spectroscopic technique: heterodyne-detected, ultrafast THz Kerr effect (TKE) spectroscopy. We implemented a heterodyne-detection scheme into a TKE spectrometer that uses a stilbazoiumbased THz emitter, 4-N,N-dimethylamino-4-N-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and high numerical aperture optics which generates THz electric field in excess of 300 kV/cm, in the sample. This allows us to report the first measurement of quantum beats at terahertz (THz) frequencies that result from vibrational coherences initiated by the nonlinear, dipolar interaction of a broadband, high-energy, (sub)picosecond THz pulse with the sample. Our instrument improves on both the frequency coverage, and sensitivity previously reported; it also ensures a backgroundless measurement of the THz Kerr effect in pure liquids. For liquid diiodomethane, we observe a quantum beat at 3.66 THz (122 cm^-1), in exact agreement with the fundamental transition frequency of the υ4 vibration of the molecule. This result provides new insight into dipolar vs. Raman selection rules at terahertz frequencies.

To conclude we discuss future directions for the nonlinear THz spectroscopy in the Blake lab. We report the first results from an experiment using a plasma-based THz source for nonlinear spectroscopy that has the potential to enable nonlinear THz spectra with a sub-100 fs temporal resolution, and how the optics involved in the plasma mechanism can enable THz pulse shaping. Finally, we discuss how a single-shot THz detection scheme could improve the acquisition of THz data and how such a scheme could be implemented in the Blake lab. The instruments developed herein will hopefully remain a part of the groups core competencies and serve as building blocks for the next generation of THz instrumentation that pushes the frontiers of both chemistry and the scientific enterprise as a whole.

Diurnal periodicity of winter activity in the perch, Perca fluviatilis L. [Translation from: Kalamies 1973(1) 3.]

Since 1967 data have been collected on the distribution of fish caught in a 24 hour period during the winter angling season. The present study on activity periods is based on data from nearly 2000 perch collected between 1967 and 1971. The distribution of number of fish caught during 24 hrs during December - May was studied. Of the total, the most productive period was found to be between 0600 - l600 hrs., with the peak period occurring between 0800 - 1000 hrs. The present data together show that during the darkest months of the year, the perch is only active in the mid-day period. Throughout the whole winter fishing season, activity only occurs during the time between surise and sunset.

DIFFERENTIAL GEOMETRICAL METHODS IN THE STUDY OF OPTICAL-TRANSMISSION (SCALAR THEORY) .2. TIME-DEPENDENT TRANSMISSION THEORY

By generalization of the methods presented in Part I of the study [J. Opt. Soc. Am. A 12, 600 (1994)] to the four-dimensional (4D) Riemannian manifold case, the time-dependent behavior of light transmitting in a medium is investigated theoretically by the geodesic equation and curvature in a 4D manifold. In addition, the field equation is restudied, and the 4D conserved current of the optical fluid and its conservation equation are derived and applied to deduce the time-dependent general refractive index. On this basis the forces acting on the fluid are dynamically analyzed and the self-consistency analysis is given.

The content of the form of Julia Alvarezs In the time of the butterflies

In the Time of the Butterflies é um romance da escritora dominicana-americana Julia Alvarez sobre a vida e a morte das Borboletas, Las Mariposas, codinome das irmãs Mirabal, membros de um movimento clandestino contra o regime ditatorial de Rafael Leonidas Trujillo na República Dominicana, que se tornaram símbolos da luta contra o Trujillato depois de serem assassinadas a mando do ditador. Essa dissertação tem como objetivo expor como forma literária e contexto social estão diretamente relacionados nesse romance. Ela defende a ideia de que o borramento de três gêneros literários distintos metaficção historiográfica, autobiografia e bildungsroman reflete o questionamento das fronteiras entre o privado e o público, o pessoal e o político, o eu e o outro, o individual e o coletivo, a literatura e a história, fato e ficção e história e subjetividade. Ela também tenta mostrar como a problematização dessas dicotomias implica na contestação de noções pré-concebidas de identidade, história e nação

Density-potential mapping in the standard and quantum electrodynamical time-dependent density functional theory

131 p.

Assessing trends in the density of Atlantic croaker (Micropogonias undulatus): a comparison of passive acoustic and trawl methods

Using data collected simultaneously from a trawl and a hydrophone, we found that temporal and spatial trends in densities of juvenile Atlantic croaker (Micropogonias undulatus) in the Neuse River estuary in North Carolina can be identified by monitoring their sound production. Multivariate analysis of covariance (MA NCOVA) revealed that catch per unit of effort (CPUE) of Atlantic croaker had a significant relationship with the dependent variables of sound level and peak frequency of Atlantic croaker calls. Tests of between-subject correspondence failed to detect relationships between CPUE and either of the call parameters, but statistical power was low. Williamson’s index of spatial overlap indicated that call detection rate (expressed by a 0–3 calling index) was correlated in time and space with Atlantic croaker CPUE. The correspondence between acoustic parameters and trawl catch rates varied by month and by habitat. In general, the calling index had a higher degree of overlap with this species’ density than did the received sound level of their calls. Classification and regression tree analysis identified calling index as the strongest correlate of CPUE. Passive acoustics has the potential to be an inexpensive means of identifying spatial and temporal trends in abundance for soniferous fish species.

Timing and duration of mating and brooding periods of Atka mackerel (Pleurogrammus monopterygius) in the North Pacific Ocean

The timing and duration of the reproductive cycle of Atka mackerel (Pleurogrammus monopterygius) was validated by using observations from time-lapse video and data from archival tags, and the start, peak, and end of spawning and hatching were determined from an incubation model with aged egg samples and empirical incubation times ranging from 44 days at a water temperature of 9.85°C to 100 days at 3.89°C. From June to July, males ceased diel vertical movements, aggregated in nesting colonies, and established territories. Spawning began in late July, ended in mid-October, and peaked in early September. The male egg-brooding period that followed continued from late November to mid-January and duration was highly dependent on embryonic development as affected by ambient water temperature. Males exhibited brooding behavior for protracted periods at water depths from 23 to 117 m where average daily water temperatures ranged from 4.0° to 6.2°C. Knowledge about the timing of the reproductive cycle provides a framework for conserving Atka mackerel populations and investigating the physical and biological processes influencing recruitment.

The potential use of time-area closures to reduce catches of bigeye tuna (Thunnus obesus) in the purse-seine fishery of the eastern Pacific Ocean

Skipjack (Katsuwonus pelamis), yellowfin (Thunnus albacares), and bigeye (Thunnus obesus) tunas are caught by purse-seine vessels in the eastern Pacific Ocean (EPO). Although there is no evidence to indicate that current levels of fishing-induced mortality will affect the sustainability of skipjack or yellowfin tunas, fishing mortality on juvenile (younger than 5 years of age) bigeye tuna has increased, and overall fishing mortality is greater than that necessary to produce the maximum sustainable yield of this species. We investigated whether time-area closures have the potential to reduce purse-seine bigeye catches without significantly reducing skipjack catches. Using catch and effort data for 1995–2002, we identified regions where the ratio of bigeye to skipjack tuna catches was high and applied simple closed-area models to investigate the possible benefits of time-area closures. We estimated that the most optimistic and operationally feasible 3-month closures, covering the equatorial region of the EPO during the third quarter of the year, could reduce bigeye catches by 11.5%, while reducing skipjack tuna catches by 4.3%. Because this level of bigeye tuna catch reduction is insufficient to address sustainability concerns, and larger and longer closures would reduce catches of this species signficantly, we recommend that future research be directed toward gear technology solutions because these have been successful in many other fisheries. In particular, because over 50% of purse-seine catches of bigeye tuna are taken in sets in which bigeye tuna are the dominant species, methods to allow the determination of the species composition of aggregations around floating objects may be important.

Size-composition of Annual Landings in the White Shrimp, Litopenaeus setiferus, Fishery of the Northern Gulf of Mexico, 1960–2006: Its Trend and Relationships with Other Fishery-dependent Variable

The potential for growth overfishing in the white shrimp, Litopenaeus setiferus, fishery of the northern Gulf of Mexico appears to have been of limited concern to Federal or state shrimp management entities, following the cataclysmic drop in white shrimp abundance in the 1940’s. As expected from surplus production theory, a decrease in size of shrimp in the annual landings accompanies increasing fishing effort, and can eventually reduce the value of the landings. Growth overfishing can exacerbate such decline in value of the annual landings. We characterize trends in size-composition of annual landings and other annual fishery-dependent variables in this fishery to determine relationships between selected pairs of these variables and to determine whether growth overfishing occurred during 1960–2006. Signs of growth overfishing were equivocal. For example, as nominal fishing effort increased, the initially upward, decelerating trend in annual yield approached a local maximum in the 1980’s. However, an accelerating upward trend in yield followed as effort continued to increase. Yield then reached its highest point in the time series in 2006, as nominal fishing effort declined due to exogenous factors outside the control of shrimp fishery managers. The quadratic relationship between annual yield and nominal fishing effort exhibited a local maximum of 5.24(107) pounds (≈ MSY) at a nominal fishing effort level of 1.38(105) days fished. However, annual yield showed a continuous increase with decrease in size of shrimp in the landings. Annual inflation-adjusted ex-vessel value of the landings peaked in 1989, preceded by a peak in annual inflation-adjusted ex-vessel value per pound (i.e. price) in 1983. Changes in size composition of shrimp landings and their economic effects should be included among guidelines for future management of this white shrimp

Spatial and temporal patterns in the demersal fish community on the shelf and upper slope regions of the Gulf of Alaska

We analyzed data from National Marine Fisheries Service bottom trawl surveys carried out triennially from 1984 to 1996 in the Gulf of Alaska (GOA). The continental shelf and upper slope (0–500 m) of the GOA support a rich demersal fish fauna dominated by arrowtooth flounder (Atheresthes stomias), walleye pollock (Theragra chalcogramma), Pacific cod (Gadus macrocephalus), Pacific halibut (Hippoglossus stenolepis), and Pacific Ocean perch (Sebastes alutus). Average catch per unit of effort (CPUE) of all groundfish species combined increased with depth and had a significant peak near the shelf break at 150–200 m. Species richness and diversity had significant peaks at 200–300 m. The western GOA was characterized by higher CPUEs and lower species richness and diversity than the eastern GOA. Highest CPUEs were observed in Shelikof Strait, along the shelf break and upper slope south of Kodiak Island, and on the banks and in the gullies northeast of Kodiak Island. Significant differences in total CPUE among surveys suggest a 40% increase in total groundfish biomass between 1984 and 1996. A multivariate analysis of the CPUE of 72 groundfish taxa revealed strong gradients in species composition with depth and from east to west, and a weak but significant trend in species composition over time. The trend over time was associated with increases in the frequency of occurrence and CPUE of at least eight taxa, including skates (Rajidae), capelin (Mallotus villosus), three flatfish species, and Pacific Ocean perch, and decreases in frequency of occurrence and CPUE of several sculpin (Myoxocephalus spp.) species. Results are discussed in terms of spatial and temporal patterns in productivity and in the context of their ecological and management implications.

An overview of decadal to century time-scale variability in the climate system

EXTRACT (SEE PDF FOR FULL ABSTRACT): Time scales extracted from high-resolution proxy records and observations indicate that the spectrum of climate variability exhibits significant power in the range of decades to centuries superimposed on a red-noise continuum. The classical view of climate variability is based on the concept that observed fluctuations have their origin in periodic forcings on the same time scale. ... Instead, it is proposed that these fluctuations are linked to interactions within and between the different climate system components.