Exploratory studies on coordination chemistry of a redox-active bridging ligand: synthesis, properties and solid state structures of the complexes

The explorative coordination chemistry of the bridging ligand TTF-PPB is presented. Its strong binding ability to Co(II) and then to Ni(II) or Cu(II) in the presence of hexafluoroacetylacetonate (hfac(-)), forming new mono-and dinuclear complexes 1-3, is described. X-ray crystallographic studies have been conducted in the case of the free ligand TTF-PPB as well as its complexes [Co(TTF-PPB)(hfac)(2)] (1) and [Co(hfac)(2)(mu-TTF-PPB)Ni(hfac)(2)] (2). Each metal ion is bonded to two bidentate hfac-anions through their oxygen atoms and two nitrogen atoms of the PPB moiety with a distorted octahedral coordination geometry. Specifically, nitrogen donor atoms of TTF-PPB adopt a cis-coordination but not in the equatorial plane, which is quite rare. Electronic absorption, photoinduced intraligand charge transfer ((1)ILCT), and electrochemical behaviour of 1-3 have been investigated. UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred pi-pi* transitions and an intense broad band in the visible region corresponding to a spin-allowed pi-pi* (1)ILCT transition. Upon coordination, the (1)ILCT band is bathochromically shifted by 3100, 6100 and 5900 cm(-1) on going from 1 to 3. The electrochemical studies reveal that all of them undergo two reversible oxidation and one reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the PPB unit, respectively.

Photodissociation dynamics of tert-butylnitrite following excitation to the S(1) and S(2) states. A study by velocity-map ion-imaging and 3D-REMPI spectroscopy

Excitation of tert-butylnitrite into the first and second UV absorption bands leads to efficient dissociation into the fragment radicals NO and tert-butoxy in their electronic ground states (2)Π and (2)E, respectively. Velocity distributions and angular anisotropies for the NO fragment in several hundred rotational and vibrational quantum states were obtained by velocity-map imaging and the recently developed 3D-REMPI method. Excitation into the well resolved vibronic progression bands (k = 0, 1, 2) of the NO stretch mode in the S(1) ← S(0) transition produces NO fragments mostly in the vibrational state with v = k, with smaller fractions in v = k - 1 and v = k - 2. It is concluded that dissociation occurs on the purely repulsive PES of S(1) without barrier. All velocity distributions from photolysis via the S(1)(nπ*) state are monomodal and show high negative anisotropy (β ≈ -1). The rotational distributions peak near j = 30.5 irrespective of the vibronic state S(1)(k) excited and the vibrational state v of the NO fragment. On average 46% of the excess energy is converted to kinetic energy, 23% and 31% remain as internal energy in the NO fragment and the t-BuO radical, respectively. Photolysis via excitation into the S(2) ← S(0) transition at 227 nm yields NO fragments with about equal populations in v = 0 and v = 1. The rotational distributions have a single maximum near j = 59.5. The velocity distributions are monomodal with positive anisotropy β ≈ 0.8. The average fractions of the excess energy distributed into translation, internal energy of NO, and internal energy of t-BuO are 39%, 23%, and 38%, respectively. In all cases ∼8500 cm(-1) of energy remain in the internal degrees of freedom of the t-BuO fragment. This is mostly assigned to rotational energy. An ab initio calculation of the dynamic reaction path shows that not only the NO fragment but also the t-BuO fragment gain large angular momentum during dissociation on the purely repulsive potential energy surface of S(2).

Integrated solar energy and absorption cooling model for HVAC (heating, ventilating, and air conditioning) applications in buildings

The demands in production and associate costs at power generation through non renewable resources are increasing at an alarming rate. Solar energy is one of the renewable resource that has the potential to minimize this increase. Utilization of solar energy have been concentrated mainly on heating application. The use of solar energy in cooling systems in building would benefit greatly achieving the goal of non-renewable energy minimization. The approaches of solar energy heating system research done by initiation such as University of Wisconsin at Madison and building heat flow model research conducted by Oklahoma State University can be used to develop and optimize solar cooling building system. The research uses two approaches to develop a Graphical User Interface (GUI) software for an integrated solar absorption cooling building model, which is capable of simulating and optimizing the absorption cooling system using solar energy as the main energy source to drive the cycle. The software was then put through a number of litmus test to verify its integrity. The litmus test was conducted on various building cooling system data sets of similar applications around the world. The output obtained from the software developed were identical with established experimental results from the data sets used. Software developed by other research are catered for advanced users. The software developed by this research is not only reliable in its code integrity but also through its integrated approach which is catered for new entry users. Hence, this dissertation aims to correctly model a complete building with the absorption cooling system in appropriate climate as a cost effective alternative to conventional vapor compression system.

Low-lying excited states and nonradiative processes of 9-methyl-2-aminopurine

he UV spectrum of the adenine analogue 9-methyl-2-aminopurine (9M-2AP) is investigated with one- and two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm−1 resolution in a supersonic jet. The electronic origin at 32 252 cm−1 exhibits methyl torsional subbands that originate from the 0A′′1 (l = 0) and 1E ″ (l = ±1) torsional levels. These and further torsional bands that appear up to 000+230 cm−1 allow to fit the threefold (V 3) barriers of the torsional potentials as ∣∣V′′3∣∣=50 cm−1 in the S 0 and ∣∣V′3∣∣=126 cm−1 in the S 1 state. Using the B3LYP density functional and correlated approximate second-order coupled cluster CC2 methods, the methyl orientation is calculated to be symmetric relative to the 2AP plane in both states, with barriers of V′′3=20 cm−1 and V′3=115 cm−1. The 000 rotational band contour is 75% in-plane (a/b) polarized, characteristic for a dominantly long-axis 1ππ* excitation. The residual 25% c-axis polarization may indicate coupling of the 1ππ* to the close-lying 1 nπ* state, calculated at 4.00 and 4.01 eV with the CC2 method. However, the CC2 calculated 1 nπ oscillator strength is only 6% of that of the 1ππ* transition. The 1ππ* vibronic spectrum is very complex, showing about 40 bands within the lowest 500 cm−1. The methyl torsion and the low-frequency out-of-plane ν′1 and ν′2 vibrations are strongly coupled in the 1ππ* state. This gives rise to many torsion-vibration combination bands built on out-of-plane fundamentals, which are without precedence in the 1ππ* spectrum of 9H-2-aminopurine [S. Lobsiger, R. K. Sinha, M. Trachsel, and S. Leutwyler, J. Chem. Phys.134, 114307 (2011)]. From the Lorentzian broadening needed to fit the 000 contour of 9M-2AP, the 1ππ* lifetime is τ ⩾ 120 ps, reflecting a rapid nonradiative transition.

Collimated Field Emission Beams from Metal Double-Gate Nanotip Arrays Optically Excited via Surface Plasmon Resonance

The generation of collimated electron beams from metal double-gate nanotip arrays excited by near infrared laser pulses is studied. Using electromagnetic and particle tracking simulations, we showed that electron pulses with small rms transverse velocities are efficiently produced from nanotip arrays by laser-induced field emission with the laser wavelength tuned to surface plasmon polariton resonance of the stacked double-gate structure. The result indicates the possibility of realizing a metal nanotip array cathode that outperforms state-of-the-art photocathodes.

The influence of physical state on shikimic acid ozonolysis: a case for in situ microspectroscopy

Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O3 in a Criegee-type reaction. We used an environmental microreactor embedded in a scanning transmission X-ray microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain near-edge X-ray absorption fine structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid–water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the timescale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.

Colored dissolved organic matter (cDOM) absorption measurements in Antarctic lakes

The datasets present measurements of cDOM absorption of lakes located in Antarctic oasis during the summer periods from 2013 to 2016. In summer season of 2013 water samples were collected on Fildes Peninsula (King George Island, West Antarctica) - Bellingshausen Station, Russia. Investigated lakes on Fides Peninsula were completely or partly free from ice cover during water sampling. In summer seasons of 2014-2016 water samples were collected on Vestfold Hills, Reuer Island and Larsemann Hills Oasis (East Antarctica) - Progress station, Russia. During 2014-2016 summer season part of lakes on Larsemann Hills Oasis were free from ice cover, some of the lakes were completely covered by ice and were drilled before sampling. Part of the water samples from Progress Station (2015) has not been filtered. cDOM is operationally defined by the chosen filter pore size. Samples have been consistently filtrated through 0.7 µm pore size glas fibre filters. cDOM filtrates have been stored in darkness and have been measured after the expedition using the dual-beam Specord200 laboratory spectrometer (Jena Analytik) at the Otto Schmidt Laboratory OSL, Arctic and Antarctic Research Institute, St. Petersburg, Russia. The OSL cDOM protocol (Heim and Roessler, 2016) prescribes 3 Absorbance (A) measurements per sample from UV to 750 nm against ultra-pure water. The absorption coefficient, a, is calculated by a = 2.303A/L, where L is the pathlength of the cuvette [m], and the factor 2.303 converts log10 to loge. The output of the calculation is a continuous spectrum of a. The cDOM a spectra are used to determine the exponential slope value for specific wavelength ranges, S by fitting the data between min and max wavelength to an exponential function. We provide cDOM absorption coefficients for the wavelengths 254, 260, 350, 375, 400, 412, 440, 443 nm [1/m] and Slope values for three different UV, VIS, wavelength ranges: 275 to 295 nm, 350 to 400 nm, 300 to 500 nm [1/nm]. All data were carried out by scientists from Arctic and Antarctic Research Institute and Saint Petersburg State University of Russia during Russian Antarctic Expedition in 2013-2016.

Colored dissolved organic matter (cDOM) absorption measurements in terrestrial water objects of Yamal, Yavai and Gydan Peninsula

The datasets present measurements of cDOM absorption in lakes, rivers and streams of Yamal and Gydan Peninsula area during the summer periods from 2012-2014 and 2016. In summer seasons of 2012 - 2013 water samples was collected during "Yamal-Arctic" Expedition. All of the research areas were located near the coastline of Yamal, Yavay, and Gydan Peninsula and Bely Island. In 2012 water samples from rivers, lakes and streams were taken near New Port, Cape Kamenny and Tambey settlements and in basins (water catchments) of the Sabetta, Seyakha, Yuribey (Baydaratskaya Bay, Gydan Peninsula) and Mongocheyakha rivers. In 2013 water samples from rivers, lakes and streams were taken in the Yavai Peninsula, Yayne Vong bay and in the basins (water catchments) of the Sabetta, Mongocheyakha and Yuribey (Gydan Peninsula) rivers. In 2014 lakes were sampled in the Erkuta River basin, south of Yamal Peninsula. In 2016 lakes and rivers were sampled it the Erkuta River basin and Polar Ural area. cDOM is operationally defined by the chosen filter pore size. Samples have been consistently filtrated through 0.7 µm pore size glas fibre filters. cDOM filtrates have been stored in darkness and have been measured after the expedition using the dual-beam Specord200 laboratory spectrometer (Jena Analytik) at the Otto Schmidt Laboratory OSL, Arctic and Antarctic Research Institute, St. Petersburg, Russia. The OSL cDOM protocol (Heim and Roessler, 2016) prescribes 3 Absorbance (A) measurements per sample from UV to 750 nm against ultra-pure water. The absorption coefficient, a, is calculated by a = 2.303A/L, where L is the pathlength of the cuvette [m], and the factor 2.303 converts log10 to loge. The output of the calculation is a continuous spectrum of a. The cDOM a spectra are used to determine the exponential slope value for specific wavelength ranges, S by fitting the data between min and max wavelength to an exponential function. We provide cDOM absorption coefficients for the wavelengths 254, 260, 350, 375, 400, 412, 440, 443 nm [1/m] and Slope values for three different UV, VIS, wavelength ranges: 275 to 295 nm, 350 to 400 nm, 300 to 500 nm [1/m]. All data were carried out by scientists from Arctic and Antarctic Research Institute and Saint Petersburg State University of Russia during "Yamal-Arctic" expeditions in 2012-2013, RFBR project No 14-04-10065 in 2014, No 14-05-00787 in 2016.

Analysis of microscopic magnitudes of radiative blast waves launched in xenon clusters with collisional-radiative steady-state simulations

Radiative shock waves play a pivotal role in the transport energy into the stellar medium. This fact has led to many efforts to scale the astrophysical phenomena to accessible laboratory conditions and their study has been highlighted as an area requiring further experimental investigations. Low density material with high atomic mass is suitable to achieve radiative regime, and, therefore, low density xenon gas is commonly used for the medium in which the radiative shocks such as radiative blast waves propagate. In this work, by means of collisional-radiative steady-state calculations, a characterization and an analysis of microscopic magnitudes of laboratory blast waves launched in xenon clusters are made. Thus, for example, the average ionization, the charge state distribution, the cooling time or photon mean free paths are studied. Furthermore, for a particular experiment, the effects of the self-absorption and self-emission in the specific intensity emitted by the shock front and that is going through the radiative precursor are investigated. Finally, for that experiment, since the electron temperature is not measured experimentally, an estimation of this magnitude is made both for the shock shell and the radiative precursor.