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One- and two-dimensional infrared spectroscopic studies of solution-phase homogeneous catalysis and spin-forbidden reactions

Description: Understanding chemical reactions requires the knowledge of the elementary steps of breaking and making bonds, and often a variety of experimental techniques are needed to achieve this goal. The initial steps occur on the femto- through picosecond time-scales, requiring the use of ultrafast spectroscopic methods, while the rate-limiting steps often occur more slowly, requiring alternative techniques. Ultrafast one and two-dimensional infrared and step-scan FTIR spectroscopies are used to investigate the photochemical reactions of four organometallic complexes. The analysis leads to a detailed understanding of mechanisms that are general in nature and may be applicable to a variety of reactions.
Date: December 12, 2008
Creator: Sawyer, Karma Rae
Partner: UNT Libraries Government Documents Department

Solar photochemistry - twenty years of progress, what`s been accomplished, and where does it lead?

Description: It has been more than 20 years since the first oil embargo. That event created an awareness of the need for alternative sources of energy and renewed interest in combining sunlight and chemistry to produce the chemicals and materials required by industry. This paper will review approaches that have been taken, progress that has been made, and give some projections for the near and longer term prospects for commercialization of solar photochemistry.
Date: January 1, 1995
Creator: Blake, D M
Partner: UNT Libraries Government Documents Department

Chemical and Photochemical Reactions of Thioctic Acid and RelatedDisulfides

Description: The carbon cycle of photosynthesis is briefly reviewed in its entirety and the experiments involving it which led to the implication of disulfide rupture in photosynthesis are indicated. A review of the organic, physical and photochemistry of disulfides, with particular reference to the five-membered disulfide rings as they appear in thioctic acid, is given.
Date: June 10, 1954
Creator: Calvin, Melvin
Partner: UNT Libraries Government Documents Department


Description: The synthesis of nonracemic yields of hexa-, hepta-, octa-, and nonhelicene with circular light was observed, and the structural and wavelength dependence of the induced optical yields was examined. The results obtained, together with a detailed consideration of the mechanism of helicene synthesis from the parent diarylolefins, indicate that the induced optical activity is due to selective reaction of enantiomeric conformations of the parent cis diarylolefins by circular light.
Date: May 1, 1971
Creator: Bernstein, William J.; Calvin, Melvin & Buchardt, Ole.
Partner: UNT Libraries Government Documents Department

Path of Carbon in Photosynthesis III

Description: Although the overall reaction of photosynthesis can be specified with some degree of certainty (CO{sub 2} + H{sub 2}O + light {yields} sugars + possibly other reduced substances), the intermediates through which the carbon passes during the course of this reduction have, until now, been largely a matter of conjecture. The availability of isotopic carbon, that is, a method of labeling the carbon dioxide, provides the possibility of some very direct experiments designed to recognize these intermediates and, perhaps, help to understand the complex sequence and interplay of reactions which must constitute the photochemical process itself. The general design of such experiments is an obvious one, namely the exposure of the green plant to radioactive carbon dioxide and light under a variety of conditions and for continually decreasing lengths of time, followed by the identification of the compounds into which the radioactive carbon is incorporated under each condition and time period. From such data it is clear that in principle, at least, it should be possible to establish the sequence of compounds in time through which the carbon passes on its path from carbon dioxide to the final products. In the course of shortening the photosynthetic times, one times, one ultimately arrives at the condition of exposing the plants to the radioactive carbon dioxide with a zero illumination time, that is, in the dark. Actually, in the work the systematic order of events was reversed, and they have begun by studying first the dark fixation and then the shorter photosynthetic times. The results of the beginnings of this sort of a systematic investigation are given in Table I which includes three sets of experiments, namely a dark fixation experiment and two photosynthetic experiments, one of 30 seconds duration and the other of 60 seconds duration.
Date: June 1, 1948
Creator: Benson, A.A. & Calvin, M.
Partner: UNT Libraries Government Documents Department

Carbon Dioxide Fixation by Green Plants

Description: Since the end of the war when the long-lived isotope of carbon, C{sup 14} became available a new tool has been applied in the study of photosynthesis. Because of the interest evoked by the tracer method, research in all areas of photosynthesis has expanded. There have been reviews on various aspects of photosynthesis such as the primary photochemical reaction, quantum efficiency products, and comparative biochemistry, many discussions of which were included in the monograph of The American Society of Plant Physiologists, ''Photosynthesis in Plants''.
Date: January 3, 1950
Creator: Benson, A.A. & Calvin, M.
Partner: UNT Libraries Government Documents Department

Chlorine-36 abundance in natural and synthetic perchlorate

Description: Perchlorate (ClO{sub 4}{sup -}) is ubiquitous in the environment. It occurs naturally as a product of atmospheric photochemical reactions, and is synthesized for military, aerospace, and industrial applications. Nitrate-enriched soils of the Atacama Desert (Chile) contain high concentrations of natural ClO{sub 4}{sup -}; nitrate produced from these soils has been exported worldwide since the mid-1800's for use in agriculture. The widespread introduction of synthetic and agricultural ClO{sub 4}{sup -} into the environment has complicated attempts to understand the geochemical cycle of ClO{sub 4}{sup -}. Natural ClO{sub 4}{sup -} samples from the southwestern United States have relatively high {sup 36}Cl abundances ({sup 36}Cl/Cl = 3,100 x 10{sup -15} to 28,800 x 10{sup -15}), compared with samples of synthetic ({sup 36}Cl/Cl = 0.0 x 10{sup -15} to 40 x 10{sup -15}) and Atacama Desert ({sup 36}Cl/Cl = 0.9 x 10{sup -15} to 590 x 10{sup -15}) ClO{sub 4}{sup -}. These data give a lower limit for the initial {sup 36}Cl abundance of natural ClO{sub 4}{sup -} and provide temporal and other constraints on its geochemical cycle.
Date: January 1, 2009
Creator: Heikoop, Jeffrey M; Dale, M; Sturchio, Neil C; Caffee, M; Belosa, A D; Heraty, Jr., L J et al.
Partner: UNT Libraries Government Documents Department

Photodissociation of ketene: CH{sub 2}CO {yields} CH{sub 2}(a{sup 1}A{sub 1}) + CO(v=1) rates and dynamics

Description: The rotational energy release in the dissociation of ketene (CH{sub 2}CO) along its singlet potential energy surface is observed and compared with several statistical and dynamical theories. Rotational distributions for the product, CO(X{sup 1}{Sigma}+)(v=1), are measured from the threshold for production of CH{sub 2}(a {sup 1}A{sub 1}) (0,0,0) + CO(X{sup 1}{Sigma}+)(v=1) to 1720 cm{sup -1} above. Near threshold (E{le} 200 cm{sup -1} over threshold), phase space theory (PST) matches the observed distributions. At 357 and 490 cm{sup -1}, PST constrained by the measured state distributions of the methylene fragment, provides a good fit to these CO(v=1) rotational distributions. For E > 490 cm{sup -1}, the constrained PST matches the average rotational energy observed but predicts distributions which are broader than observed. This contrasts to the rotational distributions of the {sup 1}CH{sub 2} fragment which become shifted to lower rotational states than PST as energy increases from 200 cm{sup -1} above threshold. Dynamical models, the impulsive model and Franck-Condon mapping, do not account for the product rotational state distributions. The CO(v=1) rotational distributions for E > 200 cm{sup -1} contain no measurable product from triplet channel fragmentation. Therefore, they can be compared with the previously determined CO(v=0) rotational distributions in order to partition the CO(v=0) yield between singlet and triplet channels and recalculate the singlet yield. This new yield is found to be at the upper limits of the range previously reported. Rate constants and quantum yields have been determined for the photodissociation of ketene to produce CH{sub 2}(a {sup 1}A{sub 1}) (0,0,0) + CO(X {sup 1}{Sigma}+)(v=1). At 57, 110, 200, 357, and 490 cm{sup -1} above this product threshold, vibrational branching ratios for the singlet products were measured and compared to phase space theory (PST), separate statistical ensembles (SSE), and variational RRKM (var. RRKM).
Date: December 1, 1996
Creator: Wade, E.A.
Partner: UNT Libraries Government Documents Department

Photopolymers designed for high resolution laser ablation at a specific irradiation wavelength

Description: We have developed novel photopolymers based on the triazeno chromophore group. The absorption properties can be tailored for a specific irradiation wavelength (e.g. 308 nm XeCl laser). With the introduction of a photolabile group into the main chain of the polymer we expected a mechanism which is mainly photochemical. This should result in high resolution etching with no thermal damage or chemical / physical modification to the material. The gaseous products of the photochemical decomposition were thought to assist the material removal, and to prevent the re-deposition of solid products which would contaminate the surface. We confirmed (SEM/AFM) that the irradiation of the polymer at 308 mn resulted in high resolution etching. No debris has been found around the etched comers. Maximum ablation rates of about 3 {mu}m / pulse were achieved due to the dynamic absorption behavior (bleaching during the pulse). No physical or chemical modifications of the polymer surface could be detected after irradiation at the tailored absorption wavelength, whereas irradiation at different wavelengths resulted in modified (physical and chemical) surfaces. The etching mechanism can be described as a laser induced microexplosion, revealed by ns-imaging. The etching of the polymer starts and ends with the laser pulse, shown by ns-interferometry, confirming that the acting mechanism is mainly photochemical at high fluences for our polymers. Our results demonstrate that the mechanism of ablation can be controlled by designing special polymers, which can be used as high resolution laser dry etching resists.
Date: April 1, 1997
Creator: Lippert, T.; Bennett, L. S.; Kunz, T. & Hahn, C.
Partner: UNT Libraries Government Documents Department

The linkage of chemical energy conversion to ultrafast photochemistry in photosynthesis

Description: High-quantum-yield, photochemical energy conversion requires that energy (photons) captured by ultra fast photophysical processes be converted to chemical or electrochemical products. Natural photosynthesis provides examples of systems in which photophysical and chemical processes are nearly optimally linked. The natural systems have a hierarchical design, consisting of discrete chemical subsystems that break photosynthesis into a sequence of individual photochemical and chemical reaction steps. This project examines the influence of specific protein microenvironments on the sequence of electron transfer and on the assembly of hierarchical, supramolecular photosynthetic assemblies.
Date: May 1, 1996
Creator: Tiede, D.M. Vazquez, J. & Cordova, J.
Partner: UNT Libraries Government Documents Department

Molecular structure determination for photogenerated intermediates in photoinduced electron transfer reactions using steady-state and transient XAFS

Description: Many photoinduced electron transfer reactions are accompanied by nuclear rearrangements of the molecules involved. In order to understand the reactivities of the molecules and the reaction mechanisms, precise information on the molecular structural changes accompanying the electron transfer is often required. We present here conventional XAFS and transient energy dispersive XAFS studies on structures of excited and photoinduced charge separated state of porphyrin and porphyrin based supermolecules, and structures of TiO{sub 2} colloid and the heavymetal ions that bind to the colloid surfaces during photocatalytic reductions.
Date: October 1, 1996
Creator: Chen, L.X.; Wasielewski, M.R. & Rajh, T.
Partner: UNT Libraries Government Documents Department

Manifestations of sequential electron transfer

Description: An essential feature of efficient photo-initiated charge separation is sequential electron transfer. Charge separation is initiated by photoexcitation of an electron donor followed by rapid electron transfer steps from the excited donor through a series of electron acceptors, so that, after one or two successive steps, charge separation is stabilized by the physical separation between the oxidized donor and reduced acceptor. The prime example of this process is the sequential electron transfer that takes place in the purple photosynthetic bacterial reaction center, resulting in the charge separation between P{sup +} and Q{sub A}{sup -} across a biological membrane. We have developed magnetic resonance tools to monitor sequential electron transfer. We are applying these techniques to study charge separation in natural photo-synthetic systems in order to gain insights into the features of the reaction center proteins that promote efficient charge separation. As we establish what some of these factors are, we are beginning to design artificial photosynthetic systems that undergo photoinduced sequential electron transfer steps.
Date: May 1, 1996
Creator: Thurnauer, M.C. & Tang, J.
Partner: UNT Libraries Government Documents Department

Photochemical coal dissolution. Final technical progress report, September 30, 1993--September 29, 1996

Description: A flowing solvent photochemical reactor was designed, built and tested. A modified ACE photochemical reactor, lamp and power supply were employed. They were modified to accommodate a silica column-constrained dispersed coal sample and a solvent flowing through the silica/coal column to sweep away coal extract. Before each experiment the column was packed with the mixture of silica and coal in the annular space around the lamp. A reflective aluminum surface (foil) reflected any light-transmitted through the column for multiple passes back through the sample. A variable speed Rainin Rabbit Plus peristaltic pump was interfaced to an IBM XT computer via a Gilson RS232/RS422 converter. The purpose of the computer control was to vary the speed of the pump so as to control the absorbance of the solution of coal extract in the solvent. Absorbances at a chosen wavelength were measured by a Spec 21 spectrophotometer with a flow cell connected to the column effluent port. A signal proportional to transmittance from the Spec 21 was delivered to the computer through a Keithley DAS 801 A/D plug-in the computer. The analysis of the Spec 21 signal and control of the pump speed was based on a QuickBasic computer program written by us.
Date: May 1, 1997
Creator: Doetschman, D.C.
Partner: UNT Libraries Government Documents Department