| 1. |
- Geng, Ting, 1987-
(författare)
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Excited-state dynamics of small organic molecules studied by time-resolved photoelectron spectroscopy
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Ultra-violet and visible light induced processes in small organic molecules play very important roles in many fields, e.g., environmental sciences, biology, material development, chemistry, astrophysics and many others. Thus it is of great importance to better understand the mechanisms behind these processes. To achieve this, a bottom-up approach is most effective, where the photo-induced dynamics occurring in the simplest organic molecule (ethylene) are used as a starting point. Simple substituents and functional groups are added in a controlled manner to ethylene, and changes in the dynamics are investigated as a function of these modifications. In this manner, the dynamics occurring in more complex systems can be explored from a known base.In this thesis, the excited state dynamics of small organic molecules are studied by a combination of time-resolved photoelectron spectroscopy and various computational methods in order to determine the basic rules necessary to help understand and predict the dynamics of photo-induced processes.The dynamics occurring in ethylene involve a double bond torsion on the ππ* excited state, followed by the decay to the ground state coupled with pyramidalization and hydrogen migration. Several different routes of chemical modification are used as the basis to probe these dynamics as the molecular complexity is increased. (i) When ethylene is modified by the addition of an alkoxyl group (-OCnH2n+1), a new bond cleavage reaction is observed on the πσ* state. When modified by a cyano (-CN) group, a significant change in the carbon atom involved in pyramidalization is observed. (ii) When ethylene used to build up small cyclic polyenes, it is observed that the motifs of the ethylene dynamics persist, expressed as ring puckering and ring opening. (iii) In small heteroaromatic systems, i.e., an aromatic ring containing an ethylene-like sub-structure and one or two non-carbon atoms, the type of heteroatom (N: pyrrole, pyrazole O: furan) gives rise to different bond cleavage and ring puckering channels. Furthermore, adding an aldehyde group (-C=O) onto furan, as a way to lengthen the delocalised ring electron system, opens up additional reaction channels via a nπ* state.The results presented here are used to build up a more complete picture of the dynamics that occur in small molecular systems after they are excited by a visible or UV photon, and are used as a basis to motivate further investigations.
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| 2. |
- Kaislahti Tillman, Päivi, 1958-
(författare)
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Holocene climate and environmental change in high latitudes as recorded by stable isotopes in peat deposits
- 2012
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis, stable carbon and oxygen isotopes in α-cellulose isolated from Sphagnum fuscum moss remains were used as climate proxies. The main focus was to implement the methods in records from high latitude peatlands in the Northern Hemisphere (west-central Canada and north-eastern European Russia), reconstruct palaeoclimate of the studied regions during the Holocene, and evaluate the compatibility of results with other proxy records, especially tree-ring isotope time-series. The variation of stable carbon and oxygen isotope ratios (δ13C, δ18O) in different moss plant components was investigated and differences between untreated plants and α-cellulose extracts were evaluated. The impact of peat decay on the stable isotope proxies was studied by colorimetric and chemical (C/N) methods. Temperature reconstructions were developed based on the statistically significant relationship between δ13C and modern summer temperature records. Wet/dry periods were derived from a combination of δ18O records, macrofossil analysis, and a peat humification record in west-central Canada. A tentative reconstruction of snow depth in north-eastern European Russian tundra and northern taiga was based on δ18O records. The most promising result of the thesis is that stable carbon isotope variability in α-cellulose isolated from Sphagnum fuscum stems can be used to reconstruct and quantify palaeotemperatures several millennia back in time and to reveal both long-term and rapid climate shifts from peat archives.
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