201 research outputs found
Computational design of metal-supported molecular switches: Transient ion formation during light- and electron-induced isomerisation of azobenzene
In molecular nanotechnology, a single molecule is envisioned to act as the
basic building block of electronic devices. Such devices may be of special
interest for organic photovoltaics, data storage, and smart materials. However,
more often than not the molecular function is quenched upon contact with a
conducting support. Trial-and-error-based decoupling strategies via molecular
functionalisation and change of substrate have in many instances proven to
yield unpredictable results. The adsorbate-substrate interactions that govern
the function can be understood with the help of first-principles simulation.
Employing dispersion-corrected Density-Functional Theory (DFT) and linear
expansion Delta-Self-Consistent-Field DFT, the electronic structure of a
prototypical surface-adsorbed functional molecule, namely azobenzene adsorbed
to (111) single crystal facets of copper, silver and gold, is investigated and
the main reasons for the loss or survival of the switching function upon
adsorption are identified. The light-induced switching ability of a
functionalised derivative of azobenzene on Au(111) and azobenzene on Ag(111)
and Au(111) is assessed based on the excited-state potential energy landscapes
of their transient molecular ions, which are believed to be the main
intermediates of the experimentally observed isomerisation reaction. We provide
a rationalisation of the experimentally observed function or lack thereof that
connects to the underlying chemistry of the metal-surface interaction and
provides insights into general design strategies for complex light-driven
reactions at metal surfaces.Comment: 14 pages, 5 figures, submitted to J. Phys. Condens. Matte
Bistability loss as key feature in azobenzene (non-)switching on metal surfaces
Coinage metal adsorbed azobenzene is investigated as prototypical molecular
switch. It is shown that switching capabilities are not just lost due to
excited state quenching, but already due to changes in the ground state
energetics. Electron demanding coadsorbates are suggested as strategy to regain
the switching function.Comment: 8 pages, 3 figure
Assessing computationally efficient isomerization dynamics: Delta-SCF density-functional theory study of azobenzene molecular switching
We present a detailed comparison of the S0, S1 (n -> \pi*) and S2 (\pi ->
\pi*) potential energy surfaces (PESs) of the prototypical molecular switch
azobenzene as obtained by Delta-self-consistent-field (Delta-SCF)
Density-Functional Theory (DFT), time-dependent DFT (TD-DFT) and approximate
Coupled Cluster Singles and Doubles (RI-CC2). All three methods unanimously
agree in terms of the PES topologies, which are furthermore fully consistent
with existing experimental data concerning the photo-isomerization mechanism.
In particular, sum-method corrected Delta-SCF and TD-DFT yield very similar
results for S1 and S2, when based on the same ground-state exchange-correlation
(xc) functional. While these techniques yield the correct PES topology already
on the level of semi-local xc functionals, reliable absolute excitation
energies as compared to RI-CC2 or experiment require an xc treatment on the
level of long-range corrected hybrids. Nevertheless, particularly the
robustness of Delta-SCF with respect to state crossings as well as its
numerical efficiency suggest this approach as a promising route to dynamical
studies of larger azobenzene-containing systems.Comment: 25 pages, 6 figure
Applications of technology and large data in statistics education and statistical graphics
This dissertation is a composite of research preformed in the fields of statistics education and statistical graphics. The three body chapters stand as the pillars of this work; tied together by the common theme of overcoming challenges and grasping opportunities that are posed by emerging technologies and prodigious data sources. In Chapter 1 a review of the literature is conducted to lay the foundation upon which the work of the main body chapters is built. Chapter 2 is an educational experiment comparing the learning outcomes from simulation-based and traditional statistical inference curricula. Chapter 3 studies the development of a shiny application to connect students to large data. Chapter 4 contributes to research on binned scatterplots as a graphical tool for visualizing large data. Each body chapter in this dissertation is intended be submitted for publication individually; therefore, more detailed abstracts may be found at the beginning of each chapter
Interpretation of X-ray Absorption Spectroscopy in the Presence of Surface Hybridization
X-ray absorption spectroscopy yields direct access to the electronic and
geometric structure of hybrid inorganic-organic interfaces formed upon
adsorption of complex molecules at metal surfaces. The unambiguous
interpretation of corresponding spectra is challenged by the intrinsic
geometric flexibility of the adsorbates and the chemical interactions with the
interface. Density-functional theory (DFT) calculations of the extended
adsorbate-substrate system are an established tool to guide peak assignment in
X-ray photoelectron spectroscopy (XPS) of complex interfaces. We extend this to
the simulation and interpretation of X-ray absorption spectroscopy (XAS) data
in the context of functional organic molecules on metal surfaces using
dispersion-corrected DFT calculations within the transition potential approach.
On the example of X-ray absorption signatures for the prototypical case of
2H-porphine adsorbed on Ag(111) and Cu(111) substrates, we follow the two main
effects of the molecule/surface interaction on XAS: (1) the substrate-induced
chemical shift of the 1s core levels that dominates in physisorbed systems and
(2) the hybridization-induced broadening and loss of distinct resonances that
dominates in more chemisorbed systems.Comment: 13 pages, 4 figure
Computational design of metal-supported molecular switches : Transient ion formation during light- and electron-induced isomerisation of azobenzene
In molecular nanotechnology, a single molecule is envisioned to act as the basic building block of electronic devices. Such devices may be of special interest for organic photovoltaics, data storage, and smart materials. However, more often than not the molecular function is quenched upon contact with a conducting support. Trial-and-error-based decoupling strategies via molecular functionalisation and change of substrate have in many instances proven to yield unpredictable results. The adsorbate-substrate interactions that govern the function can be understood with the help of rst-principles simulation. Employing dispersion-corrected Density-Functional Theory (DFT) and linear expansion Delta-Self-Consistent-Field DFT, the electronic structure of a prototypical surface-adsorbed functional molecule, namely azobenzene adsorbed to (111) single crystal facets of copper, silver and gold, is investigated and the main reasons for the loss or survival of the switching function upon adsorption are identifed. The light-induced switching ability of a functionalised derivative of azobenzene on Au(111) and azobenzene on Ag(111) and Au(111) is assessed based on the excited-state potential energy landscapes of their transient molecular ions, which are believed to be the main intermediates of the experimentally observed isomerisation reaction. We provide a rationalisation of the experimentally observed function or lack thereof that connects to the underlying chemistry of the metal-surface interaction and provides insights into general design strategies for complex light-driven reactions at metal surfaces
Excited-state potential-energy surfaces of metal-adsorbed organic molecules from Linear Expansion \Delta-Self-Consistent Field Density-Functional Theory (\Delta SCF-DFT)
Accurate and efficient simulation of excited state properties is an important
and much aspired cornerstone in the study of adsorbate dynamics on metal
surfaces. To this end, the recently proposed linear expansion \Delta
Self-Consistent Field (le\Delta SCF) method by Gavnholt et al. [Phys. Rev. B
78, 075441 (2008)] presents an efficient alternative to time consuming
quasi-particle calculations. In this method the standard Kohn-Sham equations of
Density-Functional Theory are solved with the constraint of a non-equilibrium
occupation in a region of Hilbert-space resembling gas-phase orbitals of the
adsorbate. In this work we discuss the applicability of this method for the
excited-state dynamics of metal-surface mounted organic adsorbates,
specifically in the context of molecular switching. We present necessary
advancements to allow for a consistent quality description of excited-state
potential-energy surfaces (PESs), and illustrate the concept with the
application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find
that the explicit inclusion of substrate electronic states modifies the
topologies of intra-molecular excited-state PESs of the molecule due to image
charge and hybridization effects. While the molecule in gas phase shows a clear
energetic separation of resonances that induce isomerization and backreaction,
the surface-adsorbed molecule does not. The concomitant possibly simultaneous
induction of both processes would lead to a significantly reduced switching
efficiency of such a mechanism.Comment: 12 pages, 4 figure
Angioedema quality of life questionnaire (AE-QoL) - interpretability and sensitivity to change
BACKGROUND:
The Angioedema Quality of Life (AE-QoL) is the first patient reported outcome measure developed for the assessment of quality of life (QoL) impairment in patients with recurrent angioedema (RAE). This study aimed to evaluate the clinimetric properties of the AE-QoL in Thai patients and to establish categories of QoL impairment assessed by the AE-QoL.
METHODS:
The validated Thai version of the Dermatology Life Quality Index (DLQI) and Patient Global Assessment of Quality of Life (PGA-QoL) were used to comparatively evaluate the Thai version of AE-QoL. Spearman correlations between the Thai AE-QoL and two other standard measurements (DLQI and PGA-QoL) were investigated to determine convergent validity. The Thai DLQI and PGA-QoL were used to categorize patients according to their QoL. Known-group validity of the Thai AE-QoL was later analyzed. The reliability of the Thai AE-QoL was investigated using Cronbach's alpha and intraclass correlation. Three different approaches including the distribution method, receiver operating characteristic curve analysis, and the anchor based-method were used for the interpretability.
RESULTS:
A total of 86 patients with RAE with a median age of 38.0 ± 15.1 years (range 18-76) were enrolled. Of those, 76 patients (88%) had RAE with concomitant wheals, and 10 patients (11.6%) had RAE only. The AE-QoL assessed RAE-mediated QoL impairment with high convergent validity and known-groups validity, high internal consistency and test-retest reliability, and good sensitivity to change. Although the AE-QoL did not differentiate between patients with moderate and large effect as measured by PGA-QoL or DLQI in this study, AE-QoL total values of 0-23, 24 to 38, and ≥ 39 could define patients with "no effect", "small effect", and "moderate to large effect" of RAE on their QoL, respectively.
CONCLUSIONS:
This study supports the validity and reliability of the Thai version of the AE-QoL, which is a very different language from the original version. Categories allow to classify the effect of RAE on patients' QoL as "none", "small", and "moderate to large". Further studies are needed to confirm the applicability of AE-QoL in other Asian populations"
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