Search results for "density-functional theory"
showing 10 items of 26 documents
The first example of cofacial bis(dipyrrins)
2016
International audience; Two series of cofacial bis(dipyrrins) were prepared and their photophysical properties as well as their bimolecular fluorescence quenching with C-60 were investigated. DFT and TDDFT computations were also performed as a modeling tool to address the nature of the fluorescence state and the possible inter-chromophore interactions. Clearly, there is no evidence for such interactions and the bimolecular quenching of fluorescence, in comparison with mono-dipyrrins, indicates that C-60-bis(dipyrrin) contacts occur from the outside of the "mouth" of the cofacial structure.
Plasmon-Induced Direct Hot-Carrier Transfer at Metal-Acceptor Interfaces.
2019
Plasmon-induced hot-carrier transfer from a metal nanostructure to an acceptor is known to occur via two key mechanisms: (i) indirect transfer, where the hot carriers are produced in the metal nanostructure and subsequently transferred to the acceptor, and (ii) direct transfer, where the plasmons decay by directly exciting carriers from the metal to the acceptor. Unfortunately, an atomic-level understanding of the direct-transfer process, especially with regard to its quantification, remains elusive even though it is estimated to be more efficient compared to the indirect-transfer process. This is due to experimental challenges in separating direct from indirect transfer as both processes o…
Random Structural Modification of a Low-Band-Gap BODIPY-Based Polymer
2017
International audience; A BODIPY thiophene polymer modified by extending conjugation of the BODIPY chromophore is reported. This modification induces tunability of energy levels and therefore absorption wavelengths in order to target lower energies.
Reaction Mechanism of an Intramolecular Oxime Transfer Reaction: A Computational Study
2014
Density functional theory (PBE0/def2-TZVPP) calculations in conjunction with a polarizable continuum model were used to assess the mechanism of the intramolecular oxime transfer reaction that leads to the formation of isoxazolines. Different diastereomers of the intermediates as well as different oximes (formaldehyde and acetone oxime) were considered. The computed reaction profile predicts the water-addition and -expulsion steps as the highest barriers along the pathway, a conclusion that is in line with the experimental evidence obtained previously for these reactions. peerReviewed
Growth of two-dimensional Au patches in graphene pores : a density-functional study
2016
Grafeenin löytämisen myötä kaksiulotteisten (2D) materiaalien tutkimus on edennyt huomattavasti viimeisen vuosikymmenen aikana. Myös 2D-metalleja on tutkittu, ja esimerkiksi atominpaksuinen rautakerros on onnistuttu kokeellisesti luomaan grafeenin reunalle. Metalleista erityisesti kullan on havaittu käyttäytyvän hyvin eri tavalla nanomittakaavassa. Tässä Pro gradu -tutkielmassa on simuloitu kaksiulotteisten kultasaarekkeiden kasvua grafeenin reunalle tiheysfunktionaaliteoriaa (DFT) käyttämällä. Tavoitteena oli selvittää, kuinka kulta-atomit kulkeutuvat grafeenin pintaa pitkin lopulta reunalle, ja asettuvatko kulta-atomit kaksiulotteisesti samaan tasoon grafeenin kanssa. Tulosten perusteella…
Wannier90 as a community code: new features and applications
2019
Wannier90 is an open-source computer program for calculating maximally-localised Wannier functions (MLWFs) from a set of Bloch states. It is interfaced to many widely used electronic-structure codes thanks to its independence from the basis sets representing these Bloch states. In the past few years the development of Wannier90 has transitioned to a community-driven model; this has resulted in a number of new developments that have been recently released in Wannier90 v3.0. In this article we describe these new functionalities, that include the implementation of new features for wannierisation and disentanglement (symmetry-adapted Wannier functions, selectively-localised Wannier functions, s…
Time-dependent density-functional theory in the projector augmented-wave method
2008
We present the implementation of the time-dependent density-functional theory both in linear-response and in time-propagation formalisms using the projector augmented-wave method in real-space grids. The two technically very different methods are compared in the linear-response regime where we found perfect agreement in the calculated photoabsorption spectra. We discuss the strengths and weaknesses of the two methods as well as their convergence properties. We demonstrate different applications of the methods by calculating excitation energies and excited state Born–Oppenheimer potential surfaces for a set of atoms and molecules with the linear-response method and by calculating nonlinear e…
Plasmon Excitations in Mixed Metallic Nanoarrays
2019
Features of the surface plasmon from macroscopic materials emerge in molecular systems, but differentiating collective excitations from single-particle excitations in molecular systems remains elusive. The rich interactions between single-particle electron-hole and collective electron excitations produce phenomena related to the chemical physics aspects within the atomic array. We study the plasmonic properties of atomic arrays of noble (Au, Ag, and Cu) and transition-metal (Pd, Pt) homonuclear chains using time-dependent density functional theory and their Kohn-Sham transition contributions. The response to the electromagnetic radiation is related to both the geometry-dependent confinement…
Supramolecular hierarchy among halogen and hydrogen bond donors in light-induced surface patterning
2015
Halogen bonding, a noncovalent interaction possessing several unique features compared to the more familiar hydrogen bonding, is emerging as a powerful tool in functional materials design. Herein, we unambiguously show that one of these characteristic features, namely high directionality, renders halogen bonding the interaction of choice when developing azobenzene-containing supramolecular polymers for light-induced surface patterning. The study is conducted by using an extensive library of azobenzene molecules that differ only in terms of the bond-donor unit. We introduce a new tetrafluorophenol-containing azobenzene photoswitch capable of forming strong hydrogen bonds, and show that an io…
Cobalt Electrolyte/Dye Interactions in Dye-Sensitized Solar Cells: A Combined Computational and Experimental Study
2012
We report a combined experimental and computational investigation to understand the nature of the interactions between cobalt redox mediators and TiO2 surfaces sensitized by :ruthenium and organic dyes, and their impact on. the performance of the corresponding dye-sensitized solar cells (DSSCs). We : focus: on different ruthenium dyes and fully organic dyes, to understand the dramatic loss of efficiency observed for the prototype Ru(II) N719 dye in conjunction with :Cobalt: electrolytes. Both N719- and Z907-based DSSCs showed an increased lifetime in iodine-based electrolyte compared to the cobalt-based redox-shuttle; While the organic D21L6 and D25L6 cycles endowed.With long alkoxy chains,…