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Computational Chemistry: Description and prediction of systems containing d- and f-Elements

English title Computational Chemistry: Description and prediction of systems containing d- and f-Elements
Applicant Daul Claude A.
Number 149234
Funding scheme Project funding (Div. I-III)
Research institution Département de Chimie Université de Fribourg
Institution of higher education University of Fribourg - FR
Main discipline Inorganic Chemistry
Start/End 01.10.2013 - 30.06.2015
Approved amount 162'505.00
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Keywords (6)

Density Functional Theory; Ligand Field Theory; Single Molecular Magnets; Computational Quantum Chemistry; Vibronic coupling; Warm-white light

Lay Summary (French)

Lead
Notre projet est intitulé "Prediction et description de systèmes contenant un ou plusieurs éléments d et/ou f ". Dans ce projet nous utilisons des techniques de chimie computationnelle modernes pour prédire et/ou décrire des propriétés photophysiques et/ou magnétiques de molécules et/ou matériaux complexes.
Lay summary

La quête pour un éclairage par de la lumière blanche douce est basée sur le développement d’une source de lumière économique proche de celle du soleil. Les sources de lumière les plus prometteuse sont les diodes électroluminescente (DEL). Une diode électroluminescente ou (de l'anglais light-emitting diode, LED), est un composant opto-électronique capable d’émettre de la lumière lorsqu’il est parcouru par un courant électrique. Une diode électroluminescente ne laisse passer le courant électrique que dans un seul sens (le sens passant, comme une diode classique, l'inverse étant le sens bloquant) et produit un rayonnement monochromatique ou polychromatique incohérent à partir de la conversion d’énergie électrique lorsqu'un courant la traverse. Elle compte plusieurs dérivées, principalement, l'OLED, l'AMOLED ou le FOLED (pour flexible oled). Les LED sont considérées, par beaucoup, comme une technologie d'avenir dans le domaine de l'éclairage général. En effet, on estime que d'ici à 2020, les LED pourraient représenter 75 % du marché de l'éclairage. Elles sont utilisées aussi dans la construction des écrans de télévision plats : pour le rétro-éclairage des LCD, comme source d'illumination principale dans les écrans de télévision à LED. Dans le second volet de notre projet nous nous proposerons aux industriels des DEL basée sur les lanthanides à partir de modèles numériques que nous avons développés dans notre labo de chimie computationnelle ces 20 dernières années.

Direct link to Lay Summary Last update: 05.11.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
A ligand field theory-based methodology for the characterization of the Eu2+ [Xe]4f65d1 excited states in solde state compounds
Amador Garcia-Fuente, Fanica Cimpoesu, Harry Ramanantoanina, Benjamin Herder, Claude Daul, Markus Suta, Claudia Wickleder, Werner Urland (2015), A ligand field theory-based methodology for the characterization of the Eu2+ [Xe]4f65d1 excited states in solde state compounds, in Chem. Phys. Lett., 622, 120.
Magnetic Anisotropy in “Scorpionate” First-Row Transition-Metal Complexes: A Theoretical Investigation
Marko Perić Amador García-Fuente Matija Zlatar Prof. Claude Daul Stepan Stepanović Dr. Pablo Ga (2015), Magnetic Anisotropy in “Scorpionate” First-Row Transition-Metal Complexes: A Theoretical Investigation, in Chem. A Eur. J, 21, 3716.
Photon cascade emission in Pr3+ doped fluoride with CaF2 structure: Application of a model for its prediction
Benjamin Herdern, Amador Garcia-Fuente, Harry Ramanantoanina, Thomas Jüstel, Claude Daul, Werner Urland (2015), Photon cascade emission in Pr3+ doped fluoride with CaF2 structure: Application of a model for its prediction, in Chem. Phys. Lett., 620, 29.
Tailoring the optical properties of lanthanide phosphors: a prediction and characterization of the luminescence of Pr3+-doped LiYF4
Harry Ramanantoanina, Werner Urland, Benjamin Herden, Fanica Cimpoesu, Claude Daul (2015), Tailoring the optical properties of lanthanide phosphors: a prediction and characterization of the luminescence of Pr3+-doped LiYF4, in Phys. Chem. Chem. Phys, 17, 9116.
DFT investigation of the influence of Jahn–Teller distortion on the aromaticity in square-planar arsenic and antimony clusters, Polyhedron
Marko Perić, Ljubica Andjelković, Matija Zlatar, Claude Daul, Maja Gruden-Pavlović (2014), DFT investigation of the influence of Jahn–Teller distortion on the aromaticity in square-planar arsenic and antimony clusters, Polyhedron, in Polyhedron, 80, 69.
Ligand Field Density Functional Theory for the prediction of future domestic lighting
Harry Ramanantoanina, Werner Urland, Amador Garcia-Fuente, Fanica Cimpoesu, Claude Daul (2014), Ligand Field Density Functional Theory for the prediction of future domestic lighting, in Phys. Chem. Chem. Phys., 16, 14625.
Non-empirical Prediction of the Photophysical and Magnetic Properties of Systems with Open d- and f-Shells Based on Combined Ligand Field and Density Functional Theory (LFDFT)
Claude Daul (2014), Non-empirical Prediction of the Photophysical and Magnetic Properties of Systems with Open d- and f-Shells Based on Combined Ligand Field and Density Functional Theory (LFDFT), in CHIMIA International Journal for Chemistry, 68, 633.
The Angular Overlap Model extended for two-open-shell f and d electrons
Harry Ramanantoanina, Werner Urland, Fanica Cimpoesu, Claude Daul (2014), The Angular Overlap Model extended for two-open-shell f and d electrons, in Phys. Chem. Chem. Phys., 16, 12282.
The theoretical account of the ligand field bonding regime and magnetic anisotropy in the DySc2N@C80 single ion magnet endohedral fullerene
Fanica Cimpoesu, Nita Dragoe, Harry Ramanantoanina, Werner Urland, Claude Daul (2014), The theoretical account of the ligand field bonding regime and magnetic anisotropy in the DySc2N@C80 single ion magnet endohedral fullerene, in Phys. Chem. Chem. Phys., 16, 11337.
Development and applications of the LFDFT: the non-empirical account of ligand field and the simulation of the f–d transitions by density functional theory
Harry Ramanantoanina, Mohammed Sahnoun, Andrea Barbiero, Marilena Ferbinteanu, Fanica Cimpoesu, Development and applications of the LFDFT: the non-empirical account of ligand field and the simulation of the f–d transitions by density functional theory, in Phys. Chem. Chem. Phys..
Flux Synthesis, Structure, Properties, and Theoretical Magnetic Study of Uranium(IV)-Containing A2USi6O15 (A = K, Rb) with an Intriguing Green-to-Purple, Crystal-to-Crystal Structural Transition in th
Gregory Morrison, Harry Ramanantoanina, Werner Urland, Mark D. Smith, Hans-Conrad zur Loye, Flux Synthesis, Structure, Properties, and Theoretical Magnetic Study of Uranium(IV)-Containing A2USi6O15 (A = K, Rb) with an Intriguing Green-to-Purple, Crystal-to-Crystal Structural Transition in th, in Inorg. Chem., 54, 5504.
On exchange coupling and bonding in the Gd2@C80 and Gd2@C79N endohedral dimetallo-fullerenes
Fanica Cimpoesu, Bogdan Frescus, Cornellu I. Oprea, Harry Ramanantoanina, Werner Urland, Claude Daul, On exchange coupling and bonding in the Gd2@C80 and Gd2@C79N endohedral dimetallo-fullerenes, in Mol. Phys.

Collaboration

Group / person Country
Types of collaboration
Prof. Thomasz Wesolowski, University of Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Prof. Henning Höppe, Univ. Augsbourg Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
- Industry/business/other use-inspired collaboration
Prof. Maja Gruden-Pavlovic , University of Belgrade Serbien (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Prof. Robert Glaum, University Bonn Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Dr. Ilaria Ciofini and Prof. Carlo Adamo ENSCP France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Prof. Frank Neese and Michael Atanasov MPI Mülheim an der Ruhr Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Prof. Marilena Ferbinteanu Cimpoesu and Fanica Cimpoesu, Unibersity of Bucarest Romania (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Swiss Chemical Society (SCS) fall meeting Talk given at a conference Theoretical account of the electronic structure and properties of systems with two-open-shell f and d electrons 11.09.2014 Zürich, Switzerland Ramanantoanina Harimbola; Daul Claude A.;


Knowledge transfer events

Active participation

Title Type of contribution Date Place Persons involved
Phosphor Global Summit 2015 16.03.2015 San Fransisco, United States of America Cimpoesu Fanica; Daul Claude A.; Urland Werner; Ramanantoanina Harimbola;
Swiss Chemical Society (SCS) fall meeting 11.09.2014 Zurich, Switzerland Daul Claude A.; Ramanantoanina Harimbola;
14th International Balkan Workshop on applied physics 02.07.2014 Constanta, Romania Ramanantoanina Harimbola;
European F-Elements Network (EUFEN3) 12.04.2014 Nürnberg, Germany Ramanantoanina Harimbola; Daul Claude A.;
University of Fribourg department of chemistry seminar 03.04.2014 Fribourg, Switzerland Ramanantoanina Harimbola;
Swiss Association of Computational Chemists SACC 15.02.2014 Basel, Switzerland Ramanantoanina Harimbola; Daul Claude A.;


Associated projects

Number Title Start Funding scheme
137625 Computational Chemistry: Methods and Applications to Systems containing d- and f-elements 01.10.2011 Project funding (Div. I-III)

Abstract

Our research project will be composed of three different topics that are interrelated and cover a wide range of applications in molecular sciences. However, the common feature of all these mini-projects will be that the studied systems contain d- and/or f-elements, generally with open shells. Next, we give a short description of these three topics:a) The quest for phosphor that emit warm-white lightThis is a completely new field for us, but of outmost interest for the whole society. To achieve this goal we plan to use a Ligand Field Density Functional Theory (LFDFT) based methodology for the analysis of the 4fn ? 4fn-1 5d1 transitions in rare earth compounds and apply it, in a first step, for the characterization of the 4f2 ? 4f1 5d1 transitions in the quantum cutter Cs2KYF6: Pr3+ with the elpasolite structure type. The positions of the zero-phonon energy corresponding to the states of the electron configurations 4f2 and 4f1 5d1 are calculated, where the praseodymium ion may occupy either the Cs+-, K+- or Y3+-site, and are compared with available experimental data. The theoretical results show that the occupation of the three undistorted sites allows a quantum-cutting process. However size effects due to the difference between the ionic radii of Pr3+ and Cs+ as well as K+ lead to the distortion of the Cs+- and K+- sites, which finally exclude these sites for quantum-cutting. b) Development and validation of DFT-based model to describe accurately the pseudo-Jahn-Teller effect in molecular systemsBased on the pseudo Jahn-Teller effect (PJTE) theory, an approach is developed to rationalize and predict the conformations and conformational changes in molecular systems with a common pattern, i.e. the presence of two or more states amongst the frontier orbitals that belong to the same irrep GPJTE. It is shown that starting with the high-symmetry (hs) geometry of the environment, the set of GPJTE orbitals descends from (hs) to low-symmetry (ls) which produces a variety of PJT distortions. Further PJT interactions with higher energy degenerate states may trigger additional distortions which in (ls) are classified as Gls. The realization of these conformations depends on the positions of the excited GPJTE-states and the PJTE parameter values. The emerging PJTE-problems, are formulated in the matrix form and provide a general picture of the ground and excited adiabatic potential energy surfaces. Following this scheme in combination with Multi-Determinant calculations, the possible conformations and conformational transitions are analyzed for several specific systems. c) Non-empirical prediction of molecular magnetism: In this third topic, we adress some basic aspects concerning the magnetic properties of transition metal and rare-earth ions, which are currently the subject of a renovated interest in the field of molecular magnetism, after the discovery that slow relaxation of the magnetization at liquid nitrogen temperature can occur in mononuclear complexes of these ions. Focusing on Ln(III) derivatives we will stress the relation of the crystal field parameters, which determine the anisotropy of these systems and consequently their interesting magnetic properties, with the geometry of the coordination sphere around the lanthanide centre and with the pattern of f orbitals. The problem of systems of low point symmetry is also addressed by studying how detailed single crystal investigation, coupled to more sophisticated calculation procedures, is an absolute necessity to obtain meaningful structure-property relationships in these systems.
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