NOTE: Ignore all GUI warnings A. AOC for 4f2 Add a Pr atom

Slides:

Advertisements

Similar presentations

Mysteries of polarized light Enantiomers have identical properties except in one respect: the rotation of the plane of polarization of light Enantiomers.

Advertisements

Tutorial ADF2007 The universal density functional package for chemists Graphical User Interface.

Lecture 3 THE ELECTRONIC STRUCTURE OF THE POLYELECTRONIC ATOM. PART II

CHE Inorganic, Physical & Solid State Chemistry Advanced Quantum Chemistry: lecture 4 Rob Jackson LJ1.16,

An Introduction to Ionic Bonding Unit XX, Presentation 1.

1 Bis-amides and Amine Bis-amides as Ligands for Olefin Polymerization Catalysts Based on V(IV), Cr(IV) and Mn(IV). A Density Functional Theory Study Timothy.

Excited Atoms & Atomic Structure. © 2006 Brooks/Cole - Thomson The Quantum Mechanical Picture of the Atom Basic Postulates of Quantum Theory 1.Atoms and.

Electronic Circular Dichroism of Transition Metal Complexes within TDDFT Jing Fan University of Calgary 1.

Computational Spectroscopy II. ab initio Methods Multi-configuration Self-Consistent Field Theory Chemistry 713 Trocia Clasp.

Electronic Configuration Pauli exclusion principle – no two electrons in an atom can have the same four quantum numbers.

Quantum Numbers.

Before we did: p2p2 M L & M S Microstate Table States (S, P, D) Spin multiplicity Terms 3 P, 1 D, 1 S Ground state term 3 P.

Molecular Orbital Theory

Javier Junquera Exercises on basis set generation Increasing the angular flexibility: polarization orbitals.

Electron Configuration

Density Functional Theory And Time Dependent Density Functional Theory

Columbus Program System for Molecular Electronic Structure Relativistic Quantum Chemistry Capabilities Russell M. Pitzer Department of Chemistry Ohio State.

Electronic Structure of Atoms Chapter 6 BLB 12 th.

Which method? We’re using Density Functional Theory (DFT) as it gives us the most accurate results for transition metals in the least amount of time.

+ Protons and Electrons 8.5B: The student is expected to identify that protons determine an element’s identity and valence electrons determine its chemical.

Diamagnetism and Paramagnetism Physics 355. Free atoms… The property of magnetism can have three origins: 1.Intrinsic angular momentum (Spin) 2.Orbital.

Using the Quantum Model. Periodic Table Periodic Trends Atomic Radius: Increases down a group and decreases across a period Ionization Energy (energy.

Periodicity questions. Arrange these atoms and ions in order of decreasing size: Mg 2+, Ca 2+, and Ca. Cations are smaller than their parent atoms, and.

ATOMIC/MOLECULAR SPECTROSCOPY  Various spectroscopic techniques are used to elucidate molecular structures (eg. NMR), to study molecular vibrations (IR.

NATURE OF THE LIGAND- SMALL LIGANDS APPROACH THE LIGANDS EASILY, SO THEY CAN CAUSE GREAT CRYSTAL FIELD SPLITTING. LIGANDS CONTAINING EASILY POLARISABLE.

60th International Symposium on Molecular Spectroscopy Discovery: GaAs:Er system, 1983 The coincidence of the transition wavelength with the absorption.

Molecular Geometries and Bonding Chapter Bonding Theory Valence Bond Theory Molecular Orbital Theory Complete Ch 9 problems # 29, 36, 38, 39, 42,

Relativistic effects in ADF Erik van Lenthe, SCM.

Chem The Electronic Structure of Atoms Classical Hydrogen-like atoms: + - Atomic Scale: m or 1 Å Proton mass : Electron mass 1836 : 1 Problems.

© Alejandro Strachan – Binding Curves for H2 and He2 Online simulations via nanoHUB: Binding curves for H 2 molecule In this tutorial: Density functional.

© Alejandro Strachan – Online simulations: electronic structure of oxygen Online simulations via nanoHUB: Exchange interaction in Oxygen In this tutorial:

MODELING MATTER AT NANOSCALES 6.The theory of molecular orbitals for the description of nanosystems (part II) The density matrix.

Ionic Compounds Chapter 8 I will define a chemical bond I will describe how ions form I will identify ionic bonding and the characteristics of ionic compounds.

Periodic Table and Configuration. Demetri Mendeleev Created modern periodic table (late 1800’s) Arranged by increasing atomic mass Similar elements found.

Chapter 6 Section 2. Sec 6.5 Quantum Mechanics and Atomic Orbitals Wave functions – describes the behavior of the electron, denoted with the Greek letter,

Molecular Orbital Theory Molecular orbital theory describes covalent bonds in terms of molecular orbitals, which result from interaction of the.

Chem 1001 Lecture 11 Four quantum numbers.

Electron Configurations

Introduction to Molecular Orbital Theory.

Free Ion Spectroscopic Terms for dn Configurations

Isolated Si atoms.

Molecular Orbital Theory

PHY 752 Solid State Physics 11-11:50 AM MWF Olin 103

QM2 Concept test 7.1 Choose all of the following statements that are correct. (1) The Fermi energy is only defined for fermions. (2) The degeneracy pressure.

Graphical User Interface

Chemistry 141 Monday, November 27, 2017 Lecture 33 Pi bonding and MOs

Electrons Core electrons Valence electrons Energy Levels

Statistical Mechanics and Multi-Scale Simulation Methods ChBE

Classification of Elements and Periodic Trends

XANES/NEXAFS with ADF Expert: Mauro Stener - webinar, original slides

Zeeman effect HFS and isotope shift

AS Chemistry Lesson 3 (19/09/2013) s,p,d,f notation continued

Electron Configuration

Laser spectroscopy and ab initio calculations on TaF

XPS with ADF XPS XAS Core electron binding energy

IONS and E config Ions are atoms that have lost or gained electrons.

Threshold Ionization and Spin-Orbit Coupling of CeO

Total Angular Momentum

XPS with ADF XPS XAS Core electron binding energy

Multielectron Atoms The quantum mechanics approach for treating multielectrom atoms is one of successive approximations The first approximation is to treat.

Physical Chemistry Chapter V Polyatomic Molecular Structure 2019/4/10

Matrix Addition

Representing multi-electron systems

Electron configuration explained

Multireference Spin-Orbit Configuration Interaction with Columbus; Application to the Electronic Spectrum of UO2+ Russell M. Pitzer The Ohio State University.

5-ish Slides About Bridging Hydrides and [Cr(CO)5HCr(CO)5]-1

Hands-on exercises part 1

Electron Configurations

Second quantization and Green’s functions

Presentation transcript:

9. 9. 9. NOTE: Ignore all GUI warnings A. AOC for 4f2 Add a Pr atom Simply put, Density-Functional Theory based Ligand Field (LFDFT) uses ad hoc configuration interaction to deal with near-degeneracy in open-shell d- and f-systems. The LFDFT run is preceded by a so-called average-of-configuration (AOC) calculation. In this example, we will calculate excitations from f2 to f1d1 for the Pr3+ ion NOTE: Ignore all GUI warnings A. AOC for 4f2 Add a Pr atom Select Scalar ZORA Set TZ2P basis set No frozen core Numerical quality Good Details => Symmetry => Nosymm Model => Spin & Occupations => Run ADF Guess Tick ‘Use Following Occupation’ & scroll down Set 0.2857143 for orbitals 28-34* File => Run (Save as Pr_f2) * This creates a 3+ ion and equally divides the 2 f-electrons over the f-shell 1.3 2. 3. 4. 5. 1.2 1.1 6. 9. 7. 9. 9. 9.

9. 9. 9. Example: Pr3+ ion B. LFDFT for f2 Properties => Ligand Field DFT (Could be prompted to install LFDFT database) Enter the MO indices 28-34 Set spin-orbit to 1 Set n to 4 and l to 3 (= 4f) Run Open ADFspectra to see the multiplet energies 11. 12. 13. 15. 9. 9. 9.

C. f2 excitations to f1d1 We will now set up the AOC for the f1d1 excited state and calculate the excitations to that state from our previous f2 calculation (the ground state). Model => Spin & Occupations set f-orbitals to 1/7th (0.1428571), & d-orbitals to 1/5th Properties => Ligand Field DFT Enter the MO indices for state 2 Set spin-orbit to 1 Set n to 5 and l to 2 (= 5d) Select Excitations from: => the f2 LFDFT .t21 Save as a Pr_f2_f1d1 & Run ADFspectra Spectra =>Ligand Field DFT =>LF Excitations 17. 24. 19. 20. 21. 22. 9. 9. 9.

9. 9. 9. D. Expert options: Pr3+ in LiYF4 matrix You can study the f-d transitions in a matrix, based on the work in this paper (video): Tailoring the optical properties of lanthanide phosphors: prediction and characterization of the luminescence of Pr3+-doped LiYF4, Phys. Chem. Chem. Phys., 2015,17, 9116-9125 This is quite an advanced exercise. Roughly you need these steps (you can also start with the input files): 1) Find the LiYF4 cif file, make a 6x6x3 super cell and select a central Y. Cut out a cluster of a few A so that you have a sufficiently large cluster (Li8Y5F24) and replace the central Y with a Pr3+. 2) Optimize the central PrF8 part, fixing the outer part. Use LDA (best geometries) with a TZP basis set, using an AOC for the two f-electrons. 3) Calculate the f2 and d1f1 states for PrF8- in the field of Li and Y cations. You set up the occupations and LFDFT as done previously for the bare ion. For the d1f1 there will be some unoccupied orbitals in between the d and f orbitals. 9. 9. 9.