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    1) Spin-Polarised Calculations 2) Geometry Optimisation: CHEM6085: Density Functional Theory

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    lotanna
    This document discusses unrestricted spin orbitals and spin-polarized Kohn-Sham density functional theory (DFT) calculations. It explains that restricted DFT can only describe molecules with paired electrons and fails for systems with unpaired electrons like radicals. Unrestricted DFT allows the up and down spin orbitals to have different spatial parts, allowing it to describe such systems. It provides examples of how restricted DFT cannot dissociate H2 into two H atoms but unrestricted DFT can. The document also discusses potential energy surfaces, stationary points, minima, saddle points and transition states.

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    1) Spin-Polarised Calculations 2) Geometry Optimisation: CHEM6085: Density Functional Theory

    Uploaded by

    lotanna
    55 views14 pages
    This document discusses unrestricted spin orbitals and spin-polarized Kohn-Sham density functional theory (DFT) calculations. It explains that restricted DFT can only describe molecules with paired electrons and fails for systems with unpaired electrons like radicals. Unrestricted DFT allows the up and down spin orbitals to have different spatial parts, allowing it to describe such systems. It provides examples of how restricted DFT cannot dissociate H2 into two H atoms but unrestricted DFT can. The document also discusses potential energy surfaces, stationary points, minima, saddle points and transition states.

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    20200119DFT_L10

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    This document discusses unrestricted spin orbitals and spin-polarized Kohn-Sham density functional theory (DFT) calculations. It explains that restricted DFT can only describe molecules with paired electrons and fails for systems with unpaired electrons like radicals. Unrestricted DFT allows the up and down spin orbitals to have different spatial parts, allowing it to describe such systems. It provides examples of how restricted DFT cannot dissociate H2 into two H atoms but unrestricted DFT can. The document also discusses potential energy surfaces, stationary points, minima, saddle points and transition states.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    55 views14 pages

    1) Spin-Polarised Calculations 2) Geometry Optimisation: CHEM6085: Density Functional Theory

    Uploaded by

    lotanna
    This document discusses unrestricted spin orbitals and spin-polarized Kohn-Sham density functional theory (DFT) calculations. It explains that restricted DFT can only describe molecules with paired electrons and fails for systems with unpaired electrons like radicals. Unrestricted DFT allows the up and down spin orbitals to have different spatial parts, allowing it to describe such systems. It provides examples of how restricted DFT cannot dissociate H2 into two H atoms but unrestricted DFT can. The document also discusses potential energy surfaces, stationary points, minima, saddle points and transition states.

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    © All Rights Reserved
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    of 14

    CHEM6085: Density Functional Theory

    Lecture 10

    1) Spin-polarised calculations
    2) Geometry optimisation
    C.-K. Skylaris

    CHEM6085 Density Functional Theory 1


    Unpaired electrons

    • So far we have developed Kohn-Sham DFT for the case of paired


    electrons in doubly-occupied molecular orbitals
    • Such calculations are called “restricted closed-shell” or “spin
    unpolarised”
    • Restricted because pairs of alpha and beta spin orbitals are
    restricted to have the same spatial part
    • Closed shell because each spatial orbital (a “shell”) is closed, i.e.
    doubly occupied
    • Can not describe molecules with unpaired electrons, such as free
    radicals
    • Another failure is in the description of homolytic bond breaking. For
    example with spin unpolarised calculations a H2 molecule can only be
    dissociated to H- and H+ and not to two H atoms

    CHEM6085 Density Functional Theory 2


    Unrestricted spin orbitals
    • So far we have been working with restricted spin orbitals where the up
    (“alpha”) and down (“beta”) spins have the same spatial orbital

    Spin orbital Spatial orbital Spin function

    • In the unrestricted formalism the up and down spins are free to have
    different spatial orbitals and ,

    Spin orbital Spatial orbital Spin function

    and hence different energies


    CHEM6085 Density Functional Theory 3
    Spin polarised Kohn-Sham DFT
    To deal with unpaired electrons

    • Restricted (spin unpolarised)


    Spatial orbitals are restricted to
    be the same for opposite spins

    • Unrestricted (spin polarised)


    Up and down spins in each
    electron pair are no longer
    restricted to share the same
    spatial orbital

    CHEM6085 Density Functional Theory 4


    Homolytic bond breaking
    Example: dissociation of a H2 molecule

    Restricted
    closed shell

    Can only obtain H- and H+

    Restricted or
    Unrestricted
    open shell
    Can obtain two neutral H atoms

    CHEM6085 Density Functional Theory 5


    Spin density – E.g. the methyl radical

    Total density

    Spin density

    Restricted open shell spin density Unrestricted open shell spin density

    CHEM6085 Density Functional Theory 6


    Kohn-Sham Energy

    • Separate kinetic and exchange-correlation energies for each spin


    • Coulomb and external potential energies are calculated for the total density

    CHEM6085 Density Functional Theory 7


    Kohn-Sham Hamiltonian
    • A separate exchange-correlation operator for each spin results in different
    Kohn-Sham Hamiltonians for each spin

    • The iterative solution of each Hamiltonian with provide the Kohn-Sham


    orbitals for each spin
    • However the Hamiltonians depend also on the total density (up plus down
    spins) through the Coulomb operator so these Hamiltonians are coupled
    and they have to be solved simultaneously via the SCF procedure

    CHEM6085 Density Functional Theory 8


    Moving the atoms: Potential Energy Surface (PES)
    • The electronic energy is a function of the nuclear positions. So is the
    internuclear repulsion energy
    • Their sum is called the Potential Energy Surface (PES). It is a function of
    3xNatoms variables that represents a “surface” in (3xNatoms+1) dimensions

    Electronic Repulsion
    Example: PES of a diatomic energy energy between
    nuclei I and J

    R
    EPES(R)

    Equilibrium geometry Re

    CHEM6085 Density Functional Theory 9


    Example: PES of HCl
    • The PES is a function of 6 coordinates
    • 5 of these can be removed as they correspond to entire-molecule translation
    (3 coordinates) and rotation (2 coordinates)
    • So in practice the PES depends only on 1 coordinate (the H-Cl distance)

    “single-point” DFT calculations

    Method Re (Å)
    R
    HF/STO-3G 1.31328
    EPES(R)
    HF/6-31+G* 1.26712
    HF/aug-cc_pVTZ 1.26752
    Experiment 1.27455

    Equilibrium
    geometry Re

    CHEM6085 Density Functional Theory 10


    PES for H2+H  H+H2

    This PES represents chemical interactions that can take place between 3 H atoms

    CHEM6085 Density Functional Theory 11


    Minima and saddle points
    Products, reactants and transition
    states are stationary points, i.e.
    Transition state
    (saddle point) they are points on the PES where
    the derivative of EPES with respect
    to all nuclear coordinates is zero

    A more complicated PES...

    Reactant/Product
    (minimum)
    Reactant/Product
    (minimum)

    CHEM6085 Density Functional Theory 12


    Homework

    1) Examine the form of the Kohn-Sham Hamiltonians for each spin and decide in which cases the up-spin electrons will
    experience different interactions from the down-spin ones, and hence the orbital energies for the same orbital will
    be different for each spin.

    2) Each spin function is an eigenfunction of the operator for the z-component of the spin of an electron. In atomic units
    the eigenvalue equation is as follows:

    Show that any Slater determinant wavefunction is an eigenfunction of the total z-component spin operator

    with eigenvalue regardless of whether the Slater determinant is made of restricted or unrestricted
    spin orbitals.

    3) Assume that a simple potential energy surface (PES) is defined by only two coordinates x and y and has the
    expression E(x,y)= 2xy+3x2+2y+5. Find the stationary points of this PES and determine whether they are equilibrium
    geometries or transition states.

    CHEM6085 Density Functional Theory 13


    5-minute quiz
    Name : Date :
    Surname:

    1) How do the Kohn-Sham molecular orbitals differ between a conventional and a spin-polarised DFT
    calculation?

    2) Write down the expression for the LDA exchange energy in a spin-polarised calculation (so use the up-spin and
    down-spin densities)

    3) Considering the general shape (saddle) of the energy surface on a transition state point on the PES, what do
    you expect a molecule whose geometry is a transition state to do?

    CHEM6085 Density Functional Theory 14

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