Skip to main content
Chemistry LibreTexts

7: Multielectron Atoms

  • Page ID
    424960
  • \( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \)

    \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)

    \( \newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\)

    ( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\)

    \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\)

    \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\)

    \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\)

    \( \newcommand{\Span}{\mathrm{span}}\)

    \( \newcommand{\id}{\mathrm{id}}\)

    \( \newcommand{\Span}{\mathrm{span}}\)

    \( \newcommand{\kernel}{\mathrm{null}\,}\)

    \( \newcommand{\range}{\mathrm{range}\,}\)

    \( \newcommand{\RealPart}{\mathrm{Re}}\)

    \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\)

    \( \newcommand{\Argument}{\mathrm{Arg}}\)

    \( \newcommand{\norm}[1]{\| #1 \|}\)

    \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\)

    \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\AA}{\unicode[.8,0]{x212B}}\)

    \( \newcommand{\vectorA}[1]{\vec{#1}}      % arrow\)

    \( \newcommand{\vectorAt}[1]{\vec{\text{#1}}}      % arrow\)

    \( \newcommand{\vectorB}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \)

    \( \newcommand{\vectorC}[1]{\textbf{#1}} \)

    \( \newcommand{\vectorD}[1]{\overrightarrow{#1}} \)

    \( \newcommand{\vectorDt}[1]{\overrightarrow{\text{#1}}} \)

    \( \newcommand{\vectE}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash{\mathbf {#1}}}} \)

    \( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \)

    \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)

    Electrons with more than one atom, such as Helium (He), and Nitrogen (N), are referred to as multi-electron atoms. Hydrogen is the only atom in the periodic table that has one electron in the orbitals under ground state. We will learn how additional electrons behave and affect a certain atom.

    • 7.1: Perturbation Theory and the Variational Method for Helium
      Both perturbation theory and variation method (especially the linear variational method) provide good results in approximating the energy and wavefunctions of multi-electron atoms. We address both approximations with respect to the helium atom.
    • 7.2: Hartree-Fock Equations are Solved by the Self-Consistent Field Method
      The Hartree method is used to determined the wavefunction and the energy of a quantum multi-electron system in a stationary state. The Hartree method often assumes that the exact, N-body wave function of the system can be approximated by a product of single-electron wavefucntions. By invoking the variational method, one can derive a set of N-coupled equations for the N spin orbitals.
    • 7.3: An Electron has an Intrinsic Spin Angular Momentum
      Spin is one of two types of angular momentum in quantum mechanics, the other being orbital angular momentum. The orbital angular momentum operator is the quantum-mechanical counterpart to the classical angular momentum of orbital revolution. The existence of spin angular momentum is inferred from the Stern–Gerlach experiment, in which particles are observed to possess angular momentum that cannot be accounted for by orbital angular momentum alone.
    • 7.4: Wavefunctions must be Antisymmetric to Interchange of any Two Electrons
      The probability |Ψ(r1, r2)|² should be identical to the probability |Ψ(r2, r1)|² because the electrons have no label and they cannot be told apart because of Heisenberg principle. You can naively think that Ψ(r1, r2)=±Ψ(r2, r1) but it turns out that the sign must always be minus for the electrons. This is an additional postulate of quantum mechanics.
    • 7.5: Hartree-Fock Calculations Give Good Agreement with Experimental Data
      The Hartree–Fock method is a method of approximation for the determination of the wave function and the energy of quantum many-body systems. The Hartree–Fock method often assumes that the exact, N-body wave function of the system can be approximated by a single Slater determinant of N spin-orbitals. By invoking the variational method, one can derive a set of N-coupled equations for the N spin orbitals. A solution of these equations yields the Hartree–Fock wave function and energy of the system.
    • 7.E: Multielectron Atoms (Exercises)
      These are homework exercises to accompany Chapter 8 of McQuarrie and Simon's "Physical Chemistry: A Molecular Approach" Textmap.

    Thumbnail: Neon Atom. (CC BY 3.0 Unported; BruceBlaus via Wikipedia)


    7: Multielectron Atoms is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by LibreTexts.