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Lecture 25 Molecular orbital theory I

Lecture 25 Molecular orbital theory I.

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Lecture 25 Molecular orbital theory I

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  1. Lecture 25Molecular orbital theory I (c) So Hirata, Department of Chemistry, University of Illinois at Urbana-Champaign. This material has been developed and made available online by work supported jointly by University of Illinois, the National Science Foundation under Grant CHE-1118616 (CAREER), and the Camille & Henry Dreyfus Foundation, Inc. through the Camille Dreyfus Teacher-Scholar program. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the sponsoring agencies.

  2. Molecular orbital theory • Molecular orbital (MO) theory provides a description of molecular wave functions and chemical bonds complementary to VB. • It is more widely used computationally. • It is based on linear-combination-of-atomic-orbitals (LCAO) MO’s. • It mathematically explains the bonding in H2+ in terms of the bonding andantibonding orbitals.

  3. MO versus VB • Unlike VB theory, MO theory first combine atomic orbitals and form molecular orbitalsin which to fill electrons. MO theory VB theory

  4. MO theory for H2 • First form molecular orbitals (MO’s) by taking linear combinations of atomic orbitals (LCAO):

  5. MO theory for H2 • Construct an antisymmetric wave function by filling electrons into MO’s

  6. Singlet and triplet H2 (X)2 singlet far more stable (X)1(Y)1 triplet (X)1(Y)1 singlet least stable

  7. Singlet and triplet He (review) • In the increasing order of energy, the five states of He are (1s)2 singlet by far most stable (1s)1(2s)1 triplet (1s)1(2s)1 singlet least stable

  8. MO versus VB in H2 VB MO

  9. MO versus VB in H2 VB covalent covalent MO ionic H−H+ covalent = ionic H+H− covalent

  10. MO theory for H2+ • The simplest, one-electron molecule. • LCAO MO is by itself an approximate wave function (because there is only one electron). • Energy expectation value as an approximate energy as a function of R. e rA rB A R B Parameter

  11. LCAO MO • MO’s are completely determined by symmetry: A B Normalization coefficient LCAO-MO

  12. Normalization • Normalize the MO’s: 2S

  13. Bonding and anti-bonding MO’s φ+ = N+(A+B) φ– = N–(A–B) bonding orbital – σ anti-bonding orbital – σ*

  14. Energy • Neither φ+nor φ–is an eigenfunctionof the Hamiltonian. • Let us approximate the energy by its respective expectation value.

  15. Energy

  16. S, j, and k rB rA A B R rA rB A B R R

  17. Energy R R

  18. Energy φ– = N–(A–B) anti-bonding R R φ+ = N+(A+B) bonding

  19. Energy φ– = N–(A–B) φ–is more anti-bonding than φ+is bonding anti-bonding R E1s φ+ = N+(A+B) bonding

  20. Summary • MO theory is another orbital approximation but it uses LCAO MO’s rather than AO’s. • MO theory explains bonding in terms of bonding and anti-bonding MO’s. Each MO can be filled by two singlet-coupled electrons – α and βspins. • This explains the bonding in H2+, the simplest paradigm of chemical bond: bound and repulsive PES’s, respectively, of bonding and anti-bonding orbitals.

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