1. Chemistry 700 Lectures

2. Resources Grant and Richards, Foresman and Frisch, Exploring Chemistry with Electronic Structure Methods (Gaussian Inc., 1996) Cramer, Jensen, Ostlund and Szabo, Modern Quantum Chemistry (McGraw-Hill, 1982)

3. experiments are expensive, and often indirect. structure and property prediction is of great value. We need to know where the electrons are to be able to predict how eg. light will affect them or whether they are ready to create bonds with other atoms/molecules. Possible applications include: 1. drug design. 2. development of new materials. Why is one interested in computational chemistry?

4. There exist various approximation levels, the major being: Molecular Dynamics – called also Molecular Mechanics – treats atoms as classical objects, with interactions described by predetermined potentials, usually fitted to some analytical functions. Major applications are to perform geometry optimization and eg. study docking (how a small drug molecule can bind to a molecular macromolecule). This approach allows to study systems consisting of thousands of atoms but its quality is limited by the choice of the force field/potential. Ab-initio Theory starts from fundamental equations of quantum theory and works is up from there. Since strict analytical formula exists for energies and other system properties, many various properties can be computed, including MD potentials and interaction with light or magnetic field. However, full quantum- mechanical treatment is expensive and the systems studied are severely limited in the size to tens or hundreds of atoms. This course is focused mostly on this method.

5. Schrödinger Equation H is the quantum mechanical Hamiltonian for the system (an operator containing derivatives) E is the energy of the system  is the wavefunction (contains everything we are allowed to know about the system) |  | 2 is the probability distribution of the particles

6. Hamiltonian for a Molecule Kinetic energy of the electrons Kinetic energy of the nuclei Electrostatic interaction between the electrons and the nuclei Electrostatic interaction between the electrons Electrostatic interaction between the nuclei

7. Solving the Schrödinger Equation Analytic solutions can be obtained only for very simple systems Particle in a box, harmonic oscillator, hydrogen atom can be solved exactly Need to make approximations so that molecules can be treated Approximations are a trade off between ease of computation and accuracy of the result

8. Expectation Values for every measurable property, we can construct an operator repeated measurements will give an average value of the operator the average value or expectation value of an operator can be calculated by:

9. Variational Theorem the expectation value of the Hamiltonian is the variational energy the variational energy is an upper bound to the lowest energy of the system any approximate wavefunction will yield an energy higher than the ground state energy parameters in an approximate wavefunction can be varied to minimize the E var this yields a better estimate of the ground state energy and a better approximation to the wavefunction

10. Born-Oppenheimer Approximation The nuclei are much heavier than the electrons and move more slowly than the electrons In the Born-Oppenheimer approximation, we freeze the nuclear positions, R nuc, and calculate the electronic wavefunction,  el (r el ;R nuc ) and energy E(R nuc ) E(R nuc ) is the potential energy surface of the molecule (i.e. the energy as a function of the geometry) on this potential energy surface, we can treat the motion of the nuclei classically or quantum mechanically

11. Born-Oppenheimer Approximation freeze the nuclear positions (nuclear kinetic energy is zero in the electronic Hamiltonian) calculate the electronic wavefunction and energy E depends on the nuclear positions through the nuclear- electron attraction and nuclear-nuclear repulsion terms E = 0 corresponds to all particles at infinite separation

12. Nuclear motion on the Born-Oppenheimer surface Classical treatment of the nuclei (e,g. classical trajectories) Quantum treatment of the nuclei (e.g. molecular vibrations)

13. Hartree Approximation Assume that a many electron wavefunction can be written as a product of one electron functions If we use the variational energy, solving the many electron Schrödinger equation is reduced to solving a series of one electron Schrödinger equations each electron interacts with the average distribution of the other electrons

14. Hartree-Fock Approximation the Pauli principle requires that a wavefunction for electrons must change sign when any two electrons are permuted the Hartree-product wavefunction must be antisymmetrized can be done by writing the wavefunction as a determinant

15. Spin Orbitals each spin orbital  I describes the distribution of one electron in a Hartree-Fock wavefunction, each electron must be in a different spin orbital (or else the determinant is zero) an electron has both space and spin coordinates an electron can be alpha spin ( , , spin up) or beta spin ( , , spin up) each spatial orbital can be combined with an alpha or beta spin component to form a spin orbital thus, at most two electrons can be in each spatial orbital

16. Fock Equation take the Hartree-Fock wavefunction put it into the variational energy expression minimize the energy with respect to changes in the orbitals yields the Fock equation

17. Fock Equation the Fock operator is an effective one electron Hamiltonian for an orbital   is the orbital energy each orbital  sees the average distribution of all the other electrons finding a many electron wavefunction is reduced to finding a series of one electron orbitals

18. Fock Operator kinetic energy operator nuclear-electron attraction operator

19. Fock Operator Coulomb operator (electron-electron repulsion) exchange operator (purely quantum mechanical -arises from the fact that the wavefunction must switch sign when you exchange to electrons)

20. Solving the Fock Equations 1.obtain an initial guess for all the orbitals  i 2.use the current  I to construct a new Fock operator 3.solve the Fock equations for a new set of  I 4.if the new  I are different from the old  I, go back to step 2.

21. Hartree-Fock Orbitals for atoms, the Hartree-Fock orbitals can be computed numerically the  ‘s resemble the shapes of the hydrogen orbitals s, p, d orbitals radial part somewhat different, because of interaction with the other electrons (e.g. electrostatic repulsion and exchange interaction with other electrons)

22. Hartree-Fock Orbitals for homonuclear diatomic molecules, the Hartree-Fock orbitals can also be computed numerically (but with much more difficulty) the  ‘s resemble the shapes of the H 2 + orbitals , , bonding and anti-bonding orbitals

23. LCAO Approximation numerical solutions for the Hartree-Fock orbitals only practical for atoms and diatomics diatomic orbitals resemble linear combinations of atomic orbitals e.g. sigma bond in H 2   1s A + 1s B for polyatomics, approximate the molecular orbital by a linear combination of atomic orbitals (LCAO)

24. Basis Functions  ’s are called basis functions usually centered on atoms can be more general and more flexible than atomic orbitals larger number of well chosen basis functions yields more accurate approximations to the molecular orbitals

25. Roothaan-Hall Equations choose a suitable set of basis functions plug into the variational expression for the energy find the coefficients for each orbital that minimizes the variational energy

26. Roothaan-Hall Equations basis set expansion leads to a matrix form of the Fock equations F C i =  i S C i F – Fock matrix C i – column vector of the molecular orbital coefficients  I – orbital energy S – overlap matrix

27. Fock matrix and Overlap matrix Fock matrix overlap matrix

28. Intergrals for the Fock matrix Fock matrix involves one electron integrals of kinetic and nuclear-electron attraction operators and two electron integrals of 1/r one electron integrals are fairly easy and few in number (only N 2 ) two electron integrals are much harder and much more numerous (N 4 )

29. Solving the Roothaan-Hall Equations 1.choose a basis set 2.calculate all the one and two electron integrals 3.obtain an initial guess for all the molecular orbital coefficients C i 4.use the current C i to construct a new Fock matrix 5.solve F C i =  i S C i for a new set of C i 6.if the new C i are different from the old C i, go back to step 4.

30. Solving the Roothaan-Hall Equations also known as the self consistent field (SCF) equations, since each orbital depends on all the other orbitals, and they are adjusted until they are all converged calculating all two electron integrals is a major bottleneck, because they are difficult (6 dimensional integrals) and very numerous (formally N 4 ) iterative solution may be difficult to converge formation of the Fock matrix in each cycle is costly, since it involves all N 4 two electron integrals

31. Summary start with the Schrödinger equation use the variational energy Born-Oppenheimer approximation Hartree-Fock approximation LCAO approximation

32. Ab initio methods 1. The Hartree-Fock method (HF)

33. The Hartree-Fock method We want to solve the electronic Schrödinger equation: For this, we need to make some approximations These will lead to the Hartree-Fock method (which is the simplest ab initio method)

34. The Hartree-Fock method Decompose  into a combination of molecular orbitals (MOs) MO: one-electron wavefunction (  n ) However, this is not a good wavefunction, as wavefunctions need to be antisymmetric: swapping the coordinates of two electrons should lead to sign change Approximation 1: Good wavefunction:

35. The Hartree-Fock method The antisymmetry of the wavefunction can be achieved by constructing the wavefunction as a Slater Determinant:  i is a “spinorbital”: contains also the spin of the electron

36. The Hartree-Fock method Approximation 2: The Hartree-Fock wavefunction consists of a single Slater Determinant (This implies that the electron-electron repulsion is only included as an average effect => the Hartree-Fock method neglects electron correlation)

37. The Hartree-Fock method The MOs  i are written as linear combinations of pre-defined one-electron functions (basis functions or AOs) MO AO or basis function expansion coefficients LCAO: Linear Combination of Atomic Orbitals Approximation 3:

38. The Hartree-Fock method The Hartree-Fock wavefunction is a single Slater Determinant The MOs in the Slater Determinant are expressed as linear combinations of atomic orbitals The Hartree-Fock method aims to find the optimal wavefunction The exact form of the wavefunction depends on the coefficients c  i How to obtain the optimal coefficients c  i ?

39. The Hartree-Fock method Variation Principle So, just find the coefficients c  i that give the lowest energy! “The energy calculated from an approximation to the true wavefunction will always be greater than the true energy” This leads to the Hartree-Fock equations, which can be solved by the Self-Consistent Field (SCF) method

40. The Hartree-Fock method Wavefunction consists of a single Slater Determinant Start with the electronic Schrödinger equation Approximations leading to the Hartree-Fock method Variation principle to find optimal coefficients Decompose  into a combination of MOs => antisymmetry imposed by using Slater Determinant wavefunctions MOs are linear combinations of AOs (which are predefined)

41. The Hartree-Fock method The main weakness of Hartree Fock is that it neglects electron correlation In HF theory: each electron moves in an average field of all the other electrons. Instantaneous electron-electron repulsions are ignored Post-HF methods include electron correlation Electron correlation: correlation between the spatial positions of electrons due to Coulomb repulsion - always attractive!

42. Ab initio methods Hartree-Fock Møller-Plesset Perturbation theory (MP2, MP3, MP4,…) Configuration Interaction (CI) Coupled Cluster (CCSD, CCSDT, …) Multiconfigurational SCF (MCSCF) Post-HF methods