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The Hydrogen Atom

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Model The “orbitals” we know from general chemistry are wave functions of “hydrogen-like” atoms Hydrogen-like: any atom, but it has only one electron Atomic charge Z can be anything in other words If we can understand atomic orbitals, we can use them to: Build up molecules Understand electronic spectroscopy

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Hydrogen-Like Atom an electron the nucleus is at the origin electron is “confined” to the atom by a “spherically symmetric” potential r

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Spherical Polar Coordinates It’s easier to study this “planetary like” models in terms of spherically polar coords. (r, ) than Cartesian coords. (x, y, z) x y z r can vary form 0 to can vary form 0 to r can vary from 0 to ∞ x = r sin( cos( y = r sin( sin( z = r cos( Cartesians to polar polar to Cartesians

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The Schrodinger equation for the Hydrogen atom: Hydrogen Atom

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The Schrodinger equation for the Hydrogen atom: Hydrogen Atom Luckily this splits up by separation of variables: For the Radial part of the Schrodinger equation: Gives R n,l (r)

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Hydrogen Atom For the Angular parts of the Schrodinger equation: Gives l,m ( ) Gives m ( ) Quantum number rules for hydrogen atom: n = 1, 2, 3, 4, … l = 0, 1, 2, 3, …, n-1 m = -l, …, 0, …, l

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Hydrogen Energies Summary Energies: Energies only depend on principle quantum number n Rydberg constant R H in J Orbital energy degeneracies: For every n, there are n-1 values of l For every value of l the are 2l+1 values of m l

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Orbital Energies Orbital Energy in units of R H (J) 1s1s 0 2s2s 0 2p2p 01 3s3s 0 3p3p 01 -2 3d3d 01 2 RHRH …

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Hydrogen Orbitals Summary Wave functions: n,l,m (r, ) = R n,l (r) Y l,m ( are called orbitals Orthogonalized modified associated Laguerre functions Spherical harmonic functions We used a Numerov solution to get these Tells what happens “inside” the orbital There are n-l-1 radial nodes We “Monte Carlo sampled” their probability density to look at them Text book pictures of orbitals (i.e. the outer shells) There are l angular nodes

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Rn,l(r)Rn,l(r) n = 1 l = 0 R 1,0 (r)r 2 |R 1,0 | 2

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Rn,l(r)Rn,l(r) n = 2 l = 0 R 2,0 (r)r 2 |R 2,0 | 2

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Rn,l(r)Rn,l(r) n = 2 l = 1 R 2,1 (r)r 2 |R 2,1 | 2

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Rn,l(r)Rn,l(r) n = 3 l = 0 R 3,0 (r)r 2 |R 3,0 | 2

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Rn,l(r)Rn,l(r) n = 3 l = 1 R 3,1 (r)r 2 |R 3,1 | 2

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Rn,l(r)Rn,l(r) n = 3 l = 2 R 3,2 (r)r 2 |R 3,2 | 2

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Sampled Orbital Probability Densities

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Lecture 1 THE ELECTRONIC STRUCTURE OF THE HYDROGEN ATOM

Lecture 1 THE ELECTRONIC STRUCTURE OF THE HYDROGEN ATOM

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