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BITS Pilani Campus Pilani

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General Chemistry Lecture 7:

Electron Spin, spectra and many electron atoms
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Radial wavefunction
The general form of the radial part of the hydrogenic atom wavefunctions, obtained by solving the radial Schrodinger equation, and applying the necessary conditions on the solutions, may be written • Rnl(r) ∝ r l. (Polynomial of degree n-l-1). e-Zr/na0 • The first factor determines the behaviour at r = 0 (only l = 0 wavefunctions are nonzero at the origin) Click to edit Master subtitle style • The second factor determines the number of nodes (nl-1) • The third ensures that the function goes to 0 as r → ∞

8/17/11

BITSPilani, Pilani Campus

Pilani Campus .Radial wavefunction Click to edit Master subtitle style 8/17/11 BITSPilani.

angular part is just a constant States of zero orbital angular momentum Click to edit Master subtitle style 8/17/11 BITSPilani.s orbitals Spherically symmetric. Pilani Campus .

Pilani Campus . angular part is just a constant States of zero orbital angular momentum Click to edit Master subtitle style 1s 2s 3s 8/17/11 BITSPilani.s orbitals Spherically symmetric.

ml = 1 or –1 1 nodal surface (xz) . Pilani Campus l = 1. ml = 0 1 nodal surface (xy) 8/17/11 Click to edit Master subtitle style α sin θ cos φ (px) l = 1.p orbitals – angular parts α cos θ (pz) α sin θ sin φ (p ) y l = 1. ml = 1 or –1 1 nodal surface (yz) BITSPilani.

Pilani Campus .P orbitals – boundary surfaces Click to edit Master subtitle style 8/17/11 BITSPilani.

p orbitals – density of dots Click to edit Master subtitle style 2pz 8/17/11 3pz BITSPilani. Pilani Campus .

d orbitals – angular parts Click to edit Master subtitle style 2 nodal planes 8/17/11 BITSPilani. Pilani Campus .

charge etc. Pilani Campus . Two beams emerge – the magnetic moment can take only two orientations with respect to the chosen axis. a property like its mass. Click atoms passed through a magnetic A beam ofto edit Master subtitle style field strongly inhomogeneous in. • First indicated by spectroscopic features. the doublet Na D ‘line’ • Confirmed by the Stern Gerlach experiment. and associated magnetic moment. 8/17/11 BITSPilani. the z direction. say..Electron spin • Intrinsic angular momentum. eg. characteristic of electron.

Stern Gerlach experiment Classically expected result Click to edit Master subtitle style z-axis Ag atoms Experimental Result BITSPilani. Pilani Campus 8/17/11 .

. Pilani Campus . angular momentum of magnitude [1/2(1/2 + 1)]1/2ħ = (√3/2)ħ The component of electron spin along any axis in space. denoted by the quantum number ms = 1/2 (α state) or −1/2 (β state) 8/17/11 BITSPilani.Electron spin Electron described by intrinsic spin angular momentum quantum number s=½ ie. say to edit Master subtitle styleon one of two values the z axis. can take Click ħ/2 or -ħ/2.

Pilani Campus . 1sα 8/17/11 BITSPilani. l.Spin states of electron Click to edit Master subtitle style The state of the electron in the hydrogenic atom is therefore fully specified by the four quantum numbers n. ml. Spin orbital = Spatial orbital x spin function eg. and ms..

ie.2. s = 1/2..…).. or FERMIONS (spin quantum number is a positive half-integer. s = 0. ) 8/17/11 BITSPilani. All particles may be classified as BOSONS Click to edit (spin quantumMaster subtitle style or a positive number is zero integer. Photons are spin – 1 particles. ie..Spin All fundamental particles have characteristic spin values.1. 3/2. Protons and Neutrons are also spin ½ particles like electrons. Pilani Campus ..

However. Pilani Campus . not all transitions between all available orbitals are possible.Spectral Transitions In the one electron atom. spectral line occurs when electron makes a transition between shells with principal quantum numbers ni and nf. while 2p to 1s. For example. A statement about which spectroscopic transitions are allowed is called a selection rule 8/17/11 BITSPilani. 2s to 1s or 3d to 1s are forbidden transitions. and 3p to 1s are Click to edit Master subtitle style allowed transitions.

Grotrian Diagram Click to edit Master subtitle style 8/17/11 BITSPilani. Pilani Campus .

the selection rule is just the statement of the conservation of angular momentum. keeping in mind that a photon carries (spin) angular momentum of magnitude corresponding to spin quantum number s = 1.Selection rule – one electron atom For the one electron atom. ± 1 8/17/11 BITSPilani. Pilani Campus . Click to edit Master subtitle style Selection rule: ∆l = ± 1 ∆ml = 0.

Many electron atoms The Schrodinger equation cannot be solved exactly for atoms with two or more electrons.…) = ψ1(1)ψ2(2)…. Pilani Campus . Orbital approximation: Approximate the wavefunction as a product of one electron functions or orbitals. refined approximations allow one to compute wavefunctions and energies quite accurately. Each orbital may be thought of as being hydrogen-like with an effective nuclear charge 8/17/11 BITSPilani.. (How correspondingly are Click to edit Master subtitle style we approximating the Hamiltonian?) ψ(1. However.2.

if one disregards the inter-e. For example.ectronic repulsion.Orbital approximation – He atom The orbital approximation allows us to express the electronic structure of an atom in terms of its configuration.2) = (8/πa03)1/2exp(-2r1/a0) (8/πa03)1/2 exp(-2r2/a0) corresponding to the configuration 1s2. the list of occupied orbitals. Pilani Campus . with the 1s orbital being somewhat more compact style in H. the ground state wavefunction of He may be written as ψ(1. Click to edit Master subtitle than What about Li? (Can all 3 electrons occupy 1s orbital ?) 8/17/11 BITSPilani.

The two electrons with paired spins (↑↓) have zero net spin angular momentum. and if two electrons do occupy one orbital. and molecular Click to edit Master subtitle style structure. The third electron in Li must enter the n = 2 shell. then their spins must be paired. Pilani Campus .Pauli exclusion principle No more than two electrons may occupy a given orbital. This principle forms the basis of the electronic structure of atoms. chemical periodicity. but the 2s or the 2p? 8/17/11 BITSPilani. (More later).

Pilani Campus . each electron may be thought of as experiencing an effective nuclear charge. Click to edit Master subtitle style The effective nuclear charge experienced by an electron will be determined by its probability density distribution. and this in turn by its wavefunction 8/17/11 BITSPilani. each electron is shielded from the nucleus by the others.Shielding and penetration Shielding: In a many electron atom. and to a first approximation.

Pilani Campus .Penetration Click to edit Master subtitle style 8/17/11 BITSPilani.

or [He]2s1 8/17/11 BITSPilani. Pilani Campus . the order of style is s < p < d < f. in the same shell of a manyClick to edit Master subtitle energies of the orbitals electron atom. In turn. the effective nuclear charge experienced by the ‘p’ electron will be greater than that for a ‘d’ electron in the same shell.Order of occupation The greater penetration of an ‘s’ electron compared to a ‘p’ electron of the same shell implies that it experiences a greater effective nuclear charge. In general therefore. The ground electronic configuration of Li is therefore 1s22s1.

Aufbau principle. 3. Each orbital may accommodate up to two electrons. Rules: 1. atom adopts configuration with greatest number of unpaired electrons (Hund’s rule) 8/17/11 BITSPilani. 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 5d 4f 6p… 2. In its ground state. Hund’s rule Order of occupation of atomic orbitals. Pilani Campus . Electrons occupy different orbitals of a given subshell edit Masterdoubly occupying any one of before subtitle style Click to them. 4.

periodicity Eg. This allows slight shrinkage. Na has configuration [Ne]3s1.Hund’s rule. Click to edit Master subtitle style Periodicity: Neon with ten electrons has the configuration [He]2s22p6.. leading to greater attraction to nucleus. Pilani Campus . with properties like Li 8/17/11 BITSPilani. C 1s22s22px12py1 N 1s22s22px12py12pz1 Origin of Hund’s rule: Spin Correlation – Electrons in different orbitals with parallel spins have a quantum mechanical tendency to stay apart. which completes the L shell.

Periodic Table Ar . d-block elements Sc – [Ar]3d14s2. The 3d orbitals are filled next from Sc to Zn – the first transition series.[Ne]3s23p6 – effectively like closed shell. K – [Ar]4s1 (like Na) and Ca – [Ar]4s2 (like Mg). Next the 4s orbitals are filled (penetration). Zn – [Ar]3d104s2 (Y to Cd. Click to La Master subtitle style Beyond this from Ga to Kr. Pilani Campus . and edit to Hg are second & third series). the 4p orbitals are filled (the first long period) In periods 6 and 7 – also have f-block elements 8/17/11 BITSPilani.