Lecture 2: More atoms

Multielectron atoms, Hunds rules Trends: Radii (atomic, ionic, Van der Waals), Ionization Enthalpy (ionization potential)

Last Lecture: Shielding

-

+3

Q) Does the 2s valence electron in Li experience the full attraction of the +3 nucleus, or do the 2 1s electrons fully shield it (if so it would feel like it was circling a +1 nucleus)? A) Somewhere in between

Effective Nuclear Z* Charge: Slaters Rules Reminder

Slaters rules for the prediction of for an electron: 1. Group electron configuration as follows: (1s)(2s,2p)(3s,3p)(3d)(4s,4p)(4d)(4f)(5s,5p) etc. 2. Electrons to the right (in higher subshells and shells) of an electron do not shield it. 3. If the electron of interest is an ns or np electron: a) each other electron in the same group contributes 0.35 (0.30 for 1s) b) each electron in an n-1 group contributes 0.85 c) each electron in an n-2 or lower group contributes 1.00 4. If the electron of interest is an nd or nf electron: a) each other electron in the same group contributes 0.35 b) each electron in a lower group (to the left) contributes 1.00

Slaters Approximations?
Note that these Rules are brutal by modern standards (but still science!) A good first approximation for ionization enthalpies ( X X+)

Z* = Z -

Z *2 En = R 2 n

Z* is the effective nuclear charge Z is the atomic number is the shielding or screening constant Of course, all these ionization enthalpy values are all experimentally known

Ionization Enthalpy, Hie (ionization potential, IP)

The enthalpy change for ionization by loss of electron(s) E(g) E+(g) + eE+(g) E2+(g) + eE2+(g) E3+(g) + eHie First ionization potential Hie Second ionization potential > first Hie Third ionization potential > second

First Ionization Potentials

Trends for Atomic Properties in the Periodic Table

Understanding how and why properties change from element to element requires us to consider:
1. The electron configuration of the atom or ion (the filling order) 2. The type of valence orbitals involved (size, shape, shielding and penetration) 3. The effective nuclear charge felt by electrons in valence orbitals 4. Oddities

Trends: Orbital Energies for Atoms

For atoms other than hydrogen: Orbital energy depends on n and l Ordering of orbital energies: ns < np < nd < nf

19K (3rd row) 37Rb (4th row) 58 Ce (lanthanides) Energies change as shells are filled Consequence of penetrating ability of outer orbitals into core (remember Slater, effective nuclear charge)

Building Up the Atoms in the Periodic Table

1) The Aufbau (building up) principle: lowest energy orbitals are filled first 1s, then 2s, then 2p, then 3s, then 3p, etc. 2) Remember the Pauli exclusion principle. 3) Hunds rule of maximum multiplicity. 0 1 Energy 3 2 1

Hunds Rule of Maximum Multiplicity

Multiplicity is a measure of the number of unpaired electrons. Multiplicity = number of unpaired electrons + 1 It is used because it describes the degeneracy of the state
# of unpaired Total spin electrons (S) 0 1 2 3 0 1/2 1 3/2 Multiplicity (2S+1) 1 2 3 4 Common Name singlet doublet triplet quartet

Hunds rule: Electrons must be placed in the orbitals of a subshell so as to give the maximum total spin. i.e. put as many unpaired electrons as possible in a subshell to get the most stable arrangement.

Hunds Rule of Maximum Multiplicity 1: Basis

1. Minimization of electron-electron repulsion - There is less repulsion between electrons in different orbitals (different regions in space)

Electrons in different orbitals feel a greater Z*, thus they are more stable Part 2, why both same spin?

Hunds Rule of Maximum Multiplicity 2: Basis

2. Maximization of exchange energy stabilization - This is a quantum mechanical effect that causes systems with electrons of the same energy and spin to be more stable. -Pauli Exclusion Principle - a wavefunction must be antisymmetric with respect to electron exchange. - The more exchanges (permutations where electron identities are changed) possible, the more stable the electron configuration of the subshell
For an s-orbital (subshell), the spins must are different, so no exchanges are possible.

For a p subshell, there are different orbitals of the same energy and exchanges are possible. Two electrons of opposite spin, no exchange is possible; configurations after electron exchange must look identical

Two electrons of the same spin, one exchange is possible: Initial arrangement One exchange

Three electrons of same spin, three exchanges are possible: Initial arrangement 123 One exchange Second exchange Third exchange The exchange energy explains why half-filled subshells are unusually stable. e.g. the electron configuration of Cr: [Ar]4s1 3d5 instead of [Ar]4s2 3d4 213 132 321

Building up the atoms in the periodic table: Period One

Z 1 2 Atom Electron configuration H He 1s1 1s2 para- or Hie diamagnetic (first / eV) p d 13.6 24.6

Large! l

0 Energy 3 2 1

Building up the atoms in the periodic table: Period Two

Z 3 4 Atom Electron configuration Li Be [He]2s1 [He]2s2 para- or Hie diamagnetic (first / eV) p d 5.4 9.3

0 Energy 3 2 1

Building up the atoms in the periodic table: Period Two

Z 5 6 7 8 9 10 Atom Electron configuration B C N O F Ne [He]2s2 2p1 [He]2s2 2p2 [He]2s2 2p3 [He]2s2 2p4 [He]2s2 2p5 [He]2s2 2p6 para- or Hie diamagnetic (first / eV) p p p p p d

Dropped 8.3 from 11.3 Be (9.3 eV)

14.5 13.6 17.4 21.6

???

0 Energy 3 2 1

The Hie Anomaly at Nitrogen and Oxygen

c = Coulombic repulsion
(destabilizing)

1 e

1 e

3 e

2 e

1 e

e = exchange energy
(stabilizing)

1 c + 3 e

1 c

3 e

Loss of exchange energy increases value for N Loss of Coulombic repulsion decreases value for O

Building up the atoms in the periodic table: Period Three

Z 11 12 Atom Electron configuration Na Mg [Ne]3s1 [Ne]3s2 para- or Hie diamagnetic (first / eV) p d 5.1 7.6

0 Energy 3 2 1

Building up the atoms in the periodic table: Period Three

Z 13 14 15 16 17 18 Atom Electron configuration Al Si P S Cl Ar [Ne]3s2 3p1 [Ne]3s2 3p2 [Ne]3s2 3p3 [Ne]3s2 3p4 [Ne]3s2 3p5 [Ne]3s2 3p6 para- or Hie diamagnetic (first / eV) p p p p p d 6.0 8.2 10.5 10.4 13.0

*** repeat***

Only slightly 15.8 higher than H (13.6 eV) 2 l

0 Energy 3 2 1

Building up the atoms in the periodic table: Period Four

Z 19 20 Atom Electron configuration K Ca [Ar]4s1 [Ar]4s2 para- or Hie diamagnetic (first / eV) p d 4.3 6.1

Li 5.4 eV Na 5.1 eV

0 Energy 4 3 2 1

Whoa, what about 3d?!!!

An Anomaly of the Periodic Table

The 4s orbitals are lower in energy than the 3d orbitals for K and Ca. This is only for the free atoms! In molecules 3d are lower in energy than 4s! An accident of nature but it is consistent throughout the table.

Building up the atoms in the periodic table: Period Four

Z 21 22 23 24 25 26 27 28 29 30 Atom Electron configuration Sc Ti V Cr Mn Fe Co Ni Cu Zn [Ar]4s2 3d1 [Ar]4s2 3d2 [Ar]4s2 3d3 [Ar]4s1 3d5 [Ar]4s2 3d5 [Ar]4s2 3d6 [Ar]4s2 3d7 [Ar]4s2 3d8 [Ar]4s1 3d10 [Ar]4s2 3d10 para- or Hie diamagnetic (first / eV) p p p p p p p p p d 6.5 6.8 6.7 6.8 7.4 7.9 7.9 7.6 7.7 9.4

Pretty constant Why? exchange E pairing

exchange E

Building up the atoms in the periodic table: Period Four

Z 31 32 33 34 35 36 Atom Electron configuration Ga Ge As Se Br Kr [Ar]4s2 3d10 4p1 [Ar]4s2 3d10 4p2 [Ar]4s2 3d10 4p3 [Ar]4s2 3d10 4p4 [Ar]4s2 3d10 4p5 [Ar]4s2 3d10 4p6 para- or Hie diamagnetic (first / eV) p p p p p d 6.0 7.9 9.8 9.7 11.8 14.0
***again***

Plummets from 9.4 eV!

0 4 3 2 1 Energy

Building up the atoms in the periodic table:

Period Five: - analogous to period four Period Six: - analogous to period five with the introduction of the (4f) lanthanides after the 6s elements Period Seven: - in theory, analogous to period six with the introduction of the Actinides (5f) after the 7s elements but little is known about the short-lived nuclei after Z=104 (Rutherfordium).

Ionization Potential Summary

First Ionization Potentials

Further Ionization Enthalpies, Hie

Some examples: Na(g) Na+(g) + eAl(g) Al+(g) + eAl+(g) Al2+(g) + eAl2+(g) Al3+(g) + eThus: Al(g) Al3+(g) + 3eHie = 502 kJ/mol Hie = 578 kJ/mol Hie = 1817 kJ/mol Hie = 2745 kJ/mol Hie = 5140 kJ/mol

The enthalpy change for the gain of an electron, E(g) + e- E-(g) EA ~ Hea (note ve sign) Cl(g) + e- Cl-(g) O(g) + e- O-(g) O-(g) + e- O2-(g) O(g) + 2e- O2-(g) Hea = 349 kJ/mol Hea = 142 kJ/mol first attachment is usually exothermic Hea = 844 kJ/mol second attachment is usually endothermic Hea = 702 kJ/mol

Electron Affinity (EA) and Electron Attachment Enthalpy (Hea)

Other factors favour the presence of O2- when it is found in molecules and ionic solids.

 Na: [Ne]3s1 additional electron makes [Ne]3s2 which is a full subshell. Si: [Ne]3s2 3p2 additional electron makes [Ne]3s2 3s3 which is a more stable half-filled subshell so EA is high. P: [Ne]3s2 3p3 additional electron makes [Ne]3s2 3p4 which requires electron pairing so EA is low.

The Size of Atoms and Ions Radii of neutral atoms

The atomic radius of an atom is not really an exact science Goal: predict bond lengths within a reasonable error Element Bond Length (pm) Atomic Radius F2 Cl2 Br2 I2 C (diamond) In general: - radii decrease across a period because of increasing Z*. -radii increase down a group because of the increasing distance of the electrons from the nucleus. - increasing distance from the nucleus outweighs effective nuclear charge for atomic radii down a group. 142 199 228 267 154 F = 71 Cl = 100 Br = 114 I = 133 C = 77

Remember that the maximum probability for an orbital moves further away from the nucleus with increasing n.

The d-block contraction causes Ga to be about the same size as Al. This is caused by the introduction of the 3d elements which cause a vastly larger Z* for Ga.
0.1 nm = 1 = 100 pm

Radii of ions

This is a self-consistent scale based on O-2 = 1.40 (or 1.38) . Positively charged ions are smaller than their neutral analogues . Increased Z*. Lower n. Negatively charged ions are larger than their neutral analogues because of decreased Z*.

Same periodic trends as atomic radii for a given charge

Example: Utility of Covalent and Ionic Radii

The radii tabulated in various books allow us to predict the bond length (distance between nuclei) we would expect to see for a new bond. For covalent radii, the predictions will be the best for atoms that have similar electronegativities. If the electronegativities are very different, the predicted distance will be too long. Li O Atomic 1.52 0.73 d = 2.25 Angstroms Ionic 0.68 1.40 d = 2.08 Angstroms Why the difference? Example: What is the expected bond length for a single Sb-N bond ? For N, rcov = 0.70 and for Sb, rcov = 1.41

Using these values, an Sb-N bond should be 2.11 . The experimental distance is 2.05 .

Van der Waals radii

Van der Waals radii are established from contact distances between non-bonding molecules in crystals rVDW decreases

VDW radii allow us to determine whether there can be a bonding interaction between two atoms: If the distance between the nuclei is larger than the sum of the VDW radii, then the atoms are probability not bonded.

rVDW increases
H 1.2 N 1.5 P 1.9 O 1.4 F 1.35

S 1.85 Cl 1.80 I 2.15 Angstroms

Sb 2.2 Te 2.2

Summary
Hunds rules Trends: Ionization Enthalpy (ionization potential) Electron attachment enthalpy (-electron affinity) Radii (atomic, ionic, Van der Waals)

Next Class
Lecture 3 Redox Frost Diagrams Electronegativity Polarizability, hard and soft