Energy Level Scheme of 1-electron (Hydrogenic) Atoms: En ~ 1/n2 (n- only)

HANDOUT: QM & PT: QUANTUM MECHANICS & PERIODIC TABLE (page 1)

Schrdinger Wave Equation (SWE) for MULTI-ELECTRON ATOMS contains potential energy terms which include interactions BETWEEN electrons

Nuclear attraction = !

Z e 2 Z e 2 ! , where Z = 2 for He r1 r2 e2 |r1 ! r2 |

Electron !Electron Repulsion = Electron Correlation = +

Figure 12.23 - Zumdahl - Chemical Principles (4/e)

This last term correlates (couples) electron behavior SWE can NOT be solved exactly APPROXIMATIONS
1 2

QM & PT: (page 1)

Z e Z e ! r1 r2
2 2

QM & PT: (page 2)

PRESUME that eect of e-e repulsion was INDIRECT, I.e, Each electron separately a racts the nucleusBUT The specic amount of nuclear charge felt varied with EACH electrons SUBSHELL designation (n & l). This ATTENUATED NUCLEAR CHARGE is termed EFFECTIVE NUCLEAR CHARGE (Ze = (Z - s) < Z) - subshell dep. Energy of subshell = En l = - Ze,nl2Ry/n2 , n = 1, 2, 3, Otherwise, each electron occupies a hydrogenic atomic orbital !nlml(r,",#) = Rnl(r)Ylml(",#) same pictures from before.
3 4

Nuclear attraction = !

, where Z = 2 for He

e2 Electron !Electron Repulsion = Electron Correlation = + |r1 ! r2 |

e-e repulsion

e1- (correlation)

e2-

nuclear attraction 2p+

nuclear attraction

QM & PT: (pages 2-3)

!nlml(r,",#) = Rnl(r)Ylml(",#). Rnl(r) - expresses the radial behavior [RDFs]. Radial behavior (pictures) RATIONALIZE SUBSHELL ENERGY DEPENDENCE. Ze = Z - s ; where s is the SCREENING or SHIELDING. Energy of subshell = En l = - Ze,nl2Ry/n2 , n = 1, 2, 3, Ze - for a given n - DECREASES as l INCREASES. s feels greatest & f the least. SEE RDFs
5

Radial Distributions {4r2[Rnl(r)]2}: n = 3 orbitals For the same n value, lower l value has greater degree of penetration [ns (greatest) > np > nd > nf (least)]

Figure 12.33 - Zumdahl - Chemical Principles (4/e)

Eective Nuclear Charge (Ze) & Multi-electron Atoms: Ze, n,l = Z - sn,l depends on (n,l) - subshell: ENERGY of e- SUBSHELL: En,l = -Ze2Ry/n2 . IONIZATION ENERGY of e- in subshell: IEn,l = Ef - Ei = 0 -En,l = +Ze2Ry/n2

Energy Level Scheme of Multi-electron Atoms: Depends on (n,l) - subshell - En,l = -Ze2Ry/n2 .

Figure 8.10 - Hill & Petrucci - General Chemistry (3/e)

Figure 8.1 - Hill & Petrucci - General Chemistry (3/e)

Radial Distributions {4r2[Rnl(r)]2}: 3d vs 4s subshells E4s (more stable) < E3d (less stable) :

QM & PT: (page 4)

How do we pile e-s in orbitals? First one more quantum # Spin Quantum # (ms) - 4th Quantum #: ms = +1/2 or -1/2

Figure 12.33 - Zumdahl - Chemical Principles (4/e)

Figure 7.29 - Hill & Petrucci - General Chemistry (3/e)

10

QM & PT: (page 4)

Spin Quantum # (ms) = +1/2 or -1/2 RESTRICTS Orbital Population: Pauli Exclusion Principle (PEP): (Dierent ways of saying the same thing): NO 2 e-s are allowed (zero probability) to have the SAME set of 4 quantum #s (n, l, ml , ms). IF 2 e-s are in the SAME ORBITAL (same n, l, ml ), each MUST have DIFFERENT ms values, i.e., they MUST have OPPOSITE SPINS. Any orbital can have, at MOST, ONLY 2 e-s; 1 e- with ms = +1/2 ($) & 1 e- with ms = -1/2 (%), i.e., $ % .
11

Aufbau Ordering of Energies of Subshells of Multi-electron Atoms: [1s subshell through 6s subshell]

Energy

6s 5s

5p 4d 4p 3p 3d Aufbau ordering of subshell energies. En,l = - (Zeffective)2Ry/n2

12

En,l
Not to scale.

4s 3s 2s 1s

2p

GROUND STATE (Most Stable) electron congurations: [H, He, Li, Be, & B] - Orbital Box Diagram Lowest energy ----> Highest energy (Obey PEP)

GROUND STATE (Most Stable) electron congurations: Populating subshells containing energy-degenerate orbitals Do NOT bunch up spread out

Energy

Energy

2p { B} En,l
Not to scale. 2s 1s { Li , Be } { H , He }

Aufbau ordering: (Ground State Configurations) En,l = - (Zeffective)2Ry/n2

2p En,l
Not to scale.
13

2s 1s

{ Li , Be } { H , He }

Carbon? ... NOT a Lowest Energy Ground State Config. ... actually an Excited State Config.!! En,l = - (Zeffective)2Ry/n2

14

GROUND STATE (Most Stable) electron congurations: Populating subshells containing energy-degenerate orbitals Ground State conguration of Carbon: Hunds Rule (preference) for Ground State Congurations: Singly occupy all orbitals [$ $ ] of same energy with SAME spin BEFORE lling any of them [$% ]).
Energy

GROUND STATE (Most Stable) electron congurations: Populating subshells containing energy-degenerate orbitals Ground State conguration of Nitrogen: Hunds Rule (preference) for Ground State Congurations:
Energy

2p
2p
2s 1s { Li , Be } { H , He } Carbon: Hund's Rule Aufbau ordering: (Ground State Configurations) En,l = - (Zeffective)2Ry/n2

En,l
Not to scale.

En,l
Not to scale.
15

2s 1s

{ Li , Be } { H , He }

Nitrogen: Hund's Rule

Aufbau ordering: (Ground State Configurations) En,l = - (Zeffective)2Ry/n2

16

GROUND STATE (Most Stable) electron congurations: 2nd Row: [Li, Be, B, C, N, O, F, Ne] Lowest energy ----> Highest energy (Obey PEP, & Hunds Rule)

GROUND STATE (Most Stable) electron congurations: 3rd Row: [Na, Mg, Al, Si, P, S, Cl, Ar] Lowest energy ----> Highest energy (Obey PEP, & Hunds Rule)

Energy

Energy

2p { B,C,O,N,F,Ne} En,l
Not to scale. 2s 1s { Li , Be } { H , He }

Aufbau ordering: (Ground State Configurations)

3p

{Al,Si,P,S,Cl,Ar}

Aufbau ordering: (Ground State Configurations)

En,l

3s

{ Na , Mg}

En,l = - (Zeffective)2Ry/n2

En,l = - (Zeffective)2Ry/n2
Not to scale.

2p { B,C,O,N,F,Ne}
2s 1s { Li , Be } { H , He }
18

17

Electron Conguration Correlated with Periodic Table: [Ground State (Lowest Energy) Congurations]

GROUND STATE (Most Stable) electron congurations: 4th Row - Includes 1st period of Transition Metals: [K, Ca, Sc, Ti, V, Cr*, Mn, Fe, Co, Ni, Cu*, Zn, Ga, Ge, As, Se, Br, Kr] Lowest energy ----> Highest energy (Obey PEP, & Hunds Rule)
Energy 4p {Ga,Ge,As,Se,Br,Kr} 3d {Sc,Ti,V,Cr*,Mn,Fe,Co,Ni,Cu*,Zn}

En,l

4s

{ K , Ca } 3p {Al,Si,P,S,Cl,Ar}

Aufbau ordering: (Ground State Configurations)

3s

{ Na , Mg}

En,l = - (Zeffective)2Ry/n2

2p { B,C,O,N,F,Ne}
Not to scale. 2s 1s
19

{ Li , Be } { H , He }
20

Figure 12.26 - Zumdahl - Chemical Principles (4/e)

Electron Conguration Correlated with Periodic Table: [4th Row (Period) - Ground State (note 24Cr & 29Cu)]:

Condensed Formats to Represent Electron Congurations: [page 7 of QM & PT handout] Example: Sulfur (S) [For Orbital Box Diagram - see below] Spectroscopic: 1s2 2s2 2p6 3s2 3p4 [in order of $ energy] Noble gas core abbreviation : [Ne] 3s2 3p4 (3s & 3p e-s are the VALENCE electrons)
Energy 3p SULFUR (S) Aufbau ordering: (Ground State Configurations) En,l = - (Zeffective)2Ry/n2

En,l

3s

2p
2s Not to scale.
21

1s
22

Figure 12.27 - Zumdahl - Chemical Principles (4/e)

Electron Conguration Correlated with Periodic Table:

Follow the Periodic Table to Determine Ground State Electron Congurations: [page 5 of QM & PT handout] Transition metals: [Noble gas core] ns2 (n-1)d1 --> 10 (n = row #) [Some exceptions Cr = [Ar] 4s1 3d5 , Cu = [Ar] 4s1 3d10] Lanthanides (Between 57La & 72Hf - 6th row): [Xe] 6s2 5d1 4f1 ---> 14 [58Ce through 71Lu]. [Some exceptions Dont worry about exceptions.] Actinides (Between 89Ac & 104Rf - 7th row): [Rn] 7s2 6d1 5f1 ---> 14 [90Th through 103Lr]. [Some exceptions Dont worry about exceptions.]

Figure 12.28 - Zumdahl - Chemical Principles (4/e)

23

24

Electron Conguration Correlated with Periodic Table:

Main Group Elements & Valence Shell Electron Conguration [page 8 of QM & PT handout] Group 1A 2A 3A 4A 5A 6A 7A 8A Valence Shell e- Cong*. ns1 ns2 ns2 np1 ns2 np2 ns2 np3 ns2 np4 ns2 np5 ns2 np6 # of Valence e-s 1 2 3 4 5 6 7 8

*[n is the row # (period) of the element in the group.] Figure 12.29 - Zumdahl - Chemical Principles (5/e)
25 26

Cations: Construct ground state electron conguration of NEUTRAL atom rst. Remove e-s from populated shell of HIGHEST principal quantum # (n) until proper cation charge is achieved*. * If more than one subshell of highest principal quantum # is populated, BEGIN with subshell of HIGHEST l quantum #. (i.e., subshell that is MOST [<--- corrected] shielded.) *[n is the row # (period) of the element in the group.] Examples: Fe+2 & Pb+4: 1st Fe: [Ar] 4s2 3d6 , then, Fe+2 : [Ar] 3d6 (NOT [Ar] 4s2 3d4). 1st Pb: [Xe] 6s2 4f14 5d106p2 , then, Pb+4 : [Xe] 4f14 5d10 (NOT [Xe] 6s2 4f14 5d8).
27

Ground State Electron Conguration of Ions [page 8 & page 9 of QM & PT handout]

Ground State Electron Conguration of Ions [page 8 & page 9 of QM & PT handout] Anions (page 9): Typically involve non-metals in the p-block. Construct ground state electron conguration of NEUTRAL atom rst. Continue to add electrons consistent with the Aufbau ordering scheme. Example: O-2 (oxide anion) 1st O: [He] 2s2 2p4 , then O-2 : [He] 2s2 2p6 = [Ne] (isolectronic with Ne).
28

Paramagnetism & Diamagnetism (unpaired e-s vs all e-s paired ) [page 9 & page 10 (diagram) of QM & PT handout]

Paramagnetism & Diamagnetism (unpaired e-s vs all e-s paired ) [page 9 & page 10 (diagram) of QM & PT handout] Construct electron conguration of species & determine if there are any unpaired e-s [orbital box diagram.] If ANY unpaired e-s & PARAMAGNETIC. Species is ATTRACTED by a magnetic eld. # of unpaired electrons determines degree of paramagnetism. As # of unpaired e-s $, degree of paramagnetism $s. Species is a racted more strongly by magnetic eld. If NO unpaired e-s, i.e., all are paired & DIAMAGNETIC. Species is NOT a racted by a magnetic eld.
29 30

Weights

Balance

Sample - suspended from one side of balance.

Magnet

Atomic Radii (in pm) (Main Group Elements): [pp. 11 - 16.]

Ionic Radii (in pm) (Main Group Elements): [pp. 11 - 16.]

Figure 12.38 - Zumdahl - Chemical Principles (4/e)

31

Figure 13.7 - Zumdahl - Chemical Principles (4/e)

32

1st IEs (Main Group Elements): [pp. 11 - 16.] M(gas) -----> M+(gas) + e- ; E =IE1 (+)

Electron Anities (EA) (Main Group Elements): [pp. 11 - 16.] A(gas) + e- -----> A-(gas) ; E = EA (+ or -)

Figure 12.35 - Zumdahl - Chemical Principles (4/e)

33

Figure 12.36 - Zumdahl - Chemical Principles (4/e)

34

Electronegativities (Pauling Values):

PERIODIC TRENDS - SUMMARY [See QM & Periodic Table - pages 11-14] Radius, Diameter, Size [Fig. 12.38, Zumdahl] : DECREASES L ---> R across a row (period) - generally. [Ze increases]. INCREASES Top ---> Bo om down a column (group). [Ze decreases outermost e-s farther away from nucleus.] Ionic Radius, Diameter, Size [Fig. 13.7, Zumdahl] : Radius of CATION < corresponding NEUTRAL ATOM. Radius of ANION > corresponding NEUTRAL ATOM.

Figure 13.3 - Zumdahl - Chemical Principles (4/e)

35

36

PERIODIC TRENDS - SUMMARY [See QM & Periodic Table - pages 11-14] IONIZATION ENERGY (1st IE) : A(gas) ' A+(gas) + e- IE of A = E of reaction (+). INCREASES L ---> R across a row (period) - generally. [Ze increases]. Glitches. Look at (ground state) e- congs. IE1 values [3rd row (period)] (in kJ/mol): Na Mg Al Si P S Cl Ar 500 740 580 790 1060 1000 1260 1520 3s1 3s2 3p1 3p2 3p3 3p4 3p5 3p6 [before] 3s0 3s1 3p0 3p1 3p2 3p3 3p4 3p5 [after] DECREASES Top ---> Bo om down a column (group). IE1 values [Group 2A)] (in kJ/mol): Be (900) ; Mg (740) ; Ca (590) ; Sr (550) ; Ba (500)
37

PERIODIC TRENDS - SUMMARY [See QM & Periodic Table - page 13] SUCCESSIVE IONIZATION ENERGIES (IE1 IEn). Example - Aluminum (Al) : Al(gas) ' Al+(gas) + eIE1 = 580 kJ/mol [3p1 ----> 3p0].

Al+(gas) ' Al+2(gas) + e- IE2 = 1,820 kJ/mol [3s2 ----> 3s1]. Al+2(gas) ' Al+3(gas) + e- IE3 = 2,740 kJ/mol [3s1 ----> 3s0]. Al+3(gas) ' Al+4(gas) + e- IE4 = 11,580 kJ/mol [2p6 ----> 2p5].

38

PERIODIC TRENDS - SUMMARY [See QM & Periodic Table - page 15] ELECTRON AFFINITY (EA) - energy change of reaction: A(gas) + e- ' A-(gas) EA of A = E (+ or -). More negative - more exothermic acquisition. More negative (generally) L ---> R . across a row (period). Quirky. Less negative (generally) Top ---> Bo om down a column (group). Quirky. Li Be B C N O F -59.6 (+) -26.7 -122 (+) -141 -328 Na Mg Al C P S Cl -59.6 (+) -43 -134 -72 -200 -349 Br -325
39

PERIODIC TRENDS - SUMMARY [See QM & Periodic Table - page 16] ELECTRONEGATIVITY (x) - measure of ability for atom to draw electron density from an atom to which it is chemically bonded. F = greatest = 4.0 , H = 2.1 , Group 1A metals - least. INCREASES L ---> R across a row (period). [closer to F] DECREASES Top ---> Bo om down a column (group). [farther away from F] continued
40

PERIODIC TRENDS - SUMMARY Electronegativity Dierence (x) & Covalent versus Ionic Bonds: xA & xB = electronegativity of atoms A & B, respectively. (x = | xA - xB | = magnitude of the electronegativity dierence between atoms A & B. If (x = 0 (Exactly) AB bond is purely covalent (or non-polar). If 0 < (x 1.7 AB bond is polar covalent, i.e., the electrons are polarized toward with larger x. If (x > 1.7 AB bond is ionic, i.e., the electrons in the bond are totally owned by atom with larger x (anion) & totally lost by atom with smaller x (cation).
41