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Ch 2 Many electron atom and periodic table

Ch.

Wavefunction for many e- system


B ild p principle
Build-up
QM and periodic table properties
- effective nuclear charge
- atomic radius
- ionic radius
- ionization energy
- electron affinity

Wavefunctions for Many Electron Atoms


For helium (He): function of six position variables
variables, x1, y1,
and z1 for electron 1 and x2, y2, and z2 for electron 2.

( He ) ( x 1 , y 1 , z1 , x 2 , y 2 , z2 )
For an atom with N electrons

(N - electron atom ) ( x 1 , y 1 , z1 , x 2 , y 2 , z2 ..., xN , y N , zN )

Schrodinger equation for He


2

2me

2 2 2 2 2 2
2 2 2 2 2 2 V ( x1 , y1 , z1 , x2 , y2 , z 2 ) E
z1
x2 y2 z 2
x1 y1
potential energy term

kinetic energy term

Potential energy term:

2e 2

2e 2
2e 2
V ( x1 , y1 , z1 , x2 , y2 , z 2 )

4 0 r1 4 0 r2 4 0 r12

electron-nuclear attraction
electron-electron repulsion

Electron-electron repulsions not present in


hydrogen.

Figure 2.1 The geometry of the


helium atom.

Orbital approximation
pp
for manyy e- atoms

Without electron-electron repulsions (guessed)

1s (r1 )1s (r2 )


where
h
denotes
d
an orbital
bi l ffor an iindividual
di id l electron
l
leads to unsatisfactory results.
results

Solution: self-consistent field (Hartee/SCF) method

1 (r1 )2 (r2 )

Hartees self-consistent field (SCF) method for many e(1). Each e- moves in an effective field
created by the nucleus and all the other e-,
and only depends on r.
(2). The effective
(2)
effecti e field for electron i is
obtained by averaging its Coulomb
interactions.
(3). The effective field is spherically
symmetric, no angular dependence

1 (r1 )2 (r2 )
For an atom with N electrons

1 (r1 )2 (r2 )3 (r3 )...n (rN )

Schematic representation of SCF method

-- Computationally intensive accomplished by sophisticated computer programs.


-- SCF orbitals can be described using the same set of quantum numbers (n, l, ml).
-- The four quantum number (n, l, ml, ms ) completely label an electron in any
orbital in any atom.

Multiple e- Atoms

-- on average, effective nuclear charge Zeff < Z


-- how
h muchh less
l Zeff < Z determines
d t
i
atomic
t i properties
ti

Effective nuclear charge, Zeff

Explain
- atomic size
- ionic
i i radius
di
- ionization energy (IE)

Shielding

Penetration: 2s > 2pp

better penetration lower in E

Penetration: 3s > 3p > 3d

Penetration: 4s > 4p > 4d > 4f

Hartree Orbitals and Energy


gy
Many e- atom vs. H-atom
Orbitals:
(1). Angular dependence: same for both (l and m)
(2). Radial dependence: both have n, but different effective field
(3) 4th quantum number (ms): defines the spin state
(3).
Energy:
(1) Degeneracy of p,
(1).
p d,
d f orbitals is removed (Ens < Enp < End)
(2). Energy values are distinctly shifted

Vneff (r )
En , SCF

Z eff (n)e 2
r

[ Z eff (n)]2
n2

Energy of multi-e- atoms and Aufbau Principle

n=3 l = 2
n=3
n
3l=1
n=3 l = 0
n=2
2l=0

n=2 l = 1

n=1 l = 0

In the same shell (n),


energy order: s < p < d < f

Paulis Exclusion Principle:


-- each orbital can have, at most, 2 e-- when 2 e- occupy the same orbital, it must be paired (opposite
spins)
-- no 2 e- can have the same set of quantum numbers
Hund s Rule
Hunds
The most stable arrangement of electrons in subshells is the
one with the greatest number of parallel spins

3
d4
5d
d6
d

He core (n, l, ml, ms)

He core (n, l, ml, ms)

2p electrons*
2, 1, +1, +
2, 1, +1,
2, 1, 0, +
2, 1, 0,
2, 1, 1, +

2p electrons
2, 1, +1, +
2, 1, +1,
2, 1, 0, +
2, 1, 0,
2, 1, 1, +
2, 1, 1,

* one possible assignment

Exceptions occur because electrons dont like to pair up in orbitals,


So highlighted atoms have lower energy

Ex 2-1
Which one has the largest Zeff?

A).
) H (Z=1)
(
)

B).
) H ((Z=1)) C).
) He ((Z=2))

Which one has the smallest size?

A). H (Z=1)

B). H (Z=1)

C). He (Z=2)

Ex 2-2
Whichh one has
Whi
h the
th largest
l
t atomic
t i size?
i ?
H (z=1), He (z=2), Be (z=4), C (z=6)

A) H
A).

B)
B). He

C)
C). Be

D)
D). C

Which one has the second largest atomic size?

B). He

C). Be

D). C

Ionic Radius
increases down a group

decreases across a period

(treat cations and anions separately)

atom cation
radius decreases

atom anion
radius increases

The Radii (in pm) of Ions of Familiar Elements

Ionization Energy

-- Smaller
S ll atoms harder
h d to remove e-- Subsequent ionizations are always
higher (IE2 >> IE1)

Ex 2-3
When an atom loses an electron to become a cation,
cation it
A) Releases energy
B) requires energy
C) depends?

Electron Affinity

Electron affinity (EA) vs. Ionization energy (IE)

EA of element X = IE of Anion XElectron Affinity


Can be either + or - in sign
No atom has a positive 2nd E.A.
Ionization Energy
y Positive
Always
2nd I.E.s are always > 1st I.E.s

Electron Affinity

Ex 2-4
Which one is larger?
A). N3 B). F C). Not enough information
Which one is larger?
A). Fe2+ B). Fe3+ C). Not enough information

Ex 2-5
Which one should have a smaller first ionization energy?
A) O
A).
B)
B). S
C)
C). N
Nott enough
h iinformation
f
ti
Whichh one should
Whi
h ld have
h
a higher
hi h secondd ionization
i i ti energy??
A). Li
B). Be
C). Not enough information