Lecture 19: Many Electron Atoms The material in this lecture covers the following in Atkins.

The structure of many-electron atoms 13.4 The orbital approximation (a) The helium atom (b) The Pauli principle (c) penetration and shielding (d) the building-up principle (e) The configuration of ions (f) Ionization energies and electron affinities 13.5 Self-consistent field method Lecture on-line Many electron atoms (PDF Format) Many electron atoms (PowerPoint) Handout for this lecture

Electronic Structure of Many - Electron Atoms

He atom The Helium atom and Helium like ions

Or The two electron atom

We shall consider an atom made up of two electrons and a nucleus of charge Z

r 12 r 2 Z e 1 r Z 1

Electronic Structure of Many - Electron Atoms

He atom We might also describe the two electrons in spherical coordinates

e 2 r 12 r 2 X 2 2 Z e 1

1 r Z 1 1 Y

Electron #1 : (r1,1,1) Electron #2 : (r2,2,2) The Hamiltonian of the system is given by h2 2 Ze2 h2 2 e2 Ze2 1 H= + 2m 2 4 r + 4 r 4 or1 2me e o 2 o 12

Electronic Structure of Many - Electron Atoms He atom Here h2 2 Ze2 1 ho(1) = 4 or1 2me is the Hamiltonian of a single electron in the field of a nucleus of charge Z
Z e 1 r Z 1

Z e
1

2 r 2 2 Y 2 Z

Same for h2 2 Ze2 2 ho(2) = 4 or2 2me

Electronic Structure of Many - Electron Atoms

He atom

e2 The term represents repulsion between 4 or12 two electrons at the distance r 12 .

r 12 r 2

Z e r 1 Z 1

Electronic structure of many - electron atoms

For a many electron atoms we have the exact Hamiltonian n h2 n n ee Ze2 2 H = [ i ]+ 4 ori i=1 2me j i> j 4 orij

Electron electron repulsion between electron i and electron j

ee H = h(Z, i) + i =1 j i > j 4 o rij

n n n

Here Ze 2 h2 2 h(Z, i) = i 2me 4 ori

Shielding We can approximately add this potential to the attractive potential

Electronic Structure of Many - Electron Atoms

due to the nucleus as Vi (r) to modify ho (i) as

h2 2 Ze 2 h'(Z, i) = i + Vi (ri ) i = 1, 2, 4,.... 4 ori 2me

Re pulsion from other electrons
H H' = h' i (Z, i)
i =1 N

Electronic Structure of Many - Electron Atoms Orbital approximation For the approximate Hamiltonian
H' = h'(Z, i)
i

and the corresponding Schrdinger equation is H' (1, 2, 3, 4.., n) = E(1, 2, 3, 4.., n) We shall now show that the the many - electron wavefunction (1, 2, 3,..) that is a solution to the above Schrdinger equation can be written as
r r r r r (1,2,3,..,n) = 1(r1 ) 2 (r2 ) 3 (r2 ). 4 (r4 ).... n (rn )

Where i is a solution to : for each i = 1, 2,..n, and h2 2 Ze 2 h' (Z, i) = i 4 ori 2me

' hi (ri ) i (ri ) = i i (ri )

+ Vi (ri )

Electronic Structure of Many - Electron Atoms Orbital approximation We have r r r r r H' (1, 2, 3, .., n) = { h'i (i)} 1( r1) 2 ( r2 ) 3 ( r2 ). 4 ( r4 ).... n ( rn )
i

r r r r r = h'i (i) 1( r1) 2 ( r2 ) 3 ( r2 ). 4 ( r4 ).... n ( rn )

r r r r r = i 1(r1 ) 2 (r2 ) 3 (r2 ). 4 (r4 ).... n (rn )

i
r r r r r = { i } 1( r1) 2 ( r2 ) 3 ( r2 ). 4 ( r4 ).... n ( rn )
i

Thus H' (1, 2, 3, .., n) = E(1, 2, 3, .., n) E = { i }

i=1 n

Electronic Structure of Many - Electron Atoms

Shielding

The solutions to the equations h2 2 Ze2 i + Vi (ri ) i (ri ) = i i (ri ) h'i (i) i (i) = 4 ori 2me can again be written on the form i (ri ) = Ylm ( .)Rnl (ri ) However, now Rnl (ri ) is a solution to :

Ze h 2 2Rnl (r) 2 Rnl (r) h 2 l(l + 1) { + + ) + { }Rnl (r) 2r 2 r r 2 4 or 2mr + Vi (ri )Rnl (r) = ERnl (r)

Electronic Structure of Many - Electron Atoms

Shielding

The final solution for a many - electron atom with nuclear charge Z can to a good approximation be written as : r i ( ri ) = Ylimi (i .i )Rnili (ri ) where Rnl (ri ) has the same analytical form as for the hydrogenic one - electron atom with atom charge Z. Only throughout Z is replaced by Z - nl = Znl
Shielding constant

Effective nuclear charge

With the energy Znl 2 Ze 4 Z,n = 2h 2

Electronic Structure of Many - Electron Atoms Shielding Znl = Z - nl 1. Electrons in orbitals with quantum number n = n * will be shielded from the nucleus by electrons of lower n - quantum number that are closer to the nuclei. Thus
n=1 n=2 n=3 n=4

nl increases with n and Znl (the effective nuclear charge) will decrease with n

Electronic Structure of Many - Electron Atoms

Shielding

For a given n The shielding nl increases with l and the effective nuclear charge Znl decreases with l.

3s
En =

3p
Z2e 4

3d

3s

2 32 2 oh 2n2

En

3p 3d (Zi )2 e 4 nl
2 32 2 oh 2n2

Orbitals with th same n - quantum number have different energy if l is different in many - electron atoms but the same energy in hydrogenic atoms

Electronic Structure of Many - Electron Atoms

Shielding

eff

' Znl

Z Z nl

Electronic Structure of Many - Electron Atoms Building up principle He atom To construct the wavefunction we use the Pauli exclusion principle :

Each orbital nlm (different n, l, m) can only contain two electrons .The electrons must have different spins ( (i)/(i) )
Thus : (1, 2) = 1s(1) (1)1s(2) (2)
1s(1)

He = .32; Z' = 2 - .32 1s

Z=2

E = 1s + 1s
= (Z'nl )2 e 4
2 32 2 oh 2n2

Z= 1.68 Z=1.0

r/a

Electronic Structure of Many - Electron Atoms Building up principle Li atom

Each orbital nlm (different n, l, m) can only contain two electrons .The electrons must have different spins ( (i)/(i) )
According to the Pauli exclusion principle the K - shell (1s)2 is full and the next electron must go into 2p or 2s orbitals of L - shell
In many - electron shells orbitals of same n (shell) but different l do not have the same energy. The energy increases with l as the orbitals penetrates less and less to the nuclei Thus within a subshell : s < p < d < f

Electronic Structure of Many - Electron Atoms Building up Thus the electron configuration principle og Li is 1s2 2s

(1, 2, 3) = 1s(1) (1)1s(1)(1)2s(1) (1) or (1, 2, 3) = 1s(1) (1)1s(1)(1)2s(1)(1)

1s (Z=2.68)
2s (Z= 3.0) 2s(Z=1.7) 1s (Z=3)

For Be we have 1s2 2s2

(1, 2, 3, 4) = 1s(1) (1)1s(1)(1) 2s(1)(1)2s(1)(1)

the radial functions for 1s and 2s of Li have exponents of 2.68 and 1.7, respectively, rather than 3

Electronic Structure of Many - Electron Atoms Building up principle and configuration 2 2 1 B : 1s 2s 2p x of atoms py px pz

C : 1s2 2s2 2p1 2p1 x y

px

py

pz

N : 1s2 2s2 2p1 2p1 2p1 x y z

px

py

pz

Hunds rule : Electrons occupy different orbitals of sub - shell before double occupation

Parallel spin prefered

Electronic Structure of Many - Electron Atoms Building up principle and configuration 2 2 2 1 1 O : 1s 2s 2p x 2p y 2pz of atoms py px pz
F : 1s2 2s2 2p2 2p2 2p1 x y z

px

py

pz

Ne : 1s2 2s2 2p2 2p2 2p2 x y z

px

py

pz

Electronic Structure of Many - Electron Atoms

Occupation of the sub - shells follow the order 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s with some exceptions

Electronic Structure of Many - Electron Atoms Znl 2 Ze 4 Ionization potentials Z,n = 2 2h

Electronic Structure of Many - Electron Atoms

Znl 2 Ze 4 Z,n = 2 2h

Electron affinities

What you should know from this lecture You should unders tan d the Be able to construct the concept of a shielding cons tan t electron configuration for . an atom using the Pauli You should also know that exclusion principle and depends on a particular Hundsbuild - up principle element as well as the n and l Realize that orbitalswith the same quantum number ( Z,n,l ) and n - quantumnumber but different l - quatum number have different that the effective charge energies in many electron atoms is given by
eff Zn,l = Z Z,n,l

Be aware that the orbitals in a many - electron atom can be written as Z

n,l,m(r,, )=Rn,l (R)Yl,m (, )

Understand the concept of ionization potentials and electron affinities and how they are related to shielding and the effective nuclear charge