Вы находитесь на странице: 1из 12

Electronic States of Atoms

CH2101

Electronic Levels for Individual Electrons

Electronic Configuration of Atoms

Al:

1s2 2s2 2p6 3s2 3p1

Electronic States of Atoms


Quantum numbers for electrons Quantum numbers for many-electron atoms
l: orbital angular momentum quantum
L: orbital angular momentum quantum number
number (0,1, n-1
e.g., for 2 e-: L = l1+l2, l1+l2 -1, l1+l2 -2, ,| l1-l2 |
where 0=s, 1=p, 2=d, 3=f)
0 = S, 1 = P, 2 = D, 3 = F

ml: orbital magnetic quantum number


ML: orbital magnetic quantum number (Sml)
(l, l-1, , 0, , -l )
2L+1 possible values
s: electron spin quantum number (1/2)

S: total spin quantum number


S = s1+s2, s1+s2 -1, ,| s1-s2 |
S = 0 singlet, S = 1 doublet, S = 2 triplet

ms: spin magnetic quantum number


(+1/2, -1/2)

MS: spin magnetic quantum number (Sms)


2S+1 possible values
J: total angular quantum number
J = L+S, L+S-1, , | L-S|

Spectroscopic Description of
Atomic Electronic States Term Symbols
Multiplicity (2S +1) describes the number of possible orientations of total
spin angular momentum where S is the resultant spin quantum
number (1/2 x # unpaired electrons)
Resultant Angular Momentum (L) describes the coupling of the orbital
angular momenta of each electron (add the mL values for each
electron)
Total Angular Momentum (J) combines orbital angular momentum and
intrinsic angular momentum (i.e., spin).
To Assign J Value:
if less than half of the subshell is occupied, take the minimum value J
=|LS|;
if more than half-filled, take the maximum value J = L + S;
if the subshell is half-filled, L = 0 and then J = S.

5) Hunds Rules
Hunds rules allow to establish, which of the several atomic states is the one of the lowest energy.
Consider C [He]2s22p2 as an example

Following states are possible: 1D2, 1S0, 3P2, 3P1 and 3P0
1st Hunds rule. The ground state term is that of the highest multiplicity: 3P

D2 state

2px

2pz

2py

Two electrons repel each other stronger


Exchange energy is zero

2px

2pz

2py

P state

Two electrons repel each other weaker


Exchange energy stabilizes the system

2nd Hunds rule. Among terms of the same multiplicity the term with the highest L value
corresponds to the most stable atomic state.

3rd Hunds rule. The lowest energy state is that of lowest J value if the subshell is less than halffilled and of highest J value in the opposite case.
3P is the most stable atomic state
0

ELECTRONIC STRUCTURE OF THE POLYELECTRONIC ATOM.

1) Atomic States and Atomic Terms

Any atom can exist in several electronic states of different energy (atomic states). The atomic states differ
one from another by the way available a- and/or b-electrons are distributed among atomic orbitals.
Examples of atomic states:
a) H atom in 1s1 (2S1/2), 2p1 (2P3/2 or 2P1/2) or 3s1 configuration (2S1/2 state).
b) C atom in the [He]2s22p2 configuration:
1

L=0
S=0
J=0
ml

D2 state (10194 cm-1)

S0 state (21648 cm-1)


2px

2pz

2py

-1

L=2
S=0
J=2
ml

2px

2pz

2py

-1

P states (44-0 cm-1)

L=1
S=1
ml

2px

2pz

2py

-1

Each atomic state is characterized by: (a) the electronic configuration, (b) by spin S, (c) the orbital angular
momentum L, (d) the total electron angular momentum J. The state of the lowest energy is called the
ground state.

The total spin S and the total orbital angular momentum L for light elements can be obtained as a vector
sum: S = Ssi and L = Sli (LS- or Russell-Saunders coupling).
The total electron angular momentum J is also defined as a vector sum J = L + S, which holds true in the
absence of significant spin-orbit coupling (LS-coupling). Possible values of J are L+S, L+S-1, |L-S|.

To distinguish between atomic states, besides electronic configuration, each of them is assigned an atomic
term symbol which looks like 2S+1LJ. You have to put here numerical values of the spin multiplicity 2S+1
and the total angular momentum J. Symbols S, P, D, F, G, H etc. are used for orbital angular
momentum L = 0, 1, 2, 3, 4, 5 respectively.

Spectroscopic Description of
All Possible Electronic States Term Symbols
C 1s22s22p2
Step 5: Use Hunds Rules to determine the relative energies of all
possible states.
1. The highest multiplicity term within a configuration is of lowest
energy.
2. For terms of the same multiplicity, the highest L value has the
lowest energy (D < P < S).
3. For subshells that are less than half-filled, the minimum J-value
state is of lower energy than higher J-value states.
4. For subshells that are more than half-filled, the state of maximum
J-value is the lowest energy.
Based on these rules, the ground electronic configuration for carbon has
the following energy order: 3P0 < 3P1 < 3P2 < 1D2 < 1S0

Spectroscopic Description of
Excited States Term Symbols
Write term symbols in analogous manner except consider the
orbital to which an electron is promoted.

For example, excitation of Na promotes one valence electron


into the 3p orbital. In this case, n = 3, S = , 2S+1 = 2, L
= 1 (P term), J = 3/2, 1/2.
There are two closely spaced levels in the excited term of
sodium with term symbols 2P1/2 and 2P3/2

This type of splitting (same L but


different J) is called fine structure.
Transition from 2P1/2 2S1/2

2) Assigning atomic term symbols

Any atom with completely-filled shells or subshells has the total spin S=0, multiplicity
2S+1=1, L=0, J=0 and can exist in the 1S0 atomic state only (He 1s2, Be [He]2s2 etc.).

Atoms with not completely filled subshells can exist in several atomic states. Hunds rules
define the lowest energy atomic state for each given electronic configuration.

Consider the following examples of atoms with one unpaired electron:


H 1s1 or Li [He]2s1 or H 3s1 (excited state)
total spin S (vector) = 1/2; MS (allowed projections of S) = 1/2, -1/2 (2S+1=2 values);
spin multiplicity 2S+1=2;
orbital angular momentum L (vector) = 0; ML (allowed projection of L) =0, (2L+1=1 value);
total electron angular momentum J = 1/2 (single value)
The state is 2S1/2

B [He]2s22p1 or H 2p1 (excited state)


total spin S = 1/2, MS = 1/2, -1/2 (2 values);
spin multiplicity 2S+1=2;
orbital angular momentum L = 1; ML = 1, 0, -1 (three possible values);
total electron angular momentum J = 3/2, 1/2 (two possible values)
The possible states are 2P3/2 and 2P1/2

3) Experimental evidence for electron spin


Consider two excited states of the hydrogen atom:

H 3s1 (excited state); S = 1/2; L = 0; J = 1/2;

The term is 2S1/2

H 2p1 (excited state); S = 1/2; L = 1; J = 3/2, 1/2;


There are two possible states, 2P3/2 and 2P1/2
These two terms arise only due to the fact that L 0 interacts with S 0. In turn, the latter is
due to electron spin. If electron spin did not exist, a single term would correspond the 2p1
configuration only.
As an evidence for electron spin, in the atomic hydrogen emission spectrum two lines are
observed, which both correspond to H 3s1 2p1 electron transition, at 656.3 and 656.2 nm:
2

3s

S1/2
2p

P3/2 656.3 nm
2
P1/2 656.2 nm

Spectroscopic Description of
Ground Electronic States Term Symbols
Term Symbol Form:

2S+1{L}
J

2S+1 multiplicity
L resultant angular momentum quantum number
J total angular momentum quantum number
Ground state has maximal S and L values.

Example: Ground State of Sodium 1s22s22p63s1


Consider only the one valence electron (3s1)
L = l = 0,
S = s = ,
J=L+S=
so, the term symbol is 2S

Вам также может понравиться