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H Xe
3.1 Structure and spectra of hydrogenic atoms
Hydrogenic atoms: atoms having only one electron (H, He+, Li2+, ) the Schrdinger
equation can be solved
Many-electron atoms impossible to solve the Schrdinger equation approximations
are needed to solve the SE (Hartree-Fock Theory, Density Functional Theory, etc..).
~ 1 1
H 2 2
n1 n2
where H is the Rydberg constant for H (H= 109677cm-1). One series is characterized by
n1, within this series the lines are specified with n2 that can take the values n1+1, n1+2,
For n1=1 Lyman series in the ultraviolet region
For n1=2 Balmer series in the visible region
For n1=3 Paschen series in the infrared region
Hydrogen spectrum
The gas inside the tube; that emits blue light is mercury, but the same can be
done with H2. The gas pressure in the tubes are low, because of natural
radioactivity and cosmic rays there are always few free electrons and ions. When
something around 2000-3000 volts is applied to these tubes under low pressure,
free electrons and ions are accelerated and collide with the gas molecule H2 and
dissociate them in excited H atoms. These collisions generate an avalanche of
charged particles. As a result, the gas in the discharge tube contains a lot of
ionized and highly excited atoms. The excited atoms give back this energy in the
form of light, while they are turning back to their ground states. (NB: Neon tubes
are typical examples of discharge tubes) The electromagnetic radiation emitted is
then analyzed by a spectrometer and various emission lines of hydrogen can be
observed in the visible (Balmer series), the ultraviolet (Lyman series) and infra-
red (Paschen series).
From the experimental law by Rydberg, a general principle is found: the Ritz
combination principle. It states that the wavenumber of any spectral line is the
difference between two terms. NB: its only for hydrogenic atoms that the terms have the
form: R
Tn H2 1 1
n ~ T1 T2 RH 2 2
n1 n2
Atom = 1e- + 1 nucleus of mass mN. Both move and have a kinetic energy Te and TN.
Because of the electron charge and the positive charge |Ze| of the nucleus, the Coulomb
potential energy V(r) has to be taken into account in the energetics of the system.
Ze 2
V(r) = -
40 r
The Hamiltonian of the Schrdinger equation H tot = E tot
describing the system is:
2 2 2
Ze
H Te TN V = e N
2 2
2 me 2 mN 40 r
The atom is a 2-body system: both the nucleus and e- move with respect to each other (relative
motion) and both move with respect to an outside reference point.
However, its possible to separate the relative motion of two particles from the motion of the
center of mass. Moreover, since me<< mN, well show that the simplified picture of an electron
moving in a spherical potential created by the nucleus can be envisaged.
In classical mechanics: lets try to express total energy of two bodies (electron and
nucleus) not with respect to their coordinates x1 and x2, but with respect to the position of
the center of mass X (of the atom) and the distance x between the two bodies (i.e; the
distance between the electron and the nucleus).
p12 p22
E V
2m1 2m2
m1 m m
X x1 2 x2 x1 X 2 x
m m
m
m m1 m2 m
x2 X 1 x
x x1 x2 m
m m
p1 m1 x1 m1 X 2 1 x
m
p12 p22 1 1
m m E V mX 2 x 2 V
p2 m2 x2 m2 X 2 1 x m2 m1 2m1 2m2 2 2
m m1 m2
m= total mass of the system
mX ; p x
2 p
2
2 p
2
2 2 2 2
E V H c . m. V
2m 2 2m 2
The total wavefunction tot appears as the product of a wavefunction c.m.describing the
motion of the center of mass of the system (e- + N) and an electronic wavefunction
characterizing the motion of the e- around the nucleus: tot = c.m.
The total Schrdinger equation is then split in two equations:
2 2
(1) c.m. c.m. Ec.m. c.m. Ec.m. E Etot
H tot = Etot tot 2m
2 2
V E c.m. =tot
(2)
2
NB1: Concerning equation (1), we concluded in chap 2 that the translational energy of an
atom in gas phase is not quantized and can be described in classical physics.
We now focus on Equation (2)
C. Separation of the variables in the electronic wave function
In Equation (2), me because mN>>me Equation (2) describes the electron moving in
the spherical potential of the nucleus. It should be solved to rationalize the presence of lines
in the emission spectrum of the atoms.
2 2
z
In the rest of this chapter, well only consider
V E
2
this electronic Schrdinger equation:
r
2R r 2 2Y
,
C-C 2 2 2R R 2 2
r 2r V r C
2
, Y E r 2 C
2R r r 2Y
2
NB: For the separation of the SE equation C is arbitrary. However, the angular equation is an eigenvalue equation, which has the
eigenvalues: -l(l+1). Hence, for the sake of simplicity in the mathematical development C is chosen to be directly:
2
C l (l 1)
2 2 2 R 2 R
(1) Veff R ER and (2) 2 , Y l (l 1)Y
2 r 2
r r
As seen in Chap 2, the solutions Y(,) of (2) are the spherical harmonics that are
specified by the quantum numbers l and ml.
Lets focus now on the radial wave equation (1) that describes the motion of a particle of
masse in a one-dimensional region where the potential is Veff(r).
The solutions of (1) are the Hydrogenic radial wavefunctions Rn,l(r), which are specified
by 2 quantum numbers n and l. They have the form:
L l (l 1)
Magnetic quantum number: ml= l , l-1, l-2 , , - l In an orbital characterized by ml, the
plane of rotation of the electron has a specific orientation characterized by the z-component of L :
Lz ml
NB: A spin function should be added in the wavefunction. Hence, a spin quantum number, ms
= , should also be specified in order to characterize totally the electron.
A. The energy levels and the ionization energies
hc
En atom
n2
The energies given by the formula are negative, they
correspond to a bound state of the electron.
The zero energy, reference level for the energy, corresponds to
a situation where the electron is not bound to the proton H+ and
has a zero kinetic energy. It is characterized by n =
The positive energies correspond to unbound states of the
electron. The wavefunction describing such an electron is also
solution of the SE, and it is the wavefunction of a free electron.
The energy of the unbound electron are not quantized and form
the continuum states of the atom.
Number of orbitals
with different ml
l (n-1)
n= 1 2 3 4
K L M N
l= 0 1 2 3
s p d f
n
C. s orbitals
For Hydrogen (Z=1), the 1s orbital (n= 1, l= 0, ml= 0) has T<<, V>>
spherical symmetry. The wavefunction decays exponentially
from a maximum value, 1/(a03)1/2, at the nucleus.
r
1
1Hs e a0
a
3 1/ 2
0
r * r d r | |2 d
2
r r Rn2,l | Yn,l |2 r 2 dr sin d d
0 0 0
1 l (l 1) a0
r n 2 1 1
Z
2
n ,l
2 n
For the 1s orbital of H, the maximum of P(r) occurs at r=a0, the Bohr radius.
http://www3.adnc.com/~topquark/quantum/hydrogenmain.html
For the stationary states nlm(x,y,z) of the hydrogen atom, the probability densities
|nlm(x,0,z)|2 are plotted in a plane containing the z axis.
spherical coordinates:
F. p orbitals
x= r sincos; y= r sin sin; z= r cos
5/ 2
Z
Zr
1
p0 R2,1 (r )Y1, 0 ( , )
1/ 2
r cos e 2 a0
r cos f (r ) zf (r ) p z
4(2 ) a0 z
5/ 2
1 Z
Zr
p1 R2,1 (r )Y1, 1 ( , ) 1/ 2 re 2 a0
sin e i
8 a0 r
Different rotations: clockwise, y
1
1/ 2 r sin e i f (r ) counter-clockwise
2
x
p x 1 / 2 p 1 p 1 r sin cos f (r ) x f (r ) These linear combinations are real
1
2 functions. They are also solutions of
the SE for the atom, but have no net
p y 1 / 2 p 1 p 1 r sin sin f (r ) y f (r ) angular momentum vs. the z-axis
i
2
compared to p1.
Nodal plane + -
Demonstration:
if 1 and 2 are solutions of the Schrdinger Equation,
i.e., H1= E 1 and H2= E 2,
then the linear combination = c11+ c22 is also a solution
All the possible transitions, (n1,l1,ml1) [(n2,l2,ml2)+h], are not permissible because the
global angular momentum of the system should be conserved. The photon has an intrinsic spin
angular momentum corresponding to s=1. The change in angular momentum of the electron
must compensate for the angular momentum carried away by the photon.
The probability for a transition to occur, i.e. the intensity of the different lines in the
spectrum, is given by the transition dipole moment fi between an initial state i and a final
state f :
fi e f r i d e f r i
The use of transition dipole moment to evaluate
the intensity of a line is a general method that
can be applied to any atoms or molecules. For a
hydrogenic atom, the introduction of the final
and initial states, characterized by two different
sets of numbers (n, l, ml), leads to the selection
rules indicating which transition is allowed:
l= 1 ml= 0, 1
The light emitted from the sun is absorbed by atoms contained in the
ring of the planet. The absorption spectrum gives us the composition
of the ring: ice, mineral, iron ...
The shift in frequency observed for an absorption line appearing on
both sides of the ring is explained like this: the ring is composed of
particles (from 10 cm to 10 m) rotating around the planet at a high
velocities. The spectral line appears shifted from the earth because of
the speed of rotation of the particles: the Doppler effect modifies the
apparent frequency of the line. From the measured frequency shift,
the speed of the particles can be deduced (20km/s).
3.2 Structure of many-electron atoms
The Schrdinger equation for a three-body system cannot be solved analytically (e.g.: He= 1
nucleus, 2 electrons) approximations required.
n 2 n n
1
H elect = Te Ven Vee +
i Z
i=1 2mi i=1 ri i=1 i>i ri ri '
Li: 3e- + nucleus (Z=3) using the hydrogenic orbitals, the possible electron configuration
are: 1s2 2p1, 1s2 2s1 or 1s3. The last proposal can be directly rejected because electrons are
Fermions and they follow the Pauli exclusion principle:
In the orbital approximation: each electron is associated to a spinorbital that is the product
between a spatial orbital and a spin function:
(xi)= (ri) s(i)
Lets consider a system of 2 electrons that occupy the same spatial orbital (r). The total
wave function of the system is (1,2)= [(1)(2)] S(1,2). Where the spatial part of the total
wavefunction is (1)(2) and it is symmetric: (1)(2)= +(2)(1). Hence, in order to have
the total wavefunction (1,2) antisymmetric, the total spinfunction S(1,2) must be
antisymmetric: S(1,2)= -S(2,1).
What is this antisymmetric spinfunction S(1,2)?
Only the spinfunction S4-(1,2) is antisymmetric and characterized by two different spins.
That proofs the Pauli exclusion principle: 2 electrons in the same spatial orbital must be
paired, i.e. must have different spins. The total wavefunction of a system of 2 electrons in
the same orbital is:
(1,2)= [(1)(2)] 1/21/2 {(1)(2) - (1)(2)}
If the nucleus has a charge Z, the 2s electrons do not feel the potential
created by Z, because the 1s electrons shield this nuclear charge. The
2s electrons feel an effective nuclear charge Zeff:
Zeff= Z -
is the shielding constant. This shielding constant is not the same for
an electron in 2s and 2p, because these orbitals have different radial
distributions (see Figure). A s orbital has a greater penetration
through inner shells than a p orbital of the same shell.
the 2s electrons feel a less shielded nuclear charge, i.e. more
positively charged, than the 2p electrons. The 2s electrons are then
more tightly bound to the nucleus.
Usually the energies of subshells in a many-electron atom lie in
the order: s<p<d<f
Li: 3e- + nucleus (Z=2) 1s2 2p1 is rejected, 1s2 2s1 is the correct
configuration.
32
C: 6e- + nucleus (Z=6) 1s2 2s2 2p2 . The 2 last electrons in the 2p orbitals are the valence
electrons.
But is it 2px12py1 or 2px2?
When adding electrons in the hydrogenic orbitals in order to estimate the electron
configuration of atom (building-up principle), this rule has to be followed:
electrons occupy different orbitals of a given subshell before doubly occupying any one of
them
But is it 2px1 () 2py1() or 2px1 () 2py1()?
In order to have an antisymmetric total wave function (1,2), +(1,2) should be multiplied
by an antisymmetric spinfunction S(1,2) and -(1,2) by a symmetric spinfunction.
When the two electrons are close to each other, the total wavefunction with an
antisymmetric spinfunction, S1(r1,r2=r1) 0 : two electrons with different spin (antiparallel)
have a certain probability to be at the same position.
The electrostatic repulsion is increased: the system in its singlet state is destabilized
For two electrons having a symmetric spinfunction, the total wavefunction is zero:
T2(r1,r2=r1)= T3(r1,r2=r1)= T4(r1,r2=r1)=0 : when 2 electrons in 2 different orbitals have
the same spin (parallel), they are repelled to each other thanks to their spin.
that prevents an additional electrostatic repulsion. The Triplet state (2 spins parallel) is
more stable than the singlet state (2 spins antiparallel): this is the explanation for Hunds
rule.
This quantum effect is called the spin correlation.
The carbon atom has a valence configuration: 2px1 () 2py1() and not 2px1 () 2py1() .
3.2.2 Singlet and triplet states
Triplet State : Symmetric spinfunction
During the excitation, only one electron is excited. When the atom comes back to a lower
energy state, two types of transitions are observed: Between triplet states: T T, Between
singlet states: S S. But not: T S or S T
fi e f r i d e f r i dr S f Si d