uncertainty principle; recall the discussion following Eq. (5.105).

Note that E increases as

J 2 + J, so the spacing between adjacent rotational levels increases as J increases.
Are the rotor energy levels (6.52) degenerate? The energy depends on J only, but the

Atomic Structure
wave function (6.46) depends on J and m, where mU is the z component of the rotor’s
angular momentum. For each value of J, there are 2J + 1 values of m, ranging from -J to
J. Hence the levels are 12J + 12-fold degenerate. The states of a degenerate level have dif-
ferent orientations of the angular-momentum vector of the rotor about a space-fixed axis.
The angles u and f in the wave function (6.46) are relative coordinates of the two
Two-particle Hamiltonian point masses. If we set up a Cartesian coordinate system with the origin at the rotor’s cen-
(x1, y1, system
ter of mass, u and f will be as shown in Fig. 6.3. This coordinate z1) undergoes the
same translational motion as the rotor’s center of mass but does not rotate in space.
The rotational angular momentum 3 J1J + 12U24 1>2 is the angular momentum of the
Two-particle classical energy can be written in termstwo
ofparticles
internalwith respect to an origin at the system’s center of mass C.
The rotational levels of a diatomic molecule can be well approximated
(x2, y2, zby
2) the
coordinates (x, y, z) and center-of-mass (COM) coordinates (X, Y, Z).
two-particle rigid-rotor energies (6.52). It is found (Levine, Molecular Spectroscopy,
Section 4.4) that when a diatomic molecule absorbs or emits radiation, the allowed
pure-rotational transitions are given by the selection rule
!J = {1 (6.53)
In addition, a molecule must have a nonzero dipole moment in order to show a
pure-rotational spectrum. A pure-rotational transition is one where only the rotational

FIGURE 6.3 Coordinate z

system for the two-particle
rigid rotor.
2 2 2
p ̂ ℏ d m2

⇒ Ĥ = =−
2μ 2μ dx 2
y

m1

COM coordinate system

34
e potential-energy function depends only on the relative coordinates of the two
s, and so the conclusions of Sec. 17.13 apply. The total energy Etot of the atom
um of its104 Chapter 5energy
translational | Angular
andMomentum
Atomic Structure
the energy of internal motion of the electron
to the proton. The translational energy levels can be taken as the particle-in-a-
els (17.47). The box is the container holding the gas of H atoms. We now focus
Ln x = -iUc r sin u sin f a cos u 0 - sin u 0 b
nergy EThe SE for
of internal the Hydrogen
motion. Atom(Z
The Hamiltonian = internal
H for the 1)/ Hydrogen-like
motion is given (Z) 0r atom r 0u Spherical
erms in the first pair of brackets in (17.78), and the corresponding Hamiltonian
r ĤThe Schrödinger
for the equation
internal motion is can be solved exactly for the H -r atom in spherical coordinate
0 system
cos u sin f 0 cos f coordinates
0
cos u asin u sin f + + bd
0r r 0u r sin u 0f
U 02
0 0
2 2
Ze 2 2
Ĥ ! # a " 2 " 2b # (18.5)
2m 0x2 0y 0z 4pe0r nLx = iUasin f 0 + cot u cos f 0 b (5.65)
0u 0f
, y, and z are the coordinates of the electron
Also, relative to the nucleus and r !
we find
2 2 1/2
" z ) . The reduced mass m is m ! m1m2/(m1 " m2) [Eq. (17.79)], where
Ln y = -iUa cos f 0 - cot u sin f 0 b (5.66)
m2 are the nuclear and electron masses. For a hydrogen atom, mnucleus ! mproton !
0u 0f
me and
In spherical nLz = -iU 0 (5.67)
1836.15m2e
coordinate mH ! ! 0.999456me (18.6) 0f
1837.15me n x, Ln y, and L
n z and then adding their squares, we can construct
system By squaring each of L
L̂ 2 : Angular
iffers only slightly from me. n 2 = Ln 2x + L
L n 2y + Ln 2z [Eq. (5.43)]. The result is (Prob. 5.17)
momentum operator
e H-atom Schrödinger equation Ĥ c ! Ec is difficult to solve in cartesian 0 2 co-
0 1 0 2
es but is relatively easy to solve in spherical coordinates. TheLn spherical
2 2
= -U a coordi-
2
+ cot u + 2 2
b (5.68)
0u 0u sin u 0f
u, and f of the electron relative to the nucleus are defined in Fig. 18.1. (Math
sually interchange u and f.) The projectionAlthough
of r onthethe
angular-momentum
z axis is r cos u, and operators
its depend on all three Cartesian coordi-
nates, x,between
on on the xy plane is r sin u. The relation y, and z,cartesian
they involve
andonly the twoco-
spherical spherical coordinates u and f.
es is therefore
One-Particle Orbital-Angular-Momentum Eigenfunctions and Eigenvalues 35
x ! r sin u cos f, y ! r sinWe sin f,
u now z!
find the r cos ueigenfunctions
common (18.7)n 2 and Ln z, which we denote by Y. Since these
of L
 Atomic Structure
The Schrödinger Equation for the Hydrogen Atom
Because V(r) depends only on r we can do a separation of variables:

We obtain three separate differential equations, one for each coordinate.

Energy (E) comes out of the radial R(r) equation.

36
 Atomic Structure
The Schrödinger Equation for the Hydrogen Atom
The function R(r) is not quadratically integrable except for values of E that satisfy

where n is an integer such that

The Θ factor depends on l and m and n : principle quantum number (n = 1,2,3..)

The Φ factor is
l : angular momentum quantum number
(l = 0, 1, 2, 3, …, n-1)

m : magnetic quantum number

(+l, l-1, . . , 0, . . , -l+1, -l)

Wave functions of single electrons are called orbitals

37
 Atomic Structure 641
The hydrogenlike-atom energy levels (18.14) depend only on n, but the wave Section 18.3
Thefunctions
Schrödinger
(18.9) dependEquation for numbers
on all three quantum the Hydrogen Atomthere is
n, l, and m. Therefore, The Hydrogen Atom

degeneracy. For example, the n ! 2 H-atom level is fourfold degenerate (spin consid-
Atomic
erations units the wave functions (states) 2s, 2p1, 2p0, and 2p"1 all having the
omitted),
same energy.
The defined quantity a in (18.14) has the dimensions of length. For a hydrogen
atom, substitution of numerical values gives (Prob. 18.13) a ! 0.5295 Å.
If the reduced mass m in the definition of a is replaced by the electron mass me,
we get the Bohr radius a0:
°
a0 ! U 2 14pe0 2>mee2 ! 0.5292 A (18.16)
a0 was the radius of the n ! 1 circle in the Bohr theory.

EXAMPLE 18.1 Ground-state energy of H

Calculate the ground-state hydrogen-atom energy Egs . Also, express Egs in elec-
tronvolts.
Setting n ! 1 and Z ! 1 in (18.14), we get
e2 11.6022 % 10"19 C2 2
Egs ! " !"
14pe0 22a 4p18.854 % 10"12 C2 J"1 m"1 2210.5295 % 10"10 m2
! "2.179 % 10"18 J
The use of the conversion factor (18.3) gives for an H atom
Egs ! "e 2>14pe0 2 12a 2 ! "13.60 eV (18.17)

Exercise 38

Find the wavelength of the longest-wavelength absorption line for a gas of

 Atomic Structure
tum
Hydrogen atom: Quantum numbers
An atomic orbital 0 sin u 0
Ln x = -iUc r sinisuspeci ed by
sin f a cos u three
- quantum b numbers
0r r 0u
The principal quantum number0 (n) cos u sin f 0 cos f 0
-r
• n = 1, 2, 3, …. ∞ cos u a sin u sin f + + bd
0r r 0u r sin u 0f
• The number n corresponds to the orbital energy level or ‘shell’
n 0 0
L = iUasin
• As n increases,
x + cot cos
the orbital becomes larger,
f u f b (5.65)
and the electron spends more time
0u 0f
o, we find farther from the nucleus – size of the orbital
n y = -iUa cos f 0 - cot u sin f 0 b
L (5.66)
The angular momentum 0uquantum number
0f (l)
• l = 0, 1, 2, 3, …. n − 1
n 0
• The orbitals with theL z = -iU (5.67)
same value of n but different values of l are said to form a
0f
‘subshell’ of a given shell
By squaring each of L n x, Ln y, and L
n z and then adding their squares, we can construct
= Ln 2x + L
n 2y + Ln 2z [Eq. (5.43)]. The result is (Prob. 5.17)

n2 02
2 0 1 02
L = -U a 2 + cot u + b (5.68)
0u 0u sin2u 0f2

L = | L | =operators
Although the angular-momentum l(l + 1)ℏ
depend on all three Cartesian coordi-
s, x, y, and z, they involve only the two spherical coordinates u and f. 39
fi
Momentum
Atomic Structure
110 Chapter 5 | Angular Momentum

z
z
Hydrogen atom: Quantum numbers
The magnetic quantum number (ml)
L
• ml = +l , l - 1, …, 0, …-l + 1, -l œl(l 1 1)
L
• œl(l 1 1)
•The degeneracy of a value of l is, gl = 2l +1
•The orientation of a rotating body is quantized FIGURE 5.6 Orientation of L.

FIGURE 5.6 Orientation of L.

z
z z

z
z z
h
œ2h œ2h

h œ2h
2h
œ2h œ2h
l51 m51 l51 m50 l51 m 5 21
œ2h FIGURE 5.7 Orientations of L with respect to the z axis for l = 1.
2h

l51 m51 l51 m50 l51 m 5 21Since we cannot specify L x and L y, the vector L can lie anywhere on the surface of a
FIGURE 5.7 Orientations of L with respect to the z axis for l = 1. cone whose axis is the z axis, whose altitude is mU, and whose slant height is 2l1l + 12 U
(Fig. 5.6). The possible orientations of L with respect to the z axis for the case l = 1 are
shown in Fig. 5.7. For each eigenvalue of Ln 2, there are 2l + 1 different eigenfunctions Y m ,
l 40
n 2
corresponding to the 2l + 1 values of m. We say that the L eigenvalues are 12l + 12-fold
Since we cannot specify L x and L y, the vector L can lie anywhere on the surface of a The term degeneracy is applicable to the eigenvalues of any operator, not just
degenerate.
 Atomic Structure
Shapes of atomic orbitals

41
 Atomic Structure
Shapes of atomic orbitals
The radial wavefunctions Rn,l(r)

Cusp in the hydrogen-atom ground state wave function

42
 Atomic Structure
Volume Element
 Atomic Structure
Shapes of atomic orbitals
The radial wavefunctions Rn,l(r) The radial probability densities Rn,l2(r)r2

l=1 l=2 l=3

44