Hydrogenic Atoms

atom, which co
Visible is therefore
Wavelength, λ/nm

2000
1000
800
600
500

400

300

200

150

120

100
Hˆ = Eˆ k ,electron +
!2
=− ∇
2me
Balmer Lyman
The subscripts
Analysis

spect to the ele

Paschen

Brackett
(a) The sep
Physical intuit
Figure 8A.1 The spectrum of atomic hydrogen. Both the observed ought to separ
spectrum and its resolution into overlapping series are shown. the atom as a w
Note that the Balmer series lies in the visible region. tion of the elec
The Swedish spectroscopist Johannes Rydberg noted (in
The
1890)Swedish
that thespectroscopist
wavenumbers Johannes
of all the Rydberg noted by
lines are given (inthe
1890) that
expression the wavenumbers of all the lines are given by the
expression
 1 1 
ν! = !R! H 1 2 −1 2  Spectral lines of a hydrogen atom (8A.1)
ν! = RH  n21− n2 2  Spectral lines of a hydrogen atom (8A.1)
 n1 n2 

with n1 = 1 (the Lyman series), 2 (the Balmer series), and 3 (the

with n1 = 1 (the Lyman series), 2 (the Balmer series), and 3 (the
Paschen series), and that in each case n2 = n1 + 1, n1 + 2, ….
Paschen series),!and that in each case n2 = n1 + 1, n1 + 2, ….
The constant !R is now called the Rydberg constant
The constant RH is now called the Rydberg constant for the
H for the
hydrogen atom
hydrogen atomand andisisfound
foundempirically
empiricallyto tohave
have the
the value
value
−1
109677
109 677cm
cm−1. .
 Hˆ = Eˆ k ,electron + Eˆ k,nucleus + Vˆ (r )
Hamiltonian for a
2 2 2 (8A.3)
! 2 ! 2 Ze hydrogenic atom
=− ∇e − ∇N −
2mfor
equation e the 2mN
internal 4 πε 0 rof the electron relative to the
motion
nucleus is1
2
The subscripts
2
e and2
N on ∇ indicate differentiation with re-
! 2 Ze
spect−to the
∇ electron
ψ− or
ψ nuclear
= Eψ coordinates.
2µ 4 πε 0 r Schrödinger
equation for a (8A.4)
1 1 1
= + hydrogenic atom
(a) The
µ m separation
e mN of variables
Physical intuition suggests that the full Schrödinger equation
where differentiation is now with respect to the coordinates of
 = + hydrogenic atom
µ me mN

where differentiation is now with respect to the coordinates of

the electron relative to the nucleus. The quantity μ is called the
reduced mass. The reduced mass is very similar to the electron
mass because mN, the mass of the nucleus, is much larger than
F
the mass of an electron, so 1/μ ≈ 1/me and therefore μ ≈ me.
t
In all except the most precise work, the reduced mass can be
m
replaced by me. p
Because the potential energy is centrosymmetric (independ- a
ent of angle), the equation for the wavefunction is expected to c
be separable into radial and angular components, as in a
the mass of an electron, so 1/μ ≈ 1/me and therefore μ ≈ me.
In all except the most precise work, the reduced mass can be
replaced by me.
Because the potential energy is centrosymmetric (independ-
ent of angle), the equation for the wavefunction is expected to
be separable into radial and angular components, as in
ψ (r ,θ ,φ) = R(r)Y(θ ,φ ) (8A.5)

with R(r) the radial wavefunction and Y(θ,ϕ) the angular

wavefunction. The equation does separate, and the two con-
tributions to the wavefunction are solutions of two equations:
2
Λ Y = −l(l +1)Y (8A.6a)
! 2  d 2 R 2 dR 
wavefunction. The equation does separate, and the two con-
tributions to the wavefunction are solutions of two equations: in
in
2
Λ Y = −l(l +1)Y (8A.6a) n
! d R 2 dR 
2
 2 tu
−  2 +  + Veff R = ER (8A.6b) an
2 µ  dr r dr 
(F
where co
to
2 2
Ze l(l +1)! th
Veff (r ) = − + (8A.6c)
4 πε 0 r 2 µr 2
er
co
Equation 8A.6a is the same as the Schrödinger equation for is
 8A Hydrogenic atoms 305

motion of the electron relative to the 0

l≠0

Effective potential energy, Veff

ψ
Schrödinger
equation for a (8A.4)
hydrogenic atom
l=0

w with respect to the coordinates of

nucleus. The quantity μ is called the
d mass is very similar to the electron Radius, r
of the nucleus, is much larger than
Figure 8A.2 The effective potential energy of an electron in
o 1/μ ≈ 1/me and therefore μ ≈ me.
the hydrogen atom. When the electron has zero orbital angular
cise work, the reduced mass can be
momentum, the effective potential energy is the Coulombic
potential energy. When the electron has non-zero orbital
ergy is centrosymmetric (independ- angular momentum, the centrifugal effect gives rise to a positive
for the wavefunction is expected to contribution which is very large close to the nucleus. The l = 0
d angular components, as in and l ≠ 0 wavefunctions are therefore very different near the
nucleus.
(8A.5)

efunction and Y(θ,ϕ) the angular

 So far, only th
l=0
been given. It is
fundamental co

Wavefunction, ψ
They are most
quantity ρ (rho)
1
2 2 Zr
ρ= a
3 na

The Bohr radiu

Radius, r because the sam
Figure 8A.3 Close to the nucleus, orbitals with l = 1 are of the hydrogen
proportional to r, orbitals with l = 2 are proportional to r 2, lowest energy.
and orbitals with l = 3 are proportional to r 3. Electrons are there is so littl
progressively excluded from the neighbourhood of the nucleus to use a 0 in the
as l increases. An orbital with l = 0 has a finite, non-zero value at = 1.0005a 0). In
the nucleus. ous quantum n
 Dominant Dominant
Bridges
close to theclose to the theBridges
two the two DominantDominant
far far
ends of theends
nucleus nucleus function
of the function from the nucleus
from the nucleus
% !% ##" !##
##$ "## !####
$ !#### "#### "####$ $
l
R(r ) = r R(r×)(polynomial
l
in r ) × (decaying
= r × (polynomial exponential
in r ) × (decaying in r ) in
exponential
(8A.7) (

Thewavefunction
The radial radial wavefunction therefore
therefore has the has
formthe form

−r l −r
L((rr ))e= r L(r )e
R(r ) = r R
l

with various
with various constants
constants andL(r)
and where where L(r)bridging
is the is the bridging
polyno-pol
exponentially to zero in the same way (exponential functions
−x n
e always dominate simple powers, x ).
The detailed solution also shows that, for the wavefunction to
be acceptable, the value of n that appears in the polynomial can
take only positive integral values, and specifically n = 1, 2, ….
This number also determines the allowed energies through the
expression:

µe 4
Z 2
En = − 2 2 2 × 2 Bound-state energies (8A.8)
32π ε 0 ! n
 lowest
been energy.
given. It is nowIntimepractice, how they m
to showbecause e << m
depend (so m e/μ ≈
onNvarious
lowest
there is energy.
fundamental littleIndifference
soconstants practice,
and thebecause
between
atomic m e a<<and
number mof
N (so
athe e /μ it
matom.
that ≈ 1)
is s
0
there is so little difference between a and a that it is safe1
0 in the definition of ρ for all atoms (even 1for H
They are amost
to use simply written in terms of the dimensionless 0
a 0 in the
to useρ (rho),
us quantity wheredefinition of ρ for all atoms (even for H, a
= 1.0005a 0). In terms of these quantities and with the v
at = 1.0005a 0). In terms of these quantities and with the vari-
ous quantum numbers displayed, the radial wavefuncti
ous2 Zr
quantum m numbers displayed,
4 πε ! 2 the radial wavefunctions
for =ananelectron
ρfor a = with
e
a quantum
a = 0
numbers n and l are
(8A.9)
n and l are the (real)the (r
na electron µwith quantummnumbers
0 0
e 2
functions
functions
e

The Bohr radius, a 0, has the value 52.9 pm; it is so called

It It because the same lquantity
es. −−ρappeared
ρ/2/2 in Bohr’s early model
n R R ( r ()r=) =N N ρ ρ l
LL ( ρ
ρ )e
)e
al in of the hydrogen atom as the radius of the electron orbit of
n ,l n ,l n n
,l ,l n
n ,
, l Radial
Radial wavefunctions
wavefunctions (8A
(8A.10)

lowest energy. In practice, because m e << mN (so m e/μ ≈ 1)

where
is soLn,l
where
there (ρ(ρ)) difference
Llittle
n,l an associated
isis an betweenLaguerre
associated a and a polynomial.
Laguerre 0
polynomial.
that it is TheseTh
safe
 Table 8A.1 Hydrogenic radial wavefunctions
ridging polyno- n l Rn,l(r)
ial is a constant 3/2
 Z
s the dominant 1 0 2 
 a
e − ρ /2
−1
, where n is an
3/2
wavefunctions 1  Z
2 0 (2 − ρ )e − ρ /2
−1 −r
e and decay 81/2  a 

ential functions 1  Z
3/2

2 1 ρe − ρ /2
241/2  a 
wavefunction to 1  Z
3/2

3 0 1/2   (6 − 6 ρ + ρ 2 )e − ρ /2
polynomial can 243  a 
ally n = 1, 2, …. 1  Z
3/2

gies through the 3 1 (4 − ρ )ρe − ρ /2

4861/2  a 
3/2
1  Z
3 2 ρ 2e − ρ /2
24301/2  a 

energies (8A.8) ρ = (2Z/na)r with a = 4πε0 ħ2/μe2. For an infinitely heavy nucleus (or one that may be
assumed to be), μ = me and a = a 0, the Bohr radius.
(The r2 comes from the volume element in spherical coordi- the radial
nates; see The chemist’s toolkit 21 in Topic 7F.) Specifically, the eqn 8A.5, i
components of eqn 8A.10 can be interpreted as follows:
ψ n ,l ,m (r
l
• The exponential factor ensures that the wavefunc-
tion approaches zero far from the nucleus. Brief illus
• The factor ρl ensures that (provided l > 0) the wave-

Physical interpretation
function vanishes at the nucleus. The zero at r = 0 is To calcula
tron with
not a radial node because the radial wavefunction
does not pass through zero at that point (because r
cannot be negative). ψ 1,0,0 (0
• The associated Laguerre polynomial is a function
that in general oscillates from positive to negative The proba
values and accounts for the presence of radial
nodes. ψ 1,0,0
2
(0
 ψ n ,l ,m (r ,θ ,φ ) = Rn ,l (r )Yl ,m (θ ,φ )
l l
(8A.12)
func-
Brief illustration 8A.1
wave- Physical interpretation
= 0 is To calculate the probability density at the nucleus for an elec-
tron with n = 1, l = 0, and ml = 0, evaluate ψ at r = 0:
nction
ause r 3/2 1/2
Z  1 
ψ 1,0,0 (0,θ ,φ ) = R1,0 (0)Y0,0 (θ ,φ ) = 2    4π 
 a0 
nction
gative The probability density is therefore
radial Z 3
ψ 1,0,0
2
(0,θ ,φ ) = 3
πa0

ven in Table which evaluates to 2.15 × 10−6 pm−3 when Z = 1.

the form of
 2 0.15
0.8

1.5 0.6
0.1

R(r)/(Z/a0)3/2
R(r)/(Z/a0)3/2

R(r)/(Z/a0)3/2
0.4
1 n = 1, l = 0 n = 2, l = 0 n = 2, l = 1

0.2
0.05
0.5
0

0 –0.2 0
0 1 2 3 0 5 10 15 0 5 10 15
Zr/a0 Zr/a0 Zr/a0

0.4 0.1 0.05

0.3 0.04

0.05
R(r)/(Z/a0)3/2

0.2

R(r)/(Z/a0)3/2
R(r)/(Z/a0)3/2
0.03
n = 3, l = 0 n = 3, l = 1 n = 3, l = 2

0.1 0.02
0

0 0.01

–0.1 –0.05 0
0 7.5 15 22.5 0 7.5 15 22.5
Zr/a0 Zr/a0 0 7.5 15 22.5
Zr/a0

Figure 8A.4 The radial wavefunctions of the first few states of hydrogenic atoms of atomic number Z. Note that the orbitals with l = 0
have a non-zero and finite value at the nucleus. The horizontal scales are different in each case: as the principal quantum number increases,
so too does the size of the orbital.
 l = 0, and ml = 0. Figure 8
Continuum
Atomic orbitals and their
8A.2 H +e
+
are relat
–

energies (a) The specification of orbitals 0

~
–hcRH/9
proton.
~
Each of the three quantum for numbers specifies a different at-
–hcRH/4

Energy, E
An atomic orbital is a one-electron wavefunction an elec-
tron in an atom,tribute of the orbital:
and for hydrogenic atoms has the form speci- is consi
fied in eqn 8A.12. Each hydrogenic atomic orbital is defined by Classically
8A.1, w
• The principal quantum
three quantum numbers, designated n, l, and m l . An number, n, specifies the energy energies
electron allowed
described by one of the wavefunctions in eqn 8A.12 is said to
of the orbital (through eqn 8A.8); it takes the values ~ n =
‘occupy’ that orbital. For example, an electron described by –hcRH R! N =
the wavefunction ψ1,0,01, is 2,
said3,to….
‘occupy’ the orbital with n = 1,
l = 0, and ml = 0.
• The orbital angular momentum quantum number, l, Figure 8A.5 The energy levels of a hydrogen atom
where μ
are relative to an infinitely separated, stationary e
specifies the magnitude of the angular momentum of the constan
(a) The specification of orbitals 1/2
proton.
electron as {l(l + 1)} ћ, with l = 0, 1, 2, …, n − 1. specifie
Each of the three quantum numbers specifies a different at-
• The magnetic quantum number, ismconsistent
tribute of the orbital: l , specifies
withthe z-com- result
the spectroscopic replace
sum
ponentnumber,
of then,angular
specifies momentum as m lћ, with ml = 0, ±1, theatom
valu
8A.1, with the Rydberg constant for the id
• The principal quantum the energy
±2, …,
of the orbital (through eqn±l.
8A.8); it takes the values n = µ m e 4
for R!
R! N = × R! ∞ R! ∞ = 2e 3 H
Rydberg co
1, 2, 3, …. m
 hcZ R! N 2
! µe 4
En = − RN = 2 3 Bound-state energies (8A.13)
n 2
8ε 0 ch

Continuum
d their H + + e– n
0 ∞
~
–hcRH/9 3
~
–hcRH/4 2

Energy, E
wavefunction for an elec-
toms has the form speci-
omic orbital is defined by Classically
n, l, and ml. An electron allowed
energies
ns in eqn 8A.12 is said to
~
n electron described by –hcRH 1
py’ the orbital with n = 1,
Figure 8A.5 The energy levels of a hydrogen atom. The values
are relative to an infinitely separated, stationary electron and a
tals proton.
-com- replaced by H and μ takes the appropriate value. Insertion of
0, ±1, the values of the fundamental constants into the expression
is consistent
! with the spectroscopic result summarized by eqn
for RH gives almost exact agreement with the experimental
8A.1,value
withforthehydrogen.
RydbergTheconstant for the atom identified as
only discrepancies arise from the ne-
ntrols glectµ of relativistic corrections
m e 4 (in simple terms, the increase
!
ols the RNof = mass !
× Rwith !
R∞ =which
speed),
e
2 3 the non-relativistic Schrödinger
Rydberg constant (8A.14)
me ∞
8ε 0 h c
equation ignores.
where μ is the reduced mass of the atom and R! ∞ is the Rydberg
constant;
Briefthe constant
illustration R! N is the value that constant takes for a
8A.2
specified atom N (not nitrogen!), such as hydrogen, when N is
n Fig. The value of R! ∞ is given inside the front cover and is
replaced by H and −1 μ takes the appropriate value. Insertion of
ouring 109 737 cm . The reduced mass of a hydrogen atom with mp =
the values of the fundamental
−27 constants −31into the expression
mes as ! 1.672 62 × 10 kg and me = 9.109 38 × 10 kg is
for
nergy)
RH gives almost exact agreement with the experimental
value
by eqn for hydrogen.
m m
e p
The only
(9.10938 × discrepancies
10 −31
kg) × (1.67262 arise
× 10 −27from the ne-
kg)
 in energy)
ven by eqn memp (9.10938 ×10−31 kg) × (1.67262 ×10−27 kg)
µ= =
f the atom, me + mp (9.10938 ×10−31 kg) + (1.67262 ×10−27 kg)
of the infi- = 9.10442 ×10−31 kg
which cor-
tions of the It then follows that
e solutions
−31
he states to ! 9.10442 × 10 kg −1 −1
RH = × 109737cm = 109677cm
m the atom 9.10938 ×10−31 kg
of the un-
continuum and that the ground state of the electron (n = 1) lies at

E1 = − hcR! H = −(6.62608 ×10−34 Js) × (2.997945 ×1010 cm s −1 )

× (109677cm −1 ) = −2.17870 ×10−18 J

es (8A.13) or 2.178 70 aJ. This energy corresponds to −13.598 eV.

hydrogen is 13.60 eV; its ionization potential is 13.60 V.

Example 8A.1 Measuring an ionization energy

spectroscopically
The emission spectrum of atomic hydrogen shows lines at
−1
82 259, 97 492, 102 824, 105 292, 106 632, and 107 440 cm ,
which correspond to transitions to the same lower state from
successive upper states with n = 2, 3, …. Determine the ioniza-
tion energy of the lower state.
Collect your thoughts The spectroscopic determination of
tion energy of the lower state.
Collect your thoughts The spectroscopic determination of
(
ionization energies depends on the identification of the ‘series
limit’, the wavenumber at which the series terminates and A
becomes a continuum. If the upper state lies at an energy s
! 2
−hcRH /n , then the wavenumber of the photon emitted when g
the atom makes a transition to the lower state, with energy t
Elower, is s
I = −Elower

R! H Elower R! H I
ν! = − 2 − =− 2 +
n hc n hc
2 Th
 ν! = − H
− lower
=− H
+
2
n hc n2
hc

A plot of the wavenumbers against 1/n2 should give a straight Thus, a

line of slope −R! H and intercept I/hc. Use software to calculate the atom
a least-squares fit of the data in order to obtain a result that The o
reflects the precision of the data. are said
also gen
The solution The wavenumbers are plotted against 1/n2 in
Fig. 8A.6. From the (least-squares) intercept, it follows that
I/hc = 109 679 cm−1, so the ionization energy is l=

I = hc × (109 679cm −1 )
−34 10 −1 −1 All orb
= (6.626 08 ×10 Js) × (2.997 945 ×10 cms ) × (109 679cm )
kinds o
= 2.1787 ×10−18 J letters r
 110

nimum en-
ound state, 100

ν/(103 cm–1)
gas phase.
with n = 1,
en the elec-
~

90
n = ∞ (see

(8A.15)
80
0 0.1 0.2
esponds to 1/n2

Figure 8A.6 The plot of the data in Example 8A.1 used to

ometimes determine the ionization energy of an atom (in this case, of H).
ctroscopic determination of
(d) Shells and subshells
he identification of the ‘series
ch the series terminates and All the orbitals of a given value of n are said to form a single
upper state lies at an energy shell of the atom. In a hydrogenic atom (and only in a hydro-
of the photon emitted when genic atom), all orbitals of given n, and therefore belonging to
the lower state, with energy the same shell, have the same energy. It is common to refer to
successive shells by letters:

n= 1 2 3 4…
Specification of shells
K L M N…

nst 1/n2 should give a straight Thus, all the orbitals of the shell with n = 2 form the L shell of
/hc. Use software to calculate the atom, and so on.
order to obtain a result that The orbitals with the same value of n but different values of l
. are said to form a subshell of a given shell. These subshells are
also generally referred to by letters:
s are plotted against 1/n2 in
res) intercept, it follows that
ation energy is l= 0 1 2 3 4 5 6…
Specification of subshells
s p d f g h i…
 Figure 8A.7 The energy levels of a hydrogenic atom showing the
subshells and (in square brackets) the numbers of orbitals in each
subshell. All orbitals of a given shell have the same energy.
310 8 Atomic structure and spectra

n s p d f
∞ (e) s Orbitals
4 4s [1] Subshells
4p [3] 4d [5] 4f [7]
3 The orbital occupied in the ground state is the one with n = 1
3s[1] 3p [3] 3d [5] s p d
2 (and therefore with l = 0 and ml = 0, the only possible values
2s [1] 2p[3] of these quantum numbers when n = 1). From Table 8A.1
M shell, n =and
3
Energy

1/2
with Y0,0 = (1/4 π ) (Table 7F.1) it follows that (for Z = 1):
Orbitals
1 L shell, n(8A.16)
=2
ψ= 3 1/2 e
− r /a
0

(πa0 )

1s [1] This wavefunction is independent of angle andKhas then same

Shells
shell, =1
1
value at all points of constant radius; that is, the 1s orbital
Figure 8A.7 The energy levels of a hydrogenic atom showing the (the s orbital with n = 1, and in general ns) is ‘spherically
subshells and (in square brackets) the numbers of orbitals in each Figure 8A.8 The organization of orbitals (white squares) into
symmetrical’. The wavefunction decays exponentially from a
subshell. All orbitals of a given shell have the same energy. subshells (characterized by l) and shells (characterized by n).
maximum value of 1/(πa03 )1/2 at the nucleus (at r = 0). It follows
that the probability density of the electron is greatest at the
nucleus itself.
The general
guages form
i and ofnot
j are thedistinguished).
ground-state wavefunction
Figure 8A.7 iscan be
a version
understood by considering
of Fig. 8A.5 which shows the contributions
the subshells of the
explicitly. poten-l can
Because
Subshells tial and kinetic
range from 0energies
to n − 1, to the total
giving energy
n values ofitthe
in all, atom.that
follows Thethere
(e) s Orbitals
The orbital occupied in the ground state is the one with n = 1
(and therefore with l = 0 and ml = 0, the only possible values
of these quantum numbers when n = 1). From Table 8A.1 and
1/2
with Y0,0 = (1/4 π ) (Table 7F.1) it follows that (for Z = 1):

1
ψ= 3 1/2 e
− r /a
0 (8A.16)
(πa0 )

This wavefunction is independent of angle and has the same

ure 8A.7 is a version Low potential energy
licitly. Because l can but
high kinetic energy
, it follows that there

Wavefunction, ψ
quantum number n.
a
summarized in Fig. Lowest total energy
f principal quantum c Low kinetic energy
each energy level is but
high potential energy
b

Radius, r
with l = 0, and that Figure 8A.9 The balance of kinetic and potential energies
l = 0 (the only value that accounts for the structure of the ground state of hydrogenic
our orbitals, one in atoms. (a) The sharply curved but localized orbital has high
ree in the l = 1 sub- mean kinetic energy, but low mean potential energy; (b) the
re are nine orbitals mean kinetic energy is low, but the potential energy is not very
with l = 2). favourable; (c) the compromise of moderate kinetic energy and
moderately favourable potential energy.
 z You need to ev
z
given in Table
toolkit 21 in To
(Table 7F.1) ar
π 2π
∫ ∫
θ =0 φ =0
Yl ,ml

x y The relevant in

x y The solution W
RY, the integr
ables, which is
(a) 1s (b) 2s
∞ π
〈r 〉 = ∫ ∫ ∫
0 0
Figure 8A.10 Representations of cross-sections through the (a)
1s and (b) 2s hydrogenic atomic orbitals in terms of their electron For a 1s orbita
probability densities (as represented by the density of shading).
Z
high proportion (typically about 90 per cent) of the electron
probability. For the 1s orbital, the boundary surface is a sphere
centred on the nucleus (Fig. 8A.11). (f)

Example 8A.2 Th
Calculating the mean radius of an orbital
ab
Calculate the mean radius of a hydrogenic 1s orbital. To
an
Collect your thoughts The mean radius is the expectation value
2
mu
〈r 〉 = ∫ψ * rψ dτ = ∫ r ψ dτ ap
 You need to evaluate the integral by using the wavefunctions
given in Table 8A.1 and dτ = r2dr sin θ dθ dϕ (The chemist’s
toolkit 21 in Topic 7F). The angular parts of the wavefunction
(Table 7F.1) are normalized in the sense that
π 2π 2
∫ ∫
θ =0 φ =0
Yl ,ml sinθ dθ dφ = 1

The relevant integral over r is given in the Resource section.

y The solution With the wavefunction written in the form ψ =
RY, the integration (with the integral over the angular vari-
ables, which is equal to 1, in blue) is
∞ π 2π 2 ∞
〈r 〉 = ∫ ∫ ∫ rR Yl ,ml r d r sinθ dθ dφ = ∫ r 3 Rn2,l d r
2
n ,l
2
0 0 0 0
e (a)
ectron For a 1s orbital
ing). 3/2
Z
R1,0 = 2   e − Zr /a0
 a0 

Hence

Integral E.3
!#
3
#"## $
4 Z ∞ 3 −2 Zr /a0 4Z 3 3! 3a0
〈r 〉 = 3 ∫ r e dr = 3 × 4 =
a0 0 a0 (2 Z / a0 ) 2 Z

Self-test 8A.2 Evaluate the mean radius of a 3s orbital by

integration.
Answer: 27a 0/2Z
Exercise
• Calculate the most probable radius at which an electron will be found
when it occupies a 1s orbital of a hydrogenic atom at atomic number
Z, and tabulated the values for the one-electron species from H to
Ne9+ . [ao = 52.9 pm]