PY3P05

Lectures 3-4: One-electron atoms Lectures 3-4: One-electron atoms

o Schrdinger equation for one-electron atom.
o
Solving the Schrdinger equation.
o
Wavefunctions and eigenvalues.
o Atomic orbitals.
o
See Chapter 7 of Eisberg & esnic!.

"x# y# z# t$
PY3P05
The Schrdinger equation The Schrdinger equation
o %ne-electron atom is simplest bound s&stem in nature.
o
Consists of positive and negative particles moving in '( Coulomb potential)
o
Z =* for atomic h&drogen# Z =+ for ioni,ed helium# etc.
o
Electron in orbit about proton treated using reduced mass)
o -otal energ& of s&stem is therefore#

mM
m+ M

V V"x# y# z$
Ze
+
.
/
x
+
+ y
+
+ z
+

KE + PE E
*
+
" p
x
+
+ p
y
+
+ p
z
+
$ +V"x# y# z$ E
PY3P05
The Schrdinger equation The Schrdinger equation
o 0sing the Equivalence Principle# the classical dynamical quantities can be replaced 1ith their
associated differential operators)
o Substituting# 1e obtain the operator equation:
o Assuming electron can be described b& a 1avefunction of form#
can 1rite
or
1here# is the Laplacian operator.

p
x
ih

x
# p
y
ih

y
# p
z
ih

z
E ih

h
+
+

+
x
+
+

+
y
+
+

+
z
+

_
,

+V"x# y# z$ ih

"x# y# z# t$

h
+
+

+
"x#y#z#t$
x
+
+

+
"x#y#z#t$
y
+
+

+
"x#y#z#t$
z
+

_
,

+V"x#y#z$"x#y#z#t$ ih
"x#y#z#t$
t

h
+
+

+
+V ih

+
x
+
+

+
y
+
+

+
z
+
PY3P05
The Schrdinger equation The Schrdinger equation
o Since Vx!y!z" does not depend on time# is a solution to the
Schrdinger equation and the ei#enfunction is a solution of the time$independent
%c&r'din#er equation)
o As V = Vr"# convenient to use sp&erical polar coordinates.
1here
o Can no1 use separation of varia(les to split the partial
differential equation into a set of ordinar& differential equations.

"x# y# z# t$ "x# y# z$e

iEt 2 h

h
+
+

+
"x# y# z$ +V"x# y# z$ E"x# y# z$

h
+
+

+
"r##$ + V"r$"r##$ E"r##$

*
r
+

r
"r
+

r
$+
*
r
+
sin

"sin

$+
*
r
+
sin
+

+
)"

"x# y# z$
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Separation o the Schrdinger equation Separation o the Schrdinger equation
o Assuming the eigenfunction is separable)
o 0sing the 3aplacian# and substituting *" and )")
o Carr&ing out the differentiations#
o 4ote total derivatives no1 used# as + is a function of r alone# etc.
o 4o1 multipl& through b& and ta!ing transpose#
*"

"r##$ +"r$"$"$

h
+
+
*
r
+

r
r
+
+
r

_
,
+
*
r
+
sin

sin
+

_
,
+
*
r
+
sin
+

+
+

1
]
1
+V"r$+ E+

h
+
+

r
+

r
r
+
d+
dr

_
,
+
+
r
+
sin

sin
d
d

_
,
+
+
r
+
sin
+

d
+

d
+

1
]
1
+V"r$+ E+

+r
+
sin
+
2 +h
+

d
+

d
+

sin
+

+
d
dr
r
+
d+
dr

_
,

sin

d
d
sin
d
d

_
,

+
h
+
r
+
sin
+
5E V"r$6
,"
PY3P05
Separation o the Schrdinger equation Separation o the Schrdinger equation
o As the 37S of Eqn ' does nor depend on r or and 7S does not depend on their
common value cannot depend on an& of these variables.
o Setting the 37S of Eqn ' to a constant)
and 7S becomes
o 8oth sides must equal a constant# 1hich 1e choose as ll-)":
o We have no1 separated the time-independent Schrdinger equation into three
ordinary differential equations# 1hich each onl& depend on one of ."! /" and +0".
.

d
+

d
+
m
l
+
>
d
+

d
+
m
l
+

."

*
+
d
dr
r
+
d+
dr

_
,

*
sin
d
d
sin
d
d

_
,

+
h
+
r
+
5E V"r$6
m
l
+
sin
+

>
*
+
d
dr
r
+
d+
dr

_
,
+
+r
+
h
+
5E V"r$6
m
l
+
sin
+

*
sin
d
d
sin
d
d

_
,

*
sin
d
d
sin
d
d

_
,
+
m
l
+

sin
+

l"l +*$
*
r
+
d
dr
r
+
d+
dr

_
,
+
+r
+
h
+
5E V"r$6+ l"l +*$
+
r
+
/"
0"
PY3P05
Summar! o separation o Schrdinger equation Summar! o separation o Schrdinger equation
o E9press electron 1avefunction as product of three functions)
o As V 1 Vt"! attempt to solve time$independent %c&rodin#er equation.
o
Separate into three ordinar& differential equations for and .
o Eqn. . for "$ onl& has acceptable solutions for certain value of m
l
.
o 0sing these values for m
l
in Eqn. :# "$ onl& has acceptable values for certain
values of l.
o With these values for l in Eqn. ;# +r" onl& has acceptable solutions for certain
values of E
n
.
o Schrdinger equation produces t&ree quantum num(ers2

"r##$ +"r$"$"$

+"r$#"$

"$
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"#imuthal solutions $ "#imuthal solutions $

$ $

%% %%
o A particular solution of ." is
o As the einegfunctions must be single valued# i.e.# (0)(2) <=

and using Euler>s formula#
o -his is onl& satisfied if m
l
< /# ?*# ?+# ...
o -herefore# acceptable solutions to ." onl& e9ist 1hen m
l
can onl& have certain integer
values# i.e. it is a quantum num(er.
o m
l
is called the ma#netic quantum num(er in spectroscop&.
o Called magnetic quantum number because pla&s role 1hen atom interacts 1ith magnetic
fields.

"$ e
im
l

e
im
l
/
e
im
l
+

* cosm
l
+ + i sinm
l
+
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Polar solutions $ Polar solutions $

$ $

%% %%
o @a!ing change of variables "z < rcos)# Eqn. : transformed into an associated Le#endre
equation)
o Solutions to Eqn. 7 are of form
1here are associated Le#endre polynomial functions.
remains finite 1hen < /# *# +# '# ...
m
l
< -l# -lA*# ..# /# ..# l-*# l
o Can 1rite the associated 3egendre functions using quantum number subscripts)

//
< *

*/
< cos
*?*
< "*-cos
+
$
*2+

+/
< *-'cos
+

+?*
< "*-cos
+
$
*2+
cos

+?+
< *-cos
+

d
dz
")$
+
z
$
d
dz

1
]
1
- l"l -*$ $
+
l m
*$
+
z

1
]
1
=/
3"

lm
l
"$ sin
B m
l
B
4
lB m
l
B
"cos$

4
lB m
l
B
"cos$
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Spherical harmonic solutions Spherical harmonic solutions
i.e.# product of trigonometric and pol&nomial
functions.
o Cirst fe1 spherical harmonics are)
D
/
/
< *
D
*
/
< cos D
*
?*
< "*-cos
+
$
*2+
e
?i
D

+
/
< *-'cos
+
D
+
?*
< "*-cos
+
$
*2+
cos e
?i

l m
l D
" !$ =
l
l m

" $
l m

"$
QuickTime and a
TIFF (Uncompressed) decompressor
are needed to see this picture.
o Customar& to multipl& "$ and "$ to form so called sp&erical &armonic functions
1hich can be 1ritten as)
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&adial solutions $&$ r %% &adial solutions $&$ r %%
o What is the ground state of h&drogen Z=)"5 Assuming that the ground state has n = )! l = 6
Eqn. ; can be 1ritten
o -a!ing the derivative
3"
o -r& solution # 1here 7 and a
6
are constants. Sub into Eqn. 7)
o -o satisf& this Eqn. for an& r# both e9pressions in brac!ets must equal ,ero. Setting the second
e9pression to ,ero <=
o Setting first term to ,ero <=

*
r
+
d
dr
r
+
d+
dr

_
,
+
+
h
+
E +
e
+
.
/
r

1
]
1
+ /

a
/

.
/
h
+
e
+

d
+
+
dr
+
+
+
r
d+
dr
+
+
h
+
E +
e
+
.
/
r

1
]
1
+ /

+ 7e
r 2 a
/

E
h
+
+a
/
+
*'.; eE
Same as 8ohr>s results
PY3P05
&adial solutions $&$ r %% &adial solutions $&$ r %%
o adial 1ave equation
has man& solutions# one for each positive integer of n.
o Solutions are of the form "see Appendi9 4 of Eisberg & esnic!$)
1here a
6
is the 8o&r radius. 8ound-state solutions are onl& acceptable if
1here n is the principal quantum num(er! defined b& n = l -)! l -*! l -,! 9
o E
n
onl& depends on n) all l states for a given n are de#enerate "i.e. have the same energ&$.

d
+
+
dr
+
+
+
r
d+
dr
+
+
h
+
E +
e
+
.
/
r

1
]
1
+ /

+
nl
"r$ e
Zr 2 na
/
Zr
a
/

_
,

l
:
nl
Zr
a
/

_
,

E
n

Z
+
e
.
".
/
$
+
+h
+
n
+
*'.;
Z
+
n
+
eE
PY3P05
&adial solutions $&$ r %% &adial solutions $&$ r %%
o :
nl
Zr;a
6
" are called associated La#uerre polynomials! 1hich depend on n and l.
o Several resultant radial 1avefunctions "+
nl
r "$ for the h&drogen atom are given belo1
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&adial solutions $&$ r %% &adial solutions $&$ r %%
o -he radial probabilit& function P
nl
r "# is the probabilit& that the electron is found bet1een r
and r - dr)
o Some representative radial probabilit& functions are given at right)
o Some points to note)
o -he r
*
factor ma!es the radial probabilit& densit&
vanish at the origin# even for l = 6 states.
o Cor each state "given n and l$# there are n $ l $ )
nodes in the distribution.
o -he distribution for states 1ith l = 6# have n ma9ima#
1hich increase in amplitude 1ith distance from origin.

P
nl
"r$dr +
nl
"r$<
lm
l
"#$
+
r
+
dV

.r
+
+
nl
+
r
+
dr
PY3P05
&adial solutions $&$ r %% &adial solutions $&$ r %%
o adial probabilit& distributions for an electron in several of the lo1 energ& or(itals of
h&drogen.
o -he abscissa is the radius
in units of a
6
.
QuickTime and a
TIFF (LZW) decompressor
are needed to see this picture.
s orbitals
p orbitals
d orbitals
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'!drogen eigenunctions '!drogen eigenunctions
o Ei#enfunctions for the state described b& the quantum numbers n! l! m
l
" are therefore of form)
and depend on quantum numbers)
n = )! *! ,! 9
l = 6! )! *! 9! n$)
m
l
= $l! $l-)! 9! 6! 9! l$)! l
o Energ& of state on dependent on n:
o 0suall& more than one state has same
energ&# i.e.# are degenerate.

nlm
l
"r##$ +
nl
"r$
lm
l
"$
m
l
"$

E
n

*'.;Z
+
n
+
PY3P05
(orn interpretation o the )a*eunction (orn interpretation o the )a*eunction
o Frinciple of G@) t&e =avefunction contains all t&e dynamical information a(out t&e system it
descri(es.
o 8orn interpretation of the 1avefunction) -he probabilit& "Px!t"" of finding a particle at a
position bet1een x and x-dx is proportional to Bx!t">
*
dx)
Px!t" <
?
x!t" x!t" < Bx!t">
*
o Px!t" is the pro(a(ility density.
o Hmmediatel& implies that si#n of 1avefunction has no
direct ph&sical significance.
x!t" Px!t"
PY3P05
(orn interpretation o the )a*eunction (orn interpretation o the )a*eunction
o Hn 7-atom# ground state orbital has the same sign ever&1here <= sign of orbital must be all
positive or all negative.
o %ther orbitals var& in sign. Where orbital changes sign# < / "called a node" =@ probabilit&
of finding electron is ,ero.
o Consider first e9cited state of h&drogen) sign of
1avefunction is insignificant "P =
+
< "-$
+
$.
PY3P05
(orn interpretation o the )a*eunction (orn interpretation o the )a*eunction
o 4e9t e9cited state of 7-atom is as&mmetric about origin. Wavefunction has opposite sign on
opposite sides of nucleus.
o -he square of the 1avefunction is identical on
opposite sides# representing equal distribution
of electron densit& on both side of nucleus.
PY3P05
"tomic or+itals "tomic or+itals
o Guantum mechanical equivalent of or(its in 8ohr model.
QuickTime and a
TIFF (Uncompressed) decompressor
are needed to see this picture.
QuickTime and a
TIFF (Uncompressed) decompressor
are needed to see this picture.
PY3P05
s or+itals s or+itals
o 4amed from IsharpJ spectroscopic lines.
o l < /# m
l
= /

n!6!m
= +
n!6
r " <
6!m
! "
o Angular solution)
o Ealue of <
6!6
is constant over sphere.
o Cor n < /# l = 6! m
l
= / =@ )s orbital
o -he probabilit& densit& is
-0.2
0
0.2
-0.2
0
0.2
-0.2
0
0.2
-0.2
0
0.2

<
/#/

*
.

*#/#/

Z
a
/

_
,

'2 +
e
Zr 2 a
/

P
nlm
l
"r##$
nlm
l
"r##$
K

nlm
l
"r##$

> P
*#/#/
"r##$
*

Z
a
/

_
,

'
e
+Zr 2 a
/
PY3P05
p or+itals p or+itals
o 4amed from IprincipalJ spectroscopic lines.
o l < *# m
l
= -*# /# A* "n must therefore be =*$

n!)!m
= +
n)
r " <
)!m
! "
o Angular solution)
o A node passes through the nucleus and separates the t1o lobes
of each orbital.
o (ar!2light areas denote opposite sign of the 1avefunction.
o -hree p$orbitals denoted p
x
! p
y !
p
z

+#*#/
"r##$ +
+#*
"r$
'
.

_
,

*2 +
cos +p
z

<
*#/

'
.
cos
PY3P05
d or+itals d or+itals
o 4amed from IdiffuseJ spectroscopic lines.
o l < +# m
l
= $*! -*# /# A*# A+ "n must therefore be
=+$

n!*!m
= +
n)
r " <
*!m
! "
o
Angular solution)
o
-here are five d$orbitals# denoted
o m < / is z
*
. -1o orbitals of m < -* and A* are xz
and yz. -1o orbitals 1ith m < -+ and A+ are
designated xy and x
*
$y
*
.
-1
-0.5
0
0.5
1
-1
-0.5
0
0.5
1
-2
-1
0
1
2
-1
-0.5
0
0.5
1
-2
-1
0
1
2

<
+#/

:
.
*
+
"'cos
+
*$

d
z
+
# d
xz
# d
yz
# d
xy
# d
x
+
y
+
PY3P05
,uantum num+ers and spectroscopic notation ,uantum num+ers and spectroscopic notation
o Principal quantum num(er:
o n = ) K s&ell"
o n = * L s&ell"
o n = , M s&ell"
o 9
o Hf n < * and l < / < = the state is designated )s. n = '! l = + =@ ,d state.
o -hree quantum numbers arise because time-independent Schrdinger equation contains three
independent variables# one for each space coordinate.
o -he eigenvalues of the one-electron atom depend onl& on n# b& the eigenfunctions depend on
n! l and m
l
! since the& are the product of +
nl
r "#
lml
"$ and
ml
"$.
o Cor given n# there are generall& several values of l and m
l
=@ de#enerate ei#enfunctions.
o 7n#ular momentum quantum num(er:
o l = 6 s su(s&ell"
o l = ) p su(s&ell"
o l = * d su(s&ell"
o l = , f su(s&ell"
o 9
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Or+ital transitions or h!drogen Or+ital transitions or h!drogen
o -ransition bet1een different energ& levels of
the h&drogenic atom must follo1 the
follo1ing selection rules:
l = A*
m = /! A*
o A :rotrian dia#ram or a term dia#ram sho1s
the allo=ed transitions.
o -he thic!er the line at right# the more probable
and hence more intense the transitions.
o -he intensit& of emission2absorption lines
could not be e9plained via 8ohr model.
PY3P05
Schrdinger *s- (ohr models Schrdinger *s- (ohr models
o Schrodinger>s G@ treatment had a number of advantages over semi-classical
8ohr model)
*. Frobabilit& densit& orbitals do not violate the 7eisenberg 0ncertaint&
Frinciple.
*. %rbital angular momentum correctl& accounted for.
*. Electron spin can be properl& treaded.
*. Electron transition rates can be e9plained.