Chemistry 482

Homework Set #6
Due Apr 1, 2013


1. The hydrogenic 1s spatial orbital has the wavefunction:
3/2
1/2
/
100
1
( , , )
Zr a
Z
r e
a
u |
t

| |
| |
=
| |
\ .
\ .
,
where a

( the Bohr radius) is

2
2
4
e
a
m e
tc

= . For the ground state of Li

2+
calculate:
(a) The most probable radial position of the electron from the nucleus
(b) The average radial position, r


2. The hydrogen atom wave function for one of the 3p orbitals is
3/2
2
/3
311 2
1 1
( , , ) 2 6 sin
81 3
r a i
r r
r e e
a a a
|
u | u
t

| | | |
=
| |
\ . \ .


(a) Provide the equation for the radial distribution function
(b) Provide the number of radial nodes and the position of each radial node.


3: Let's now explore the size of a hydrogen atom, in which the electron occupies the 1s orbital. We will define size
by setting the probability for the electron to fall within the distance r from the nucleus.
(a) First set the probability for locating the electron at 90%. What is the corresponding atomic "size"?
(b) If we increase the probability to 99%, what is the orbital "size"?

4. For a two-electron system consider the possible spin functions S
1
and

S
2:


S
1
=
(1) (2) (2) (1)
2
o | o | +
and S
2
=
(1) (2) (2) (1)
2
o | o |
,
Where o and | are the usual electron spin functions and the electron number is shown in parenthesis.

(a) Show that these spin functions are eigenfunctions of the operator
2

,
Tot
S where
1 2

Tot
S S S = +

(b) Find the eigenvalues of
2

Tot
S for each of these spin functions
1
.2.
(() )
n- $ - J = 3- 1-/ ~ r (n ode )
:I ~
let r R3/ ( r) ==- a -=>
r
3.
(() )
Prob
- ~ fA r;l. e-2rfao I -= 0 q
ao 0 01 r ~J
Jet r/0.0 =?( J ~ r= ~o?(
P
_ -.. fMo.o :2:2. - 2'X I
~ - a}J () Oo?< e .OoDi 'X
- 4 rAJJ.D '- -2X_1
- ex e otX o _____
----
I JAro
o
4 . 4 ~-2X (~11< (?< +f ) - I) 0
:::;> Alao == 1,1
== 0,9
A= 2,TC1o -10
~ /,596 x/a rn
Lb) The <;o.,me procedure:
f
b/ao
~ -2X {-2X ('X t I ) - I ) 0 = 0, q 9
~ B I a17:= (;. 8q B =: 3, 8~a 0
.::. .2,30 x'O-fO rn
4.
-
Also f ~1'lI = 0 I~_\!i = -h P
lSt ? := ]()( $- ~ '" 0
~ :). <:.;:: (~2. + ~2 + J P OA. + S' A + SA SA ) ( \)(c/)t>{7-) + (j{)) f3.1) )
0t-()T e) l /) ::> I -:> 2 ::>~ :> 1.~ 1+ 02- /- 'J-t- 12
I [J\ /\. A. A. ~L /\
=$ ~(:l-) S't 0.(1) +- O<'tlJ S; ~2) +- 2. )1'% D1U) ~2i' f!r.2) +- ~ "\ (I) $,- ~[2)
1\ /\..If A A 1'\ 1'\
+ '3,-\)ill S'1&[~)+ ()((2) c;t .(Il +- (3t1l S; 1)((2) +-:1)fz (3J))2O IY[].)
"A 1\ /\. ]
+ <)/-j- ~cI) ~ 2- ()(t~) + SI ~I) S2+ ex (1.)
I [ .
==J3 f>(~)t:'tD{(/) T o((})h\~ P(2) + ..21hrx(()(-~tj)~(2)
+ oI(2)t2.$ ~C/) + ~{)~-2i (X (1.) + 2(- it) ~(/)(t-n )[X{.2)
+ 1i\\lO) 1i{?>b) ~ + h(3llrn- (X(2) J
1-[ .:2 .. ]
= 13 211 (cxa) @>(2) + Df(2) fO) ') ~ 1t<- ~Ci)
E ~e)J v~ue == 2112
A
:2
~ :)lJ) = 0 E~0f)vaJu~ = D