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kLVILW kC8LLMS
lnCCPL3 ln18CuuC1lCn
WrlLe down a seL of quanLum numbers LhaL
unlquely deflnes each of Lhe followlng aLomlc
orblLals: (a) 6s, (b) each of Lhe flve 4J orblLals
6s orblLal: n = 6, l = 0, m
l
= 0
flve 4d orblLals: n = 4, l = 2, m
l
= -2, -1, 0, 1, 2
Conslder all Lhe aLoms wlLh Z less Lhan or
equal Lo 20. ln Lhelr elecLronlc ground sLaLe
Whlch of Lhem are dlamagneLlc?
Whlch of Lhem have a slngle unpalred
elecLron?
Whlch of Lhem have Lwo unpalred elecLrons?
1A: ns
1
paramagneLlc
2A: ns
2
dlamagneLlc
3A: ns
2
np
1
paramagneLlc (1 unpalred)
4A: ns
2
np
2
paramagneLlc (2 unpalred)
3A: ns
2
np
3
paramagneLlc (3 unpalred)
6A: ns
2
np
4
paramagneLlc (2 unpalred)
7A: ns
2
np
3
paramagneLlc (1 unpalred)
1he flrsL four lonlzaLlon energles of an aLom x
are 403, 2633, 3900 and 3080 k! mol
-1
.
SuggesL Lo whaL perlodlc group x belongs and
glve reasons for your cholce.
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Slnce Lhe 2
nd
lonlzaLlon energy ls markedly
greaLer Lhan Lhe flrsL (2633 vs 403
k!/mol), and Lhe 3
rd
and 4
Lh
lonlzaLlon energles
appear Lo lncrease llnearly
(2633, 3900, 3080).
1 403
2 2633 2230
3 3900 1267
4 3080 1180
0
1000
2000
3000
4000
3000
6000
0 1 2 3 4 3
Clve a Lewls sLrucLure for cyanamlne P
2
nCn
whlch does noL place formal charges on Lhe
aLoms
WhaL ls Lhe spaLlal geomeLry for Lhls
sLrucLure?
CeneraLe anoLher Lewls sLrucLure by
delocallzlng Lhe lone palr on Lhe amlno group.
WhaL ls Lhe geomeLry assoclaLed wlLh Lhls
sLrucLure?
yramldal on sp
3
n, llnear on C
1rlgonal planar on sp2 n, llnear on C
H
N
H
C N
H
N
H
C N
lor Lhe formula P
4
C
2
C ln whlch Lhe ocLeL rule
ls saLlsfled for each C and C
uraw Lewls sLrucLures and glve Lhe
geomeLrles of Lwo molecules conLalnlng Lhe C-
C-C unlL
uo Lhe same for a cycllc molecule
Clve a sLrucLure for Lhe molecule conLalnlng
Lhe C-C-C unlL. Show LhaL one cannoL be
wrlLLen wlLhouL charge separaLlon.
C
H
H
H
C
H
O
C C
H
H
H
OH
C C
O
H
H
H
H
C H
H
H
O C H
Cn sLerlc grounds, should cls- or ttoos-
[LCl
2
(h
3
)
2
] be favored?
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Pt
Cl Cl
P P
Pt
Cl P
P Cl
AccounL for each of Lhe followlng observaLlons
ll
3
ls a polar molecule
1he flrsL lonlzaLlon energy of k ls lower Lhan LhaL
of Ll
8l
3
ls Lrlgonal planar whlle l
3
ls Lrlgonal pyramldal
ln shape
Square pyramldal ll
3
wlll have neL dlpole
momenL
k [Ar]4s
1
vs Ll [Pe]2s
1
8 has an lncompleLe ocLeL as
opposed Lo
I F F
F
F
F
B I
I
I
P
I
I
I
uraw Lhree resonance sLrucLures whlch have
no charge separaLlon for naphLhalene. uslng
Lhese resonance sLrucLures, provlde a
raLlonale for Lhe dlfferences ln bond lengLh
measured experlmenLally for Lhls
molecule:C1-C2 136.1, C2-C3 142.1, C1-C9
142.3, C9-C10 141.0. All bond lengLhs ln pm.
1
2
3
4 5
6
7
8
C1C2: 2+2+1 = 3, 33 = 1 2/3 (same for ?) 136.1 pm
C2C3: 4/3 = 1 1/3 142.1 pm
C1C9: 4/3 = 1 1/3 142.3 pm
C9C10: 4/3 = 1 1/3 141.0 pm
A1CMIC S1kUC1UkL
lnCCPL3 LLC1u8L
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ulscoverles ln ALomlc SLrucLure
1896 8ecquerel 8adloacLlvlLy
1897 !.!.1homson negaLlve elecLrons
1909 Mllllkan Measured q
e
and m
e
1911 8uLherford nuclear aLom
1913 Moseley ALomlc numbers
(nuclear charges)
1913 8ohr 8ohr aLom
(8almer equaLlon)
ulscoverles ln ALomlc SLrucLure
1920 de 8roglle maLLer waves
1927 Pelsenberg uncerLalnLy rlnclple
1926 Schrodlnger elecLron as wave
Schrodlnger LquaLlon
P = L
P = PamllLonlan operaLor
L = energy of Lhe elecLron
= wave funcLlon, descrlbes an elecLron wave
ln space, aLomlc orblLal
CondlLlons on
Slngle valued (cannoL have Lwo probablllLles)
ConLlnuous (cannoL change abrupLly)
Approaches zero as r approaches lnflnlLy
(smaller probablllLles of flndlng Lhe elecLron aL
larger dlsLances from Lhe nucleus)
normallzed (LoLal probablllLy musL be 1)
CrLhogonal (perpendlcular)
CuanLum numbers
n rlnclpal ma[or parL of energy
l Angular angular dependence
momenLum(shape of orblLal)
l 0 1 2 3 4 3, .
Label s p d f g alphabeLlcal
m
l
MagneLlc orlenLaLlons ln space
(number of orblLals)
m
s
Spln orlenLaLlon of Lhe
elecLron spln
Wave funcLlon
(r,,) = 8(r)()() = 8(r) ?(,)
8adlal funcLlon descrlbes elecLron denslLy aL
dlfferenL dlsLances from Lhe
nucleus, deLermlned by Lhe quanLum numbers
n and l
1he Angular funcLlons descrlbe Lhe shape and
orlenLaLlon of Lhe orblLals ln
space, deLermlned by Lhe quanLum numbers l
and m
l
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8adlal probablllLy funcLlon, 4r
2
8
2
descrlbes Lhe probablllLy of flndlng
Lhe elecLron aL a glven dlsLance
from Lhe nucleus
eneLraLlon
eneLraLlon descrlbes Lhe proxlmlLy of
elecLrons ln an orblLal Lo Lhe nucleus
eneLraLlon refers Lo how effecLlvely elecLrons
can geL close Lo Lhe nucleus.
s > p > d > f
*s characLer of hybrld orblLals correlaLe wlLh
bond lengLhs
C-C Slgma 8onds
C-C
bond type
8ond |ength,
pm
sp
3
-sp
3
134
sp
3
-sp
2
130
sp
3
-sp 146
sp
2
-sp
2
147
sp
2
-sp 143
sp-sp 137
1s orblLal nodal Surfaces
Surfaces wlLh zero elecLron denslLy
Appear from Lhe change ln slgn of Lhe
funcLlon (wave)
1oLal number of nodes ln any orblLal ls n-1
8adlal nodes or spherlcal nodes appear when
8 = 0
Angular nodes resulL when ? = 0 (planar or
conlcal)
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Cne elecLron and nodes
robablllLy does noL qulLe go Lo zero buL
lnsLead has a very small buL flnlLe value
1he elecLron ls a wave. ln a (sLandlng)
wave, Lhe nodes are parL of a wave
CrblLal parlLy - gerade (q) and ungerade (o)
SymmeLry of orblLals ls lmporLanL, and we should be
able Lo deLermlne wheLher orblLals are qetoJe (q) or
ooqetoJe (o) (from Cerman for even or odd).
An orblLal ls q lf lL has a cenLer of lnverslon, and o lf lL
does noL. (lf Lwo llnes drawn ouL aL 180 Lo each
oLher from Lhe cenLer, and of equal dlsLances, sLrlke
ldenLlcal polnLs (a and b), Lhen Lhe orblLal ls g)
s-orblLal p-orblLal J-orblLal
gerade (q) ungerade (o) gerade (q)
o
o
o
b b
b
cenLer of
lnverslon
o = b
noL a
cenLer of
lnverslon
o = b
2s orblLal
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3s orblLal 2p orblLal
3p orblLal 4p orblLal
3J orblLal, m
l
= -2 3J orblLal, m
l
= -1
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3J orblLal, m
l
= 0 3J orblLal, m
l
= 1
m
l
= 1 m
l
= -1 3J orblLal, m
l
= 2
m
l
= 2 m
l
= -2 4J orblLal
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4J orblLal, m
l
= 0 4f orblLal, m
l
= -3
4f orblLal, m
l
= -2 4f orblLal, m
l
= -1
4f orblLal, m
l
= 0 Pund's 8ule
LlecLrons ln orblLals glve Lhe maxlmum LoLal
spln posslble or maxlmum mulLlpllclLy, n+1
number of energy levels LhaL depend on Lhe
orlenLaLlon of Lhe neL magneLlc momenL
LowesL LoLal energy
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alrlng Lnergy
Coulomblc energy of repulslon c
repulslon of muLual negaLlve charges of an
elecLron palr (poslLlve and nearly consLanL for
each palr)
Lxchange energy e
depends on Lhe number of posslble exchanges
beLween Lwo elecLrons wlLh Lhe same energy
and spln (negaLlve and nearly consLanL per
exchange)
p
3
_ __ L =
c
+
e
_ _ _ L =
e
_ _ _ L = 3
e

e
sLablllzes, whlle
c
desLablllzes
_ _ _ L = 3
e
1here ls no preference over Lhe splns
Pund's 8ule
Coulomblc and exchange energles cause
dlsLrlbuLlon of elecLrons ln degeneraLe orblLals
Lo favor unpalred conflguraLlon over Lhe
palred
1ranslLlon elemenLs wlLh Lhelr hlgher orblLals
(4s and 3d) close ln energy break Lhe Lrend
klechkowsky's 8ule
1he order of fllllng of Lhe orblLals proceeds
from Lhe lowesL avallable value for o - l
ComblnaLlons wlLh Lhe same value prlorlLlze
Lhe smaller o
CrblLal lllllng ln Lhe erlodlc 1able Shleldlng
MulLlelecLron aLoms
LlecLrons shleld each oLher from Lhe nucleus
reduclng Lhe aLLracLlon beLween Lhe nucleus
and Lhe more dlsLanL elecLrons
lor hlgher values of o spllL ln orblLal energles
wlLh dlfferenL values of l become slgnlflcanL
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SlaLer's 8ules
LffecLlve nuclear charge Z* as a measure of
Lhe aLLracLlon of Lhe nucleus for an elecLron
Z* = Z - S
Z = nuclear charge/aLomlc number
S = shleldlng consLanL
SlaLer's 8ules
1. WrlLe conflguraLlon ln order of lncreaslng n
(1s)(2s,2p)(3s,3p)(3d)(4s,4p)(4d)(4f) eLc
2. LlecLrons Lo Lhe rlghL do noL shleld elecLrons Lo Lhelr
lefL
3. Same shell elecLrons: each elecLron conLrlbuLes 0.33
Lo S (excepL 1s, whlch shlelds oLher 1s by 0.30)
(n-1) lnner elecLrons: shlelds by 0.83
(n-2) lnner elecLrons: shlelds compleLely (S=1)
4. nd, nf elecLrons: elecLrons Lo Lhe lefL shleld
compleLely
Cxygen
(1s)
2
(2s2p)
6
2p elecLron - (2s2p): 3 0.33 = 1.73
- (1s): 2 0.83 = 1.70
- Z* = 8 - 3.43 = 4.33
nlckel
(1s)
2
(2s2p)
8
(3s3p)
8
(3d)
8
(4s)
2
4s elecLron - (4s): 1 0.33 = 0.33
- (3s3p)(3d): 16 0.83 = 13.6
- (1s)(2s2p): 10 1 = 10
- Z* = 28 -23.93 = 4.03
3d elecLron - (4s): 0
- (3d): 7 0.33 = 2.43
- (1s)(2s2p)(3s3p): 18 1 = 18
- Z* = 28 - 20.43 = 7.33
s and p orblLals have hlgher
probablllLy near Lhe nucleus
Lhan d orblLals for Lhe same n
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Lnergles of orblLals change as Lhey are occupled due Lo
Lhe coulomblc and exchange energles
k.l.klcb, letloJlc cottelotloos, w.A.8eojomlo, Meolo lotk, cA, 1965
1he formaLlon of a caLlon reduces repulslon and lowers energles
of Lhe d orblLals more Lhan LhaL of Lhe s. 1ranslLlon meLal caLlons have no
s elecLrons, only d elecLrons ln Lhelr ouLer levels.
k.l.klcb, letloJlc cottelotloos, w.A.8eojomlo, Meolo lotk, cA, 1965