6/10/2013

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kLVILW ÞkC8LLMS
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?
• Þyramldal 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-
[ÞLCl
2
(ÞÞh
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 Þl
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 Þ
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, 3÷3 = 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 Þrlnclple
• 1926 Schrodlnger elecLron as wave
Schrodlnger LquaLlon
PΨ = LΨ
• P = PamllLonlan operaLor
• L = energy of Lhe elecLron
• Ψ= wave funcLlon, descrlbes an elecLron wave
ln space, aLomlc orblLal
CondlLlons on Ψ
• 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 Þrlnclpal 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
• Ψ(r,θ,φ) = 8(r)Θ(θ)Φ(φ) = 8(r) ?(θ,φ)
• 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, 4πr
2
8
2
descrlbes Lhe probablllLy of flndlng
Lhe elecLron aL a glven dlsLance
from Lhe nucleus
ÞeneLraLlon
• ÞeneLraLlon descrlbes Lhe proxlmlLy of
elecLrons ln an orblLal Lo Lhe nucleus
• ÞeneLraLlon 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
• ÞrobablllLy 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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Þalrlng Lnergy
• Coulomblc energy of repulslon Πc
repulslon of muLual negaLlve charges of an
elecLron palr (poslLlve and nearly consLanL for
each palr)
• Lxchange energy Πe
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 = Π
c
+ Π
e
• ↑_ ↑_ ↓_ L = Π
e
• ↑_ ↑_ ↑_ L = 3Π
e
Π
e
sLablllzes, whlle Π
c
desLablllzes
↓_ ↓_ ↓_ L = 3Π
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 Þerlodlc 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

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