department of chemistry (chemicum) research in society from basics to applications research-based...
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Department of Chemistry (Chemicum)
research
in society
from basics to applications
research-based education
knowledge in service Welcome to the Department of Chemistry!
Department Composition (education)
• Laboratory of Analytical Chemistry Inorganic Chemistry Organic Chemistry Physical Chemistry Polymer Chemistry Radiochemistry
• Centre for Chemistry Education
• Chemistry ICT Center (eChemicum)
• Laboratory for Instruction in Swedish
• VERIFIN
Strategic Focuses in Research (2004-2006)
Green chemistry
Material and nanochemistry
Computational and theoretical chemistry
Science teacher education and its
reseach
Green Chemistry is the use of chemistry for pollution prevention.
More specifically, green chemistry is the design of chemical
products and processes that are more environmentally benign.
.
Micro- and optoelectronics
Space applications
Nuclear waste purification
Biomaterials
Pharmaceuticals
MATERIALS CHEMISTRY
Application areas
MOSFET transistor
Grid filter for X-ray detector
Polysilicon
Spacer, by ALD?
Metal oxide gate-dielectric, by ALD?
Metal gate,by ALD?
SourceSi-substrate Drain
CoSi2
Channel
.
Templating by porous materials→ nanowires, nanorods Templating by fibers → nanotubes Electrospinning → nanowires, nanotubesPatterning with SAMsNanoparticlesSmart polymers and materials
MAKING OF NANOMATERIALS
.
Nanowires, nanorods coated by ALDGlancing angle evaporation Patterning with SAMsStar polymersBlock copolymers
MAKING OF NANOSTRUCTURES
+ oblique evaporation
+ electrodeposition
+ dissolution of alumina
+ ALD
free standing porous alumina
.
Dielectrics for gate oxides in MOSFETs
Dielectric films for DRAMs and FERAMs
Metal films
Nitride films for barriers
THIN FILM MATERIALS FOR MICROELECTRONICS
Al2O3 film deposited by ALD from AlCl3 and Al(OiPr)3.
14 nm TiN
TiCl4 + Zn + NH3 TiNin collaboration with Intel
In collaboration
with NIST
S
HOOC
S
ON
CH3
CNH
CN
(Cpa-RAFT-PNIPAM Mn = 6450 PDI = 1.11)
55
CH3
HOOCS
S
(Cpa-RAFT-PS Mn = 10000 PDI = 1.07)
94
Gold nanoparticles with hydrophilic and hydrophobic polymer grafts
PNIPAM
PS
+ HAuC l4 Au
PNIPAM /PS-M PC
Development of miniaturized analytical devices
• Electrospray devices–PDMS
–SU-8
• Miniaturized atmospheric pressure chemical ionization (APCI) and photoionization sources (APPI)
(B ) (C )
m/z
100 150 200 250 300 350 400 450 500
Abso
lute
inte
nsi
ty [
cps]
0
1e+7
2e+7
3e+7
4e+7
5e+7
[M+H]+
(A)
O
H
H
OH
H
TIC +MRM: 455,2/165,1amu ja 455,2/ 303,4 amu
0,00E+00
1,00E+05
2,00E+05
3,00E+05
4,00E+05
5,00E+05
6,00E+05
0 10 20 30 40 50 60
time, min
inte
nsit
y, c
ps
Development of miniaturized analytical devices
• Methods based on porous silicon–Desorption Ionization On Silicon (DIOS)
–Filtration devices
• SU-8 microchannels for CE
laser MS
porous area sample
Midazolam MW: 325
Milestones in noble-gas chemistry
• First compounds predicted already in 1902!
• Pauling 1933: XeF6 and KrF6 should be preparable.
• Bartlett 1962: first noble-gas compound, Xe[PtF6].
• In matrices: First : KrF2 (Turner and Pimentel, 1963). Others: XeCl2 (Nelson and Pimentel, 1967); ClXeF (Bondybey, 1971).
• Strong interactions in matrices: Cr(CO)5---Rg (Perutz and Turner, 1975); Rg---BeO (Thompson and Andrews, 1994).
• XeAuF (Cooke and Gerry, 2004).
• HRgY Pettersson et al., 1995-)
2300 2200 2100 1300 1250 1200 1150 1100
0.0
0.5
1.0
1.5
2.0
2.5
C
B
A
XeH
2
HXeIab
sorb
ance
wavenumber (cm-1)
HI
photolyzedinitial sampleHI/Xe, 1:1000
annealed to 45 K
18
Noble gas hydrides
Ar Kr Xe
HXeHHXeIHXeBr
HKrCl HXeClHArF HKrF
HKrCN HXeCNHXeNCHXeOHHXeOHXeSHHXeNCO
HKrCCH HXeCCHHXeCCXeHHXeCC
HKrC4H HXeC4H
H Xe I1.68 Å 3.1 Å
+0.129 +0.347 -0.476MP2/43333/433111/41111(Xe, I)/6-311++G(3d,3p) (H)
Van der Waals -distances:
H Xe3.8 Å 4.3 Å
I
Experimental: 1-
Xe-H cm11931-
Xe)-(Hcm2200
(HNg)+ + Y-
H + Ng + Y
Avoided crossing
HNgY molecules correlate with neutral atomic asymptote
H-Ng-Y
1980 1970 1960
-0.1
0.0
0.1
HF / 36Ar
HF / 40Ar
H-A
r st
r.
Abso
rbance
690 680
H-A
r-F b
end.
440 430
F-A
r st
r.
1480 1470 1460 1450
0.0
0.1
DF / 40Ar
D-A
r st
r.
Abso
rbance
520 510
Wavenumber (cm-1)D
-Ar-
F b
end.
440 430
F-A
r st
r.
Effect of isotopic substitution on the fundamentals of HArF
Predicted organo-Ng-molecules
• Numerous Xe-containing organic molecules are known, normally containing F.
Examples:• R2Xe, where R = C6F5 or 2,4,6-C6H2F3
• [CF3CCXe][BF4]
• So far, no organic Ar compounds known. • Non-halogen containing organic molecules predicted in 2002:
Lundell et al. J. Phys.Chem. A 106 (2002) 11950.
HXeC6H5
HXeCCH
HXeOC6H5
HXeCCXeH
Predicted organo-Ng-molecules
• The MP2/LJ18/6-311++G(2d,2p) calculated structure and Mulliken charges of HCOOXeH
• Works for larger acids, glycine, alanine and valine.
• J. Lundell et al., Computers&Chemistry, 24 (2000) 325-330.
Xe H
Acetylenic systems
• HNgC6H and HNgC8H-molecules expected to be more stable than HNgC4H and HNgC2H
• First halogen-free organic Xe compounds.
• First organic Kr compounds.
• Challenge: Organic Ar-compound!
C2H 2.956
C4H 3.558
C6H 3.809
C8H 3.996
Electron affinity:
• Electron affinity of C2nH radicals localized at the C end.
Bond lengths
(Kr) 1.58 2.26 1.24 1.37 1.22 1.06
(Xe) 1.74 2.33 1.24 1.37 1.22 1.06
(Xe) 1.75 2.32 1.23 1.06
(Kr) 1.60 2.25 1.23 1.06
MP2/LJ18(Xe)/6-311++G(2d,2p) level
Recent computational predictions
• H-Xe-CC-H
• H-Xe-CC-Xe-H
• H-Xe-CC-Xe- CC-Xe-C C-Xe-...-H• E. C. Brown, A. Cohen and B. Gerber, JCP, 122 (2005) 171101.
• F-Kr-CC-H
• F-Kr-SiF3
• S. Yockel, A. Garg, A. Wilson, CPL., 411(2005)91.
Applications?
• Very high energy compounds, could form solids!
• Specific activation of functional groups: ”Xe-catalysis”.
• Function of Xe in aenesthesia
• Solving the ”missing Xe-problem”