julie m. michaud and michael c. l. gerry university of british columbia, vancouver, bc canada
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The Study of Noble Gas – Noble Metal Halide Interactions: Fourier Transform Microwave Spectroscopy of XeCuCl. Julie M. Michaud and Michael C. L. Gerry University of British Columbia, Vancouver, BC Canada June 2005 International Symposium on Molecular Spectroscopy. XeCuCl. - PowerPoint PPT PresentationTRANSCRIPT
The Study of Noble Gas – Noble Metal Halide Interactions: Fourier Transform Microwave Spectroscopy of XeCuCl
Julie M. Michaud and Michael C. L. GerryUniversity of British Columbia, Vancouver, BC Canada
June 2005International Symposium on Molecular
Spectroscopy
2
XeCuClAnticipated properties: Short Xe-Cu bond length; Small centrifugal distortion constant; Large changes in nuclear quadrupole
coupling constants (131Xe, Cu and Cl) on bond formation;
Significant theoretical evidence of strong interactions between the Xe and Cu atoms in XeCuCl.
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The Experiment
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132Xe63Cu35Cl Spectrum
Natural abundance:14.1%
I(63Cu) = 3/2
I(35Cl) = 3/2
Total of 10 transitionsin this one spectrum
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131Xe63Cu35Cl Spectrum
Natural abundance: 11.1%
I(131Xe) = 3/2
I(63Cu) = 3/2
I(35Cl) = 3/2
Total of 15 transitionsin this one spectrum
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Representative Spectroscopic Constants
Parameter 129Xe63Cu35Cl 131Xe63Cu35Cl 132Xe63Cu35ClBo /MHz 757.30669(9) 753.0300(2) 750.93467(5)
DJ /kHz 0.0794(7) 0.104(2) 0.0782(4)
eQq(Cu) /MHz 41.81(9) 41.6(1) 41.57(6)
eQq(Cl) /MHz -26.10(6) -26.4(1) -26.01(4)
eQq(131Xe) /MHz - -81.4(2) -
eQq(63Cu) /MHz = 16.17 eQq(35Cl) /MHz = -32.1
Nuclear quadrupole coupling constants of the CuCl monomer:
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Xe-Cu bond lengths in XeCuCl
Experimental rm(2)(Xe-Cu) = 2.4669(4) Å
MP2 results r(Xe-Cu) = 2.497 Å a
van der Waals limit:
Covalent limit:
a Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett. 2002, 368, 589.b Pyykkö, P. Chem. Rev. 1997, 97, 597.c Huheey, J. E. et al. Inorganic Chemistry, Principles of Structure and Reactivity, 4th Ed.; Harper-Collins: New York, 1993.d Bartlett, N et al. In Comprehensive Inorganic Chemistry; Bailar, J. C. et al. Eds.;Pergamon:Oxford, 1973; 213-330.e Pyykkö, P. Chem. Rev. 1988, 88, 579.
(rvdW(Xe)b + rion(Cu+)c) = 2.78 Å
(rcov(Xe)d + rcov(Cu(I))e) = 2.36 Å
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Centrifugal Distortion Constants
2
34
oJ
BD
k21
Small centrifugal distortion constants Highly rigid molecules
DJ
/kHz X 102 k(Ng-M)
/Nm-1
XeCuF 20 94XeAuF 7 137ArAgCl 35 34
Ar-NaCla 900 0.6a Mizoguchi, A.; Endo, Y.; Ohshima, Y. J. Chem. Phys. 1998, 109, 10539.
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Nuclear Quadrupole Coupling Constants (MHz) for 131Xe
131Xe 0131Xe-Ara 0.723
131Xe-HClb -4.9131Xe63CuX -81.4 to -87.8
131Xe107AgXc -78.1 to -82.8131XeAuFd -134.5131XeH+ e -369.5
131Xe [Kr]5s24d105p56s1 f -505
a Xu, Y. et al. JCP, 1993, 99, 919. b Keenan, M. R. et al. JCP, 1980, 73(8), 3523.c Cooke, S.A. et al. PCCP, 2004, 6, 3248. d Cooke S.A. et al. JACS, 2004, 126, 17000. e Kellö, V. et al. Chem. Phys. Lett., 2001, 346, 155. f Faust, W. L. et al. Phys. Rev., 1961, 123, 198.
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Ab initio calculations A large dissociation energy was
calculated for XeCuCl (55 kJ mol-1); Charge-induced dipole induction energy for
XeCuCl: 21 kJ mol-1;
Mulliken and NBO populations show significant donation of electron density from the Xe to the Cu;
Donation of ~0.1-0.2 of an elementary charge donated from Xe to Cu.
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0
20
40
60
80
100
20 40 60 80 100 120 140
Force constant, k (N/m)
Dis
soci
atio
nE
nerg
y,D
e(k
J/m
ol)
ArMX
KrMX
XeMX
ArMX
KrMX
XeMXArAgClArAgF
KrAgClKrAgF
XeAgClXeAgF
ArCuCl
KrCuClArAuCl
ArCuF
KrCuF
KrAuCl
KrAuF
ArAuF
XeAuF
XeCuClXeCuF
From the Morse Potential:k = 2D âe
2
Plots of dissociation energy vs. force constant for all studied NgMX molecules
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MOLDEN plots of valence MOs
X e
C u
C l
3 σ 1 π
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Local Energy Densitiesa
H(r) = G(r) + V(r)
Values are calculated at the bond critical point of the maximum electron density (MED) path between bonded atoms.
Negative H(r) implies … V(r) dominates … e- density accumulates
at rB
… a covalent bond forms!!a Cremer, D.; Kraka, E. Angew. Chem. 1984, 96, 612; see also Angew. Chem. Int. Ed. Engl., 1984, 23, 627.
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Local Energy DensitiesLocal Energy Densities at rB
(Hartree Å-3) for several NgMX molecules
ArCuF -0.0151ArCuCl -0.0148KrCuF -0.0400KrCuCl -0.0390XeCuF -0.0699XeCuCl -0.0667
XeAgF -0.0542XeAgCl -0.0457XeAuF -0.1799
!All negative values
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Conclusion
First preparation and characterization XeCuCl;
Very strong Xe-Cu interactions observed; Strong Ng-M interactions similar to those
expected from previous NgMX studies; XeCuCl shows convincing evidence of
covalent Xe-Cu bonding.
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AcknowledgementsThank you to Mike Gerry, Steve Cooke and Christine
Krumrey.
This research has been supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada.
Thank you for your attention.