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<Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Columbus 2010 Columbus 2010
MICROWAVE SPECTROSCOPY OF ALKALOIDS:
THE CONFORMATIONAL SHAPES OF NICOTINE
Jens-Uwe Grabow, Santiago Mata, Juan Carlos López,I. Pena, C. Cabezas, Susanna Blanco, Jóse Luis Alonso
Departamento de Química-Física y Química-InorgánicaUniversidad de Valladolid
Institut für Physikalische Chemie & Elektrochemie
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Rotational Spectra:Unambiguous Fingerprint
Sevoflurane
A. Lesarri, A. Vega-Toribio, R. D. Suenram, D. J. Brugh, J.-U. Grabow, Phys.Chem.Chem.Phys., in press(2010).
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Large Species/Multiple Conformers:Challenging Identification of
Fingerprints Enflurane
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Coaxial oriented Beam-Resonator Arrangement (COBRA):molecular excitation
tMW pulse
1μs
before excitation pulse: dipole moments cancel
single particle, Schrödinger equation:
iH
iH ,ensemble properties, von Neumann equation
wavefunction
density matrix
J.-U. Grabow, W. Stahl, Z. Naturforsch. 45a, 1043 (1990).
)()(
)()(
tt
tt
bbba
abaa
density matrix:
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
molecular interaction with radiationshort stimulus Density Matrix formalism
00
01
0 baab (no) coherence:
thermal population: 0 bbaa
Eb
Ea
many two-level systems
21
2
221
i
i
0, baab coherence:
population equillibration: 0 bbaa
„π/2“ pulse
bbaaw
baabu )( baabiv
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Coaxial oriented Beam-Resonator Arrangement (COBRA):molecular response
E
t
T = 100μs
MW signal
after excitation pulse: oscillating macroscopic dipole moment
Fourier Transform
Frequency Domain, Spectrum
Time Domain, FID
U. Andresen, H. Dreizler, J.-U. Grabow, W. Stahl, Rev.Sci.Instrum. 61, 3694 (1990).
J.-U. Grabow, W. Stahl, H. Dreizler, Rev.Sci.Instrum. 67, 4072 (1996).
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<Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Columbus 2010
“coaxially oriented beam resonator arrangement“(COBRA) FTMW-Spectrometer
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
COBRA FT-MW SpectrometerHannover
J.-U. Grabow, W. Stahl, H. Dreizler, Rev. Sci. Instr. 67 (1996) 4072.
FWHM: 3 kHzbandwidth: < 1 MHzrange: 2-26.5 GHz
10mW…200mW
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<Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Columbus 2010
molecular interaction with radiationfast passage Density Matrix formalism
00
01
0 baab (no) coherence:
thermal population: 0 bbaa
Eb
Ea
many two-level systems
21
2
221
i
i
0, baab coherence:
population equillibration: 0 bbaa
„π/2“ pulse
bbaaw
baabu )( baabiv
Ins
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
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Materialien
IMPACT FT-MWValladolid
Inphase/Quadraturephase-Modulation-Passage Acquired-Coherence-Technique
1W…20W
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Inphase/Quadraturephase-Modulation-Passage Acquired-Coherence-Technique
(IMPACT) FTMW - Spectrometer
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
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Materialien
Inphase/Quadraturephase-Modulation-Passage Acquired-Coherence-Technique
(IMPACT) FTMW - Spectrometer
Computer
Pulse Sequence Generation
Arbitrary Waveform Generation
Digitizer
HF electronics
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
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Materialien
IMPACT FT-MW Spectrometerfirst-day spectral examples
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
Nicotine:Two Conformations
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
&Neue
Materialien
IMPACT FT-MW SpectrometerThe alkaloid nicotine
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
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Materialien
Trans-a Trans-b Th Exp. Th Exp. A / MHz 2063,676 2059,56080 (70) 2048,750 2045,68593 (92)
B / MHz 580,305 579,870499 (173) 583,709 583,257787 (144)
C / MHz 550,970 549,322724 (203) 554,739 552,824539 (151)
-0.96106215 -0.96121897
Qua N1 Qua N5
aa / MHz 2,180927 2,1327 (165) 2,099717 2,0620 (178)
bb / MHz 2,661291 2,5793 (152) 2,604833 2,5666 (322)
cc / MHz -4,842218 -4,7119 (152) -4,704551 -4,6286 (322) Qua N8 Qua N21
aa / MHz -1,130406 -1,1672 (128) 0,912761 0,8753 (178)
bb / MHz 3,148936 3,3328 (131) 3,175922 3,1669 (319)
cc / MHz -2,018530 -2,1656 (131) -4,088683 -4,0423 (319)
a 2,266 -1,490
b -0,151 0,439
c -1,258 -2,635
total 2,596 3,059
E (h) -497,6200972 -497,6191493
ΔE zpe MP2 / cm-1 0 208,040002
Nicotine:Two Conformations
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
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Materialien
IMPACT FT-MW Spectrometerfield focussing reflector / coaxial LASER ablation
LASER
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
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Materialien
IMPACT FT-MW Spectrometer / LASER ablationamino acid proline: first results
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Columbus 2010 <Dateiname>.ppt
Zentrum für Festkörperchemie
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Materialien
IMPACT FT-MW Spectrometer
Inphase/Quadraturephase-Modulation-Passage Acquired-Coherence-Technique
targeted resolution: FWHM: ~3 kHzbandwidth: 1 GHz (x n)range: 2-26.5 GHz
1W…20W
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<Dateiname>.ppt
Zentrum für Festkörperchemie
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Materialien
Columbus 2010
AcknowledgementAcknowledgement
Deutsche Forschungsgemeinschaft (DFG)
Land Niedersachsen
Ministerio de Ciencia e Innovacion
Junta de Castilla y Leon
Wolfgang Rogge
Feinmechanikwerkstatt Institut für Physikalische Chemie
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