Germanium quadrupole coupling in the rotational spectrum of (CH 3 ) 3 73 Ge 35 Cl Juliane Fritzsche a Jens-Uwe Grabow a Melanie Schnell b 61 st International.

Präsentation zum Thema: "Germanium quadrupole coupling in the rotational spectrum of (CH 3 ) 3 73 Ge 35 Cl Juliane Fritzsche a Jens-Uwe Grabow a Melanie Schnell b 61 st International."—  Präsentation transkript:

1 Germanium quadrupole coupling in the rotational spectrum of (CH 3 ) 3 73 Ge 35 Cl Juliane Fritzsche a Jens-Uwe Grabow a Melanie Schnell b 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) a Universität Hannover Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover b Fritz-Haber-Institut der Max-Planck-Gesellschaft Abteilung Molekülphysik Faradayweg 4-6, D-14195 Berlin

2 (CH 3 ) 3 GeCl 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) Chlorine Germanium Hydrogen Carbon 1 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

3 (CH 3 ) 3 GeCl 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) Chlorine Germanium Hydrogen Carbon 2 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

4 Isotopomers abundance nuclear spin Ge Cl total Ge Cl (CH 3 ) 3 70 Ge 35 Cl 0,2055 0,754 0,1549 0 3/2 (CH 3 ) 3 70 Ge 37 Cl 0,2055 0,246 0,0506 0 3/2 (CH 3 ) 3 72 Ge 35 Cl 0,2737 0,754 0,2025 0 3/2 (CH 3 ) 3 72 Ge 37 Cl 0,2737 0,246 0,0673 0 3/2 (CH 3 ) 3 74 Ge 35 Cl 0,3674 0,754 0,2770 0 3/2 (CH 3 ) 3 74 Ge 37 Cl 0,3674 0,246 0,0904 0 3/2 (CH 3 ) 3 76 Ge 35 Cl 0,0767 0,754 0,0578 0 3/2 (CH 3 ) 3 76 Ge 37 Cl 0,0767 0,246 0,0189 0 3/2 (CH 3 ) 3 73 Ge 35 Cl 0,0767 0,754 0,0578 9/2 3/2 (CH 3 ) 3 73 Ge 37 Cl 0,0767 0,246 0,0189 9/2 3/2 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 3 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

5 Characteristics of the rotational spectrum of (CH 3 ) 3 GeCl J+1,K J,K-transition frequency area 37 Cl-isotopomers 17 groups due to internal rotation (K=0, K=1) 35 Cl-isotopomers 5 Ge-isotopomers 17 groups due to internal rotation (K=0, K=1) 5 Ge-isotopomers Cl-HFS 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 4 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover 7072737476 7072737476

6 Internal rotation 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 5 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover determined in previous investigation of 72 Ge- and 74 Ge-isotopomers combination of permutation-inversion (PI) group theory and multidimensional high-barrier tunneling formalism characteristic pattern

7 A 1 I 2 I 1 I 4 E 2 I 3 Stat. weights 24 64 32 32 8 16 Characteristic pattern J0J0 AA E2E2 A EA,AE EE EEE EEA,EAE,AEE EAA,AEA, AAE AAA A1A1 E 2 +I 3 A1A1 I 1 +I 4 I2I2 E I4I4 I3I3 I1I1 I2I2 Top 1 Top 2 Top 3 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) J: 2 1, K = 0 7958.3 MHz7959.6 6 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

8 Spectrum (CH 3 ) 3 GeCl 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 70 Ge 1-3 K=0 5-5 K=0 3-5 K=1 3-3 K=1 5-5 K=1 5-3 K=0 1-1 K=0 5-7 K=0 3-5 K=0 1-3 K=1 5-3 K=1 5-7 K=1 72 Ge 1-3 K=0 5-5 K=0 3-5 K=1 3-3 K=1 5-5 K=1 5-3 K=0 1-1 K=0 5-7 K=0 3-5 K=0 1-3 K=1 5-3 K=1 5-7 K=1 1-3 K=1 3-3 K=0 1-1 K=1 74 Ge 1-3 K=0 5-5 K=0 3-5 K=1 3-3 K=1 5-5 K=1 5-3 K=0 1-1 K=0 5-7 K=0 3-5 K=0 1-3 K=1 5-3 K=1 5-7 K=1 1-3 K=1 3-3 K=0 1-1 K=1 76 Ge 3-3 K=1 5-5 K=1 5-3 K=0 1-1 K=0 5-7 K=0 3-5 K=0 1-3 K=1 5-3 K=1 5-7 K=1 1-3 K=1 3-3 K=0 1-1 K=1 3-1 K=0 7 J=21 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

9 (CH 3 ) 3 73 GeCl 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) Chlorine Germanium Hydrogen Carbon 8 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

10 Characteristics of the rotational spectrum of (CH 3 ) 3 73 GeCl J+1,K J,K-transition frequency range 37 Cl-isotopomers 35 Cl-isotopomers 17 groups due to internal rotation (K=0, K=1) 5 Ge-isotopomers Cl-HFS 7072737476 Ge-HFS 5 Ge-isotopomers Cl-HFS 7072737476 Ge-HFS 17 groups due to internal rotation (K=0, K=1) 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 9 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

11 Spectrum (CH 3 ) 3 GeCl 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 10 J=21 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover 1-3 K=0 5-5 K=0 3-5 K=1 3-3 K=1 5-5 K=1 5-3 K=0 1-1 K=0 5-7 K=0 3-5 K=0 1-3 K=1 5-3 K=1 5-7 K=1 1-3 K=1 3-3 K=0 1-1 K=1 73 Ge

12 A1A1 I2I2 I1I1 I4I4 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) (CH 3 ) 3 73 GeCl 11 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover frequency / MHz intensity / mVrms J=21 which transition? several calculations by varying the value of eQq (Ge) using sym2qs only one reasonable assignment F 1 ´,F´ F 1,F = 5/2,75/2,6

13 Proceeding 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 12 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover due to relative magnitude of 2nd order effects two fitting results reproduce experimental observation F 1 ´,F´ F 1,F 5/2,75/2,6 eQq(Ge)= -16.01 MHzeQq(Ge)= -34.61 MHz requires unusual small field gradient q at 73 Ge nucleus no corresponding other hyperfine components observed at predicted position large nuclear quadrupole moment Q of 73 Ge consistent with plausible field gradient q at 73 Ge nucleus consistent with F 1,F F 1,F 7/2,6 5/2,6 components at 7960.07 MHz

14 (CH 3 ) 3 73 Ge 35 Cl B / MHz 1990.549113(23)* D J / kHz 0.3121(0)* eQq / MHz (Cl) -40.0656(41)* eQq / MHz (Ge) -34.61 Results and Outlook 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 13 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover measurement of J=10 (adapt antennas to low frequencies) only 29 quadrupole components: less overlap, easier assigment Next steps

15 Acknowledgement mechanical workshop: H. Bieder, W. Becker, W. Egly electronical workshop: W. Rogge Deutsche Forschungsgemeinschaft Land Niedersachsen 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) 14 Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

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17 Internal rotation 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover E, 2C 3, 3σ v 6 symmetry elements G 162 H R : rotation of 1 single CH 3 -group H A : anti-geared rotation of 2 CH 3 -groups H G : geared rotation of 2 CH 3 -groups H E : rotation of 3 CH 3 -groups with the same sense H L : rotation of 3 CH 3 -groups with different sense 5 topologically inequivalent tunneling pathways:

18 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) sixfold degenerate I 1 –I 4 twofold degenerate E non-degenerate A Tunneling Hamiltonian matrix for K=0 characteristic pattern Internal rotation Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

19 Experimental setup 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover

20 flow rate reaction source 61 st International Symposium on Molecular Spectroscopy, Columbus (OH) Institut für Physikalische Chemie und Elektrochemie Callinstraße 3-3a, D-30167 Hannover