Kelly Hotopp June 22, 2010 Purdue University.  Demonstration of 2D CP-FTMW spectroscopy ◦ Non-Selective Excitation ◦ Selective Excitation  2D CP-FTMW.

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Kelly Hotopp June 22, 2010 Purdue University

 Demonstration of 2D CP-FTMW spectroscopy ◦ Non-Selective Excitation ◦ Selective Excitation  2D CP-FTMW spectroscopy exploits the fast frequency switching time of arbitrary waveform generation to produce exotic pulses that would not be possible using traditional frequency sources. 2D CP-FTMW DevelopmentTheory Applications

13.0 GHz PDRO 12 GHz Oscilloscope (40 Gs/s) 13 GHz Filter 200W Arbitrary Waveform Generator 100 MHz Quartz Oscillator Chirped Pulse GHz 8-18 GHz Pulsed Nozzle GHz 1) 2) 3) Free Induction Decay 18.9 GHz PDRO 1)Pulse Generation 2)Molecular Interaction 3)Detection

Time Domain Excitation pump t1t1 probe (Scan) 100 ns 0 00 F= F=1.5 F=0.5 F=2.5 Energy Level Scheme t2t2 A B C D A)preparation B) t 1 evolution C) mixing D) t 2 detection

←1 01 (8391 MHz) 2 12 ←1 01 (11,377 MHz) 3 13 ←2 12 (11,659 MHz) 3 03 ←2 02 (12,380 MHz) 4 14 ←3 13 (15,459 MHz) 4 14 ←3 03 (17,723 MHz) Pulse Sequence

* Energy Level Scheme 1D slice of the 2 12 ←1 01 (11,377MHz) rotational transition of DFA

Energy Level Scheme D slice of the 4 04 ←3 03 (16,168 MHz) transition of DFA * Mixing Peak

←1 01 (11,377 MHz) 2 02 ←1 01 (8,391 MHz) 3 03 ←2 02 (12,380 MHz) 4 04 ←3 03 (16,168 MHz)

Low Barrier  Cis ~ 35 cm -1  Trans ~ 4.5 cm -1 m-methylbenzaldehyde Excitation Regions: Selected K 0 Regions of Cis and Trans Arbitrary Intensity Two Conformers Amanda Shirar RH15 Thurs. 5:42 PM Dense Rotational Spectrum

Cis A Cis A Cis A Cis A Coherences Transferred Through Coupled Energy Levels Disentangles 1D Spectrum Relative Frequency (MHz) Normalized Intensity

Not Phase Sensitive Addition of 90° Quadrature Hybrid will provide phase sensitive detection(05/11/2 010) 13.0 GHz PDRO 12 GHz Oscilloscope (40 Gs/s) 13 GHz Filter 200W Arbitrary Waveform Generator 100 MHz Quartz Oscillator Chirped Pulse GHz 8-18 GHz Pulsed Nozzle GHz 1) 2) 3) Free Induction Decay 18.9 GHz PDRO

Density Matrix Consider 3-Level System with the Following Pulse Sequence: Equation of Motion During Mixing Period (  =  ): Where  and  are proportional to the transition moment operator  a and  b respectively. t0t0 SIGN OF TRANSITION MOMENT PRESERVED! B. Vogelsanger and A. Bauder, J. Chem. Phys. 92, 4101 (1990)

 Chiral Molecules ◦ Phase Detection ◦ (S)-2-butanol and (R)-2-butanol  Quantum Logic Gates ◦ Make a superposition of two states and then transfer the coherence to different energy levels.  X-gate: π pulse  Hadamard gate: π /2 pulse  Z-gate: 2 π pulse (R)-2-butanol (S)-2-butanol