Proton Sponges: A Rigid Organic Scaffold to Reveal the Quantum Structure of the Intramolecular Proton Bond Andrew F. DeBlase, Michael T. Scerba, Thomas.

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Presentation transcript:

Proton Sponges: A Rigid Organic Scaffold to Reveal the Quantum Structure of the Intramolecular Proton Bond Andrew F. DeBlase, Michael T. Scerba, Thomas Lectka, and Mark A. Johnson June 22,

Background Tom Lectka (organic): Isolate exotic charged H-bonds Scerba et. al. J. Org. Chem e.g. Charged H-bond to F Our work: Shared proton often a distinct feature in cold ions Roscioli et. al. Science 2007 Ar-predissociation of cryogenic ions Photon Energy (cm -1 ) Stoyanov and Reed J. Phys. Chem. A 2006 Room temperature FTIR

Background Tom Lectka (organic): Isolate exotic charged H-bonds Scerba et. al. J. Org. Chem e.g. Charged H-bond to F Our work: Shared proton often a distinct feature in cold ions “I think this is the beginning of a beautiful friendship.”

Background Tom Lectka (organic): Isolate exotic charged H-bonds Scerba et. al. J. Org. Chem e.g. Charged H-bond to F Our work: Shared proton often a distinct feature in cold ions “I think this is the beginning of a beautiful friendship.” Can you make an H-bond to the ether oxygen of an ester?

Why Is This Unusual? The carbonyl O has a much higher proton affinity!

Why Is This Unusual? The carbonyl O has a much higher proton affinity! Very Fast Bohme Int. J. Mass Spectrom Blue shift? ν CO

Experimental Setup Ion optics Electrospray Needle RF Only Quadrupoles Octopoles Pressure (Torr) 3D Quadrupole Ion Trap with Temperature Control to 8 K TOF to IR Spectrometer New Cryogenic Ion Source 3× × × Heated Capillary 90 ° Ion Bender Wiley- McLaren Extraction Region

+ D 2 13 C m/z The Experiment *

+ D 2 13 C m/z The Experiment hνhν OPO/OPA LaserVision Mid Infrared Laser Apply mass gate to ion of interest

+ D 2 13 C Time of Flight Monitor photofragment as a function of laser energy The Experiment

Photon Energy (cm -1 ) ν NH Predissociation Yield, Calculated Intensity Blue Shifted Carbonyl: Evidence for a Strong Intramolecular H-Bond Scerba et. al. J. Phys. Chem. A ν CO ν OH = 3313 ν CO = B3LYP/ G** (unscaled) B3LYP/ G** (CH scaled by 0.961, NH scaled by 0.945) Douberly, et. al. PCCP 2008 Course, et. al. JOC 1981 Wow!!!

Photon Energy (cm -1 ) ν NH Predissociation Yield, Calculated Intensity Blue Shifted Carbonyl: Evidence for a Strong Intramolecular H-Bond Scerba et. al. J. Phys. Chem. A ν CO 1792 B3LYP/ G** (unscaled) B3LYP/ G** (CH scaled by 0.961, NH scaled by 0.945) Is the complexity from the reaction coordinate?

Predissociation Yield, Calculated Intensity Photon Energy (cm -1 ) Calculated: B3LYP/ G** Scaled by Tuning the Shared Proton Frequency · D · D 2

Predissociation Yield, Calculated Intensity Photon Energy (cm -1 ) Calculated: MP2/ G** Scaled: OH = 0.945, CH/NH = 0.957, below 2000 cm -1 = Alcohol Isotopologues Case 1: ND OH Case 2: NH OD

Photon Energy (cm -1 ) Predissociation Yield, Calculated Intensity Calculated: MP2/ G** Scaled: OH = 0.945, CH/NH = 0.957, below 2000 cm -1 = Alcohol Isotopologues

Photon Energy (cm -1 ) Predissociation Yield, Calculated Intensity ~ X 4 Laser Power Alcohol Isotopologues

Photon Energy (cm -1 ) Predissociation Yield, Calculated Intensity Ester Isotopologues Woof, woof!!

Conclusions/Future Work Revealed signature carbonyl of O ether H-bond interaction NH stretching region complicated through couplings to other oscillators and possibly dark states - Can we tune through these by making Δ PA even smaller? Can the shared proton launch a chemical reaction?

Acknowledgements Labmates: Past and Current Mark: New science, new hobbies! Tom Lectka’s group at JHU for making the molecules! Ken Jordan for help with calculations Anne McCoy for useful conversations about anharmonicity Funding: National Science Foundation, Air Force