The Interior of Single Molecules Wilson Ho University of California, Irvine

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The Interior of Single MoleculesWilson
HoUniversity of California, Irvine
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Imaging Single Atoms Molecules
? Scanning Tunneling Microscope (1982)

• Field Ion
• Microscope (1955)

Muller, Platinum Metals Rev. (1965).
Ohtani, Wilson, Chiang, Mate, PRL (1988).
? Laser Induced Fluorescence (1990)
Moerner Orrit, Science (1999)
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Why ?

• ? Structure ? where are the atoms and bonds?
• ? Function ? motions (vibration, rotation,
  translation)
• ? electron transfer (oxidation,
  reduction)
• ? energy transfer
  (e-vibrational coupling, IVR,
• radiative and nonradiative
  decay)
• ? Reactivity where, how, why?
• ? new synthesis
• Understand Control Chemistry!

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Seeing LUMO of Mg-Porphine
Seeing is Believing
STM Image _at_ 0.6 V
HF Calculations
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Visualization of Single Molecules
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Visualization of Single Molecules
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Scanning Tunneling Microscope (STM)
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Elastic vs. Inelastic Tunneling
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Single H Atom
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Chemical Identification Single Acetylene
Molecules on Cu(100)
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Inside Single Acetylene
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Structural Determination
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Single Molecule RotationAcetylene on Cu(001)
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Vibration-Rotation Coupling
Acetylene on Cu(001)
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C2HD Rotation on Cu(001)
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Acetylene Thermal Rotation
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Acetylene Thermal Rotation Rate
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Thermal DiffusionAcetylene on Cu(001) at 200 K
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Acetylene Thermal Hopping Rate
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Molecular Shuttle
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Making a Molecule
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Making Molecules One by One
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Singles Close-Up View
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Sub-Å Vibrational Spectroscopy
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Single Molecules Made
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Bonding Structure
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On-Top Manipulation
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Single Gold Atoms on NiAl(110)
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Gold Chains 1 to 20 Atoms
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Pd20 Chain DOS an e? in a 1-D Box
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Single CO Adsorption on 11-Atom Au Chain
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CO Adsorbed at End of 7-Atom Au Chain
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CuPc_at_2Au6
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Assembly of CuPc_at_2Au6
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Missed Trajectory
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The Right Gap for Molecular Bridge
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DOS maps for CuPc and CuPc_at_2Au1
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Perturbation of CuPc states by the Au atoms
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Tuning of Electronic States
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Beating the Diffraction Limit Atomic Scale
Optical Phenomena - from an ensemble to single
molecules
Electron Transfer via Photo-induced Tunneling
Tunneling Electron Induced Fluorescence
Zn-etioporphyrin
Mg-porphine
Al2O3/NiAl
(LUMO1)
(LUMO e? )
h?
e?
relax ?
electron transfer probability shows spatial
variations inside molecule
vibronically resolved fluorescence spectra from
electron tunneling at four points of molecule
spatially resolved electron tunneling ? ?(ro,to),
evolves in t ? final states (fluorescence or
charging) that depends on ?(ro,to)
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Acknowledgment

• Christian Bobisch Ning Liu Chi Chen Gary
  Mikaelian
• Xi Chen George Nazin
• Jennifer Gaudioso Niklas Nilius
• Jae Ryang Hahn Naoki Ogawa
• Ungdon Ham Nilay Pradhan
• Qing Huan Xiaohui Qiu
• Xiaoming Huang Mohamad Rezaei
• Martin Janson Christophe Silien
• Jeelung Jiang Barry Stipe
• Ying Jiang Freddy Toledo
• Kiyeo Kim Xiuwen Tu
• Markus Lackinger Mitch Wallis
• Lincoln Lauhon Shiwei Wu
• Hyojune Lee Wendong Xing
• Joonhee Lee Shichao Yan