Mapping the electronic resonances of single molecule STM ... - AtMol

Mapping the electronic resonances of single molecule STM tunnel junctionW.–H. Soe 1 , C. Manzano 1 and C. Joachim 1,2 1IMRE, A*STAR, Singapore2GNS-CEMES, CNRS, France

outline• STM with single molecule• molecular states imaging• simple to complex

Pentacene/Cu (J.Lagoute et al. PDI)Pentacene/NaCl/Cu(J.Repp et al. IBM)*Neaton et al. PRL97 (216405) 2006

Pentacene/Cu (J.Lagoute et al. PDI)Pentacene/NaCl/Cu(J.Repp et al. IBM)Cu Ag AuNaClSi-Hourplayground!*Neaton et al. PRL97 (216405) 2006

HOMO@NaCl (IBM)LUMO@NaCl (IBM)

3D theoretical imagein the gap(HOMO & HOMO-1)HOMO-2HOMO-1HOMOESQCSUMexperiment

Pentacene• D2h symmetry• each state: well separated• no degeneracyCu-Phthalocyanine• D4h symmetry• each state: well separated• two states: degenerate(LUMO & LUMO+1)

C4ground state1st excited statesC4C4 C2 C2HOMOLUMO & LUMO+1(degenerated)

ground state

1st excited statesgold surface plays as a jellium,i.e. not considered its structural factor.thinking aboutadsorption sitesadsorption sites

adsorption sitesfcc(111) grid

C2C4950mV1000mV1100mV

C2C4950mV1000mV1100mVbridge-site or on-top site

18E. R. Johnson and otherswater (Esler et al. in press) typically show a shock downstream of the ridgefollowed by a wavetrain of finite-amplitude Poincare waves of limiting amplitude(Shrira 1981, 1986; Grimshaw et al. 1998b). Numerical integrations (not shownhere) of a fully nonlinear, finite-volume, shallow water model show shocksappearing behind obstacles in non-dispersive rotating flows, providing furtherevidence of the nonlinearity of the sharp-crested waves of figure 5. Theexperiments of figure 5 also show that rotation confines the wake to within adistance of order the internal Rossby radius, c 0 /f for critical speed c 0 and Coriolisparameter f, of the axis. More rapid rotation confines the wake more closely tothe axis and experiments for rotation periods of TZ60 s and TZ90 s (so fZ0.06,0.08 s K1 ), giving Rossby radii of 50 and 75 cm, gave a clearly visible wake withlittle signature away from the axis and so not shown here.The presentation of the experimental results as a fixed wave pattern travellingwith the obstacle assumes that the flow has had sufficient time to become steadybefore the waves arrive at the probe spar. The obstacle reaches the spar in themiddle of the tank in non-dimensional time in the range tZ3.8–6.4, althoughwaves forming the outer edges of the pattern can take twice as long to arrive.Some indication of the extent to which this is sufficient for nonlinear bow wavesto develop may be gauged from figure 9, which shows the temporal developmentof the bow waves in the case of the non-rotating multiple bow wave numericalsolution with hZ5 cm, UZ13.5 cm s K1 . The steady state for this experiment isshown in figure 7 (right panel). Figure 9 shows the wavefield at tZ2, 4 and 8. AttZ2 a single bow wave has separated from the dispersive wake, while by tZ4 asecond bow wave has begun to separate. It is not until tZ8, however, that thebow wave pattern begins to resemble the final state shown in figure 7 (rightpanel). It is clear, therefore, that although significant development of nonlinearbow waves has taken place by the time the wave pattern passes the probe spar inthe experiments, it is by no means certain that the bow wave pattern hasattained its steady state. Experiments intended to detect multiple bow wavepatterns would thus need careful design to ensure that t is sufficiently large whenmeasurements are taken.This work was funded by the UK Natural Environment Research Council GrantNER/A/S/2000/01323 and under the European Union contract HPRI-2001-CT-00168, ‘Accessto Research Infrastructures’ of the program ‘Improving Human Potential’. The authors aregrateful to Henri Didelle and Samuel Viboud for their expert technical assistance.ReferencesAkylas, T. R. 1994 Three-dimensional long water-wave phenomena. Ann. Rev. Fluid Mech. 26,191–210. (doi:10.1146/annurev.fl.26.010194.001203)Benjamin, T. 1967 Internal waves of permanent form in fluids of great depth. J. Fluid Mech. 29,559–592.Burk, S. D. & Haack, T. 1999 The dynamics of wave clouds upwind of coastal orography. Mon.Weather Rev. 28, 1438–1455.Davis, R. E. & Acrivos, A. 1967 Solitary internal waves in deep water. J. Fluid Mech. 29, 593–607.Durran, D. R. 2000 Small-amplitude coastally trapped disturbances and the reduced-gravityshallow-water approximation. Q. J. R. Meteorol. Soc. 126, 2671–2689. (doi:10.1256/smsqj.56903)Proc. R. Soc. A (2006)

LUMOLUMO+1

Pentacene• D2h symmetry• each state: well separated• no degeneracyCu-Phthalocyanine• D4h symmetry• each state: well separated• two states: degenerate(LUMO & LUMO+1)

Pentacene• D2h symmetry• each state: well separated• no degeneracyCu-Phthalocyanine• D4h symmetry• each state: well separated• two states: degenerate (LUMO & LUMO+1)• D6h symmetry• some states: close• degenerateHexabenzocoronene(HBC)

2nd excitedLUMO+1 statesground stateHOMO1st excitedLUMOstates

summarywe showed• from Pentacene, the way to disentangle the MOcomponents in higher resonance molecular states.• from Cu-Phthalocyanine, the tip-molecule interactionscapture the MO components of the molecular states asa mixture of different phases and weight contributions.• from HBC and its dimer, a STS resonance results froma complex contribution to the local conductance ofmany molecular states.

MPIP, GermanySynth.Mol.> Xinliang Feng& Klaus MuellenCEMES-CNRS, FranceESQC> Maricarmen GrioliaPM6-MO CI> Mohamed HliwaChristian Joachimthanks!IMRE, SingaporeSTM Exp.> Carlos ManzanoHon Seng Wong