Role of molecular electronic structure in inelastic electron tunneling spectroscopy:<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mtext>O</mml:mtext><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:math>on Ag(110)

Monturet, Serge; Alducin, M.; Lorente, Nicolás

doi:10.1103/physrevb.82.085447

Cited by 30 publications

(50 citation statements)

References 54 publications

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“…One paradigmatic test case of this kind is the scattering of vibrationally excited NO molecules off the Au(111) surface, [10,[16][17][18][19][20][21][22][23][24][25] where both neutral (NO/Au) and negative ion (NO 2 /Au 1 ) molecular states appear to be involved and coupled to the continuum of metal e-h excitations, resulting in a rather fast vibrational de-excitation of the projectile molecules.…”

Section: Electronic Frictionmentioning

confidence: 99%

Classical and quantum dynamics at surfaces: Basic concepts from simple models

Bonfanti

Martinazzo

2016

Int J of Quantum Chemistry

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Elementary processes involving atomic and molecular species at surfaces are reviewed. The emphasis is on simple classical and quantum models that help to single out unifying dynamical themes and to identify the basic physical mechanisms that underlie the rich variety of phenomena of surface chemistry. Starting from an elementary description of the energy transfer between a gas‐phase species and a surface—for both classical and quantum lattices—the key processes establishing the formation of an adsorbed phase (sticking, diffusion and vibrational relaxation) are discussed. This is instrumental for introducing the simplest chemical transformations involving adsorbed species and/or scattering of gas‐phase molecules: Langmuir–Hinshelwood, Hot‐Atom, and Eley–Rideal reactions forming complex molecules from elementary constituents, and dissociative chemisorption of molecules into smaller fragments. Applications are also provided illustrating the ideas developed along the way at work in real‐world gas‐surface problems.

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Section: Electronic Frictionmentioning

confidence: 99%

Classical and quantum dynamics at surfaces: Basic concepts from simple models

Bonfanti

Martinazzo

2016

Int J of Quantum Chemistry

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“…In addition to hydrocarbon molecules, vibrational modes of simple molecules such as CO and O 2 on metal surfaces have also been reported using STM with atomic spatial resolution [71][72][73]. Following these experimental findings, theory has progressed based on the short-range interactions between the tunneling electrons and the vibrational mode [74][75][76][77][78][79][80]. State-of-the-art theory was able to reproduce the features observed by experiment, for example, preferential observation of C-H stretching signal for acetylene molecules [74].…”

Section: Inelastic Electron Tunneling Spectroscopymentioning

confidence: 99%

Inelastic electron tunneling process for alkanethiol self-assembled monolayers

Okabayashi

Paulsson

Komeda

2013

Progress in Surface Science

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Recent investigations of inelastic electron tunneling spectroscopy (IETS) for alkanethiol self-assembled monolayers (SAMs) are reviewed. Alkanethiol SAMs are usually prepared by immersing a gold substrate into a solution of alkanethiol molecules, and they are very stable, even under ambient conditions. Thus, alkanethiol SAMs have been used as typical molecules for research into molecular electronics. Infrared spectroscopy and electron energy loss spectroscopy (EELS) have frequently been employed to characterize SAMs on the macroscopic scale. For characterization of alkanethiol SAMs on the nanometer scale region, or for single alkanethiol molecules through which electrons actually tunnel, IETS has proven to be an effective method. However, IETS experiments for alkanethiol SAMs employing different methods have shown large differences, i.e., there is a lack of standard data for alkanethiol SAMs with which to understand the IET process or to satisfactorily compare with theoretical investigations.An effective means of acquiring standard data is the formation of a tunneling junction with scanning tunneling microscopy (STM). After explanation of the STM experimental techniques, standard IETS data are presented whereby a contact condition between the tip and SAM is tuned. We have found that many vibrational modes are detected by STM-IETS, as is also the case for EELS. These results are compared with IET spectra measured with different tunneling junctions. In order to precisely investigate which vibrational modes are active in IETS, isotope labeling of alkanethiols with specifically synthesized isotopically substituted molecule has been examined. This method provides unambiguous assignments of IET spectra peaks and site selectivity for alkanethiol SAMs such that all parts of the alkanethiol molecules almost equally contribute to the IET process. The IET process is also discussed based on density functional theory and nonequilibrium Green's function calculations. These results quantitatively reproduce many the experimentally observed features, whereas Fermi's golden rule for IETS qualitatively explains the propensity rule and site selectivity observed in the experiments. However, comparison between experiment and theory reveals a large difference in IETS intensity for the C-H stretching mode that originates from the side chains of the alkanethiol molecules. In order to explain this difference, we discuss the importance of an intermolecular tunneling process in the SAM. Application of STM-IETS to identify a hydrogenated alkanethiol molecule inserted into a deuterated alkanethiol SAM matrix is also demonstrated.

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“…Density functional theory (DFT) calculations by Gravil et al [40][41][42] studied the underlying electronic structure of the O 2 -surface bond and confirmed the chemisorption geometry observed by experiment. Molecular dynamics simulations by Pazzi et al 43,44 investigated the incidence-energydependent and coverage-dependent sticking probabilities of O 2 on Ag(110), and more recently, DFT calculations by Olsson et al, 45 Alducin et al, 46 and Monturet et al 47 studied the STM images and IETS of O 2 on Ag(110).…”

Section: Introductionmentioning

confidence: 98%

Chemistry at molecular junctions: Rotation and dissociation of O2 on the Ag(110) surface induced by a scanning tunneling microscope

Roy

Mújica

Ratner

2013

The Journal of Chemical Physics

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The scanning tunneling microscope (STM) is a fascinating tool used to perform chemical processes at the single-molecule level, including bond formation, bond breaking, and even chemical reactions. Hahn and Ho [J. Chem. Phys. 123, 214702 (2005)] performed controlled rotations and dissociations of single O2 molecules chemisorbed on the Ag(110) surface at precise bias voltages using STM. These threshold voltages were dependent on the direction of the bias voltage and the initial orientation of the chemisorbed molecule. They also observed an interesting voltage-direction-dependent and orientation-dependent pathway selectivity suggestive of mode-selective chemistry at molecular junctions, such that in one case the molecule underwent direct dissociation, whereas in the other case it underwent rotation-mediated dissociation. We present a detailed, first-principles-based theoretical study to investigate the mechanism of the tunneling-induced O2 dynamics, including the origin of the observed threshold voltages, the pathway dependence, and the rate of O2 dissociation. Results show a direct correspondence between the observed threshold voltage for a process and the activation energy for that process. The pathway selectivity arises from a competition between the voltage-modified barrier heights for rotation and dissociation, and the coupling strength of the tunneling electrons to the rotational and vibrational modes of the adsorbed molecule. Finally, we explore the "dipole" and "resonance" mechanisms of inelastic electron tunneling to elucidate the energy transfer between the tunneling electrons and chemisorbed O2.

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Role of molecular electronic structure in inelastic electron tunneling spectroscopy:O2on Ag(110)

Cited by 30 publications

References 54 publications

Classical and quantum dynamics at surfaces: Basic concepts from simple models

Classical and quantum dynamics at surfaces: Basic concepts from simple models

Inelastic electron tunneling process for alkanethiol self-assembled monolayers

Chemistry at molecular junctions: Rotation and dissociation of O2 on the Ag(110) surface induced by a scanning tunneling microscope

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