Abortive reaction leads to selective adsorbate rotation.

Electron-induced dissociation of a fluorocarbon adsorbate CF3 (ad) at 4.6 K is shown by Scanning Tunnelling Microscopy (STM) to form directed energetic F-atom 'projectiles' on Cu(110). The outcome of a collision between these directed projectiles and stationary co-adsorbed allyl 'target' molecules was found through STM to give rotational excitation of the target allyl, clockwise or anti-clockwise, depending on the chosen collision geometry. Molecular dynamics computation linked the collisional excitation of the allyl target to an 'abortive chemical reaction', in which the approach of the F-projectile stretched an H-C bond lifting the allyl above the surface, facilitating isomerization from 'Across' to 'Along' a Cu row.

Direct Observation of Knock-on in Surface Reactions at Zero Impact Parameter.

Reaction dynamics examines molecular motions in reactive collisions. The aiming of reagents at one another has been achieved at selected miss distances (impact parameters, b) by using the corrugations on crystalline surfaces as collimator. Prior experimental work and ab initio calculation showed single atoms aimed at chemisorbed molecules with b = 0 gave knock-on of atomic reaction products through a linear transition state. Here we report a study of b = 0 collision between directed CF2 and stationary chemisorbed CF3. Experiments and ab initio calculations again show linear reaction with a linear transition state, despite the additional degrees of freedom for CF2. The directed motion of CF2 is conserved through this linear transition state. Conservation of directionality is evidenced experimentally by the observation of a knock-on chain reaction along a line of chemisorbed CF3.

Contrasting Efficiency of Electron-Induced Reaction at Cu(110) in Aliphatic and Aromatic Bromides.

We report a comparative study of the electron-induced reaction of pentyl bromide (PeBr) and phenyl bromide (PhBr) on Cu(110) at 4.6 K, observed by scanning tunneling microscopy (STM). The induced dissociation of the intact adsorbed molecule for both reagents occurred at an energy of 2.0 eV, producing a hydrocarbon radical and a Br atom. Electron-induced C-Br bond dissociation was found to be a single-electron process for both reagents. The impulsive two-state (I2S) model was used to describe the Br atom recoil as due to molecular excitation to a repulsive anti-bonding state, in which recoil of the dissociation products occurred due to C·Br repulsion along the prior C-Br bond direction. The measured reaction yield was 3 orders of magnitude greater for PeBr, 2.0 × 10-7 reactive events per electron, than for PhBr with a yield of 1.7 × 10-10. The low yield of dissociation products from the aromatic PhBr was attributed to the presence of two additional anionic states below the 2.0 eV energy limit, absent for the aliphatic PeBr; these additional anionic states for PhBr could provide a pathway for electron transfer to the surface in the case of the aromatic, but not the aliphatic, anion. The consequent shorter lifetime of the repulsive aromatic anion of PhBr is consistent with the observation of shorter mean recoil distance (3.2 Å) of its Br dissociation product, as compared with the markedly longer recoil (8.7 Å) of Br observed from the anion of PeBr.

Electron-induced molecular dissociation at a surface leads to reactive collisions at selected impact parameters.

Crossed molecular beams of gases have provided definitive information concerning the dynamics of chemical reactions. The results have, however, of necessity been averaged over collisions with impact parameters ranging from zero to infinity, thus obscuring the effect of this important variable. Here we employ a method through which impact parameter averaging is suppressed in a surface reaction. We aim a highly collimated reactive 'projectile' molecule along a surface at a stationary adsorbed 'target' molecule, with both the projectile and target being observed by Scanning Tunnelling Microscopy (STM). The projectile was CF2 recoiling from electron-induced bond-breaking in chemisorbed CF3 on Cu(110) at 4.6 K. The collimation of the resulting CF2 'surface-molecular-beam' restricted it to a lateral spread of ±1° as a consequence of its interaction with the Cu rows below. This collimation was modelled by molecular dynamics simulations. In the experiments the recoiling CF2 projectile was aimed, successively, at impact parameters of b = 0 and +3.6 Å at a chemisorbed second CF2, b = +1.8 Å at a chemisorbed I-atom, or b = -4.0, b = -0.4 and b = +3.2 Å at a chemisorbed vinyl radical. The pattern of reactive and non-reactive scattering was determined by STM. These collimated surface-molecular-beams have the potential to aim molecular projectiles with selected impact parameters at the many target species identifiable at a surface by STM.

Direct and Delayed Dynamics in Electron-Induced Surface Reaction.

The electron-induced reaction of physisorbed vinyl bromide (ViBr) and allyl bromide (AllBr) on Cu(110) at 4.6 K was studied experimentally by scanning tunneling microscopy and theoretically by molecular dynamics. ViBr and AllBr were found to react by two pathways: "Direct", in which the molecule reacted under the tip, and "Delayed", in which reaction occurred spontaneously after the molecule had diffused across the surface away from the tip. The novel pathway of Delayed reaction constituted a major route for both vinyl bromide (68%) and allyl bromide (53%). The observed reaction dynamics for ViBr and AllBr gave evidence of a long-lived vibrationally excited intermediate for both Direct and Delayed reactions. Molecular dynamics simulations with reagent excitation by way of selected vibrational normal modes resulted in either Direct or Delayed reaction, depending on the vibrational mode.

Clocking Surface Reaction by In-Plane Product Rotation.

Electron-induced reaction of physisorbed meta-diiodobenzene (mDIB) on Cu(110) at 4.6 K was studied by Scanning Tunneling Microscopy and molecular dynamics theory. Single-electron dissociation of the first C-I bond led to in-plane rotation of an iodophenyl (IPh) intermediate, whose motion could be treated as a "clock" of the reaction dynamics. Alternative reaction mechanisms, successive and concerted, were observed giving different product distributions. In the successive mechanism, two electrons successively broke single C-I bonds; the first C-I bond breaking yielded IPh that rotated directionally by three different angles, with the second C-I bond breaking giving chemisorbed I atoms (#2) at three preferred locations corresponding to the C-I bond alignments in the prior rotated IPh configurations. In the concerted mechanism a single electron broke two C-I bonds, giving two chemisorbed I atoms; significantly these were found at angles corresponding to the C-I bond direction for unrotated mDIB. Molecular dynamics accounted for the difference in reaction outcomes between the successive and the concerted mechanisms in terms of the time required for the IPh to rotate in-plane; in successive reaction the time delay between first and second C-I bond-breaking events allowed the IPh to rotate, whereas in concerted reaction the computed delay between excitation and reaction (∼1 ps) was too short for molecular rotation before the second C-I bond broke. The dependence of the extent of motion at a surface on the delay between first and second bond breaking suggested a novel means to "clock" sub-picosecond dynamics by imaging the products arising from varying time delays between impacting pairs of electrons.

Imprinting self-assembled patterns of lines at a semiconductor surface, using heat, light, or electrons.

The fabrication of nano devices at surfaces makes conflicting demands of mobility for self-assembly (SA) and immobility for permanence. The solution proposed in earlier work from this laboratory involved pattern formation in physisorbed molecules by SA, followed by localized reaction to chemically imprint the pattern substantially unchanged, a procedure we termed molecular-scale imprinting (MSI). Here, as proof of generality we extended this procedure, previously applied to imprinting circles on Si(111)-7 × 7, to SA lines of 1-chloropentane (CP) on Si(100)-2 × 1. The physisorbed lines consisted of pairs of CP that grew perpendicular to the Si dimer rows, as shown by scanning tunneling microscopy and ab initio theory. Chemical reaction of these lines with the surface was triggered in separate experiments by three different modes of energization: heat, electrons, or light. In all cases the CP molecules underwent MSI with a Si atom beneath so that the physisorbed lines of CP pairs were imprinted as chemisorbed lines of Cl pairs.

Single-electron induces double-reaction by charge delocalization.

Injecting an electron by scanning tunneling microscope into a molecule physisorbed at a surface can induce dissociative reaction of one adsorbate bond. Here we show experimentally that a single low-energy electron incident on ortho-diiodobenzene physisorbed on Cu(110) preferentially induces reaction of both of the C-I bonds in the adsorbate, with an order-of-magnitude greater efficiency than for comparable cases of single bond breaking. A two-electronic-state model was used to follow the dynamics, first on an anionic potential-energy surface (pes*) and subsequently on the ground state pes. The model led to the conclusion that the two-bond reaction was due to the delocalization of added charge between adjacent halogen-atoms of ortho-diiodobenzene through overlapping antibonding orbitals, in contrast to the cases of para-dihalobenzenes, studied earlier, for which electron-induced reaction severed exclusively a single carbon-halogen bond. The finding that charge delocalization within a single molecule can readily cause concerted two-bond breaking suggests the more general possibility of intra- and also intermolecular charge delocalization resulting in multisite reaction. Intermolecular charge delocalization has recently been proposed by this laboratory to account for reaction in physisorbed molecular chains (Ning, Z.; Polanyi, J. C. Angew. Chem., Int. Ed. 2013, 52, 320-324).

Charge delocalization induces reaction in molecular chains at a surface.

The molecular dynamics of an electron-induced reaction in a self-assembled molecular chain of four dimethyldisulfide molecules on Au(111) are studied. Charge delocalization weakens all the S-S bonds causing a concurrent reaction along the entire chain. All the original S-S bonds are broken and new S-S bonds form giving three altered S-S bonds and two chemisorbed thiyl radicals.

Localized reaction at a smooth metal surface: p-diiodobenzene at Cu(110).

Halogenation at a semiconductor surface follows simple dynamics characterized by "localized reaction" along the direction of the halide bond being broken. Here we extend the study of halide reaction dynamics to the important environment of a smooth metal surface, where greater product mobility would be expected. Extensive examination of the physisorbed reagent and chemisorbed products from two successive electron-induced reactions showed, surprisingly, that for this system product localization and directionality described the dynamics at a metal. The reagent was p-diiodobenzene on Cu(110) at 4.6 K. The first C-I bond-breaking yielded chemisorbed iodophenyl and I-atom(#1), and the second yielded phenylene and I-atom(#2). The observed collinear reaction resulted in secondary encounters among products, which revealed the existence of a surface-aligned reaction. The molecular dynamics were well explained by a model embodying a transition between an a priori ground state and a semiempirical ionic state, which can be generally applied to electron-induced chemical reactions at surfaces.

Surface aligned reaction.

This paper reflects on three decades during which the study of surface aligned reaction (SAR) has advanced. The objective in SAR, which in considerable part still lies ahead, is the simultaneous control of atomic and molecular "collision energies, collision angles, and impact parameter." Following a discussion of the benefits of such an approach we review the progress made, and, as a stimulus to experiment, present new calculations of SAR dynamics for bimolecular reaction at a metal surface. It seems reasonable to suppose that we are now entering a decade in which a combination of scanning tunneling microscopy and femtosecond laser spectroscopy will bring the full realisation of SAR.

Molecular calipers control atomic separation at a metal surface.

If a molecule controls the length of some other moiety, it can be termed a "molecular caliper". Here we image individual molecular calipers of this type by scanning tunneling microscopy. These consist of linear polymers of p-diiodobenzene, (pDIB)n, of varying length, 0.7-2.9 nm, physisorbed on Cu(110) at 4.6 K. Through electron-induced reaction these chemically imprint their terminal I-atoms on the copper, 0.7 nm further apart than their initial separations. The physisorbed monomer or polymer, therefore, constitutes a molecular-caliper with variable terminal I..I separation. The localized nature of the I-atom reaction at the copper surface relative to the parent molecule, constitutes a novel finding reported here. It ensures that the separation of the I-atoms in the physisorbed molecular caliper correlates with their subsequent separation when chemisorbed at the surface.

Adsorbate alignment in surface halogenation: standing up is better than lying down.

Bromine atom transfer to a silicon surface as a function of physisorbed adsorbate alignment (see picture: left, vertical 1-bromopentane; right, horizontal 1-bromopentane) of 1-bromopropane and 1-bromopentane on Si(111)-7×7 has been studied by STM. In both thermal and electron-induced bromination reactions, the vertical alignment is more reactive.

Multiple pathways of dissociative attachment: CH3Br on Si(100)-2×1.

We describe the dissociative attachment (DA) of methyl bromide to form chemisorbed CH(3) and Br on a Si(100)-2×1 surface at 270 K. The patterns of DA were studied experimentally by ultra-high vacuum scanning tunneling microscopy (STM) and interpreted by ab initio theory. The parent molecules were found to dissociate thermally by breaking the C-Br bond, attaching the resulting fragments CH(3) and Br at adjacent Si-atom sites. The observed DA resulted in three distinct attachment geometries: inter-row (IR, 88%), inter-dimer (ID, 11%), and on-dimer (OD, 1%). Ab initio computation agreed in predicting these three DA reaction pathways, with yields decreasing down the series, in accord with experiment. The three computed physisorption geometries, each of which correlated with a preferred outcome, IR, ID, or OD, exhibited similar heats of adsorption, the choice of pathway being governed by the energy barriers to DA chemisorption predicted to increase along the series: E(IR) = 0.48 eV, E(ID) = 0.57 eV, and E(OD) = 0.63 eV.

Facile charge-displacement at silicon gives spaced-out reaction.

Adsorbates on metals, but not previously on semiconductors, have been observed to display long-range repulsive interactions. On metals, due to efficient dissipation, the repulsions are weak, typically on the order of 5 meV at 10 Å. On the 7×7 reconstruction of the Si(111) surface, charge transport through the surface has been demonstrated by others using charge injection by STM tips. Here we show that for both physisorbed brominated molecules, and for chemisorbed Br-atoms, induced charge-transfer in the Si(111)-7×7 surface can lead to a strong repulsive interaction between adsorbates, calculated as 200 meV at 13.4 Å. This large repulsive interaction must be channeled through the surface since it causes widely spaced "one-per-corner-hole" patterns of physisorption (three cases--directly observed here) and subsequent chemisorption (four cases observed). The patterns were observed by ultrahigh vacuum scanning tunneling microscopy for four different brominated hydrocarbon adsorbates; 1,2-dibromoethane, 1-bromopropane, 1-bromopentane, and bromobenzene, deposited individually on the surface. In every case, adsorbates were overwhelmingly more likely to be found singly than multiply adjacent to a corner-hole, constituting a distinctive pattern having a probability p = 7 × 10(-5) compared to a random distribution.

Reversible 1D chain-reaction gives rise to an atomic-scale Newton's cradle.

An F-atom with ∼1 eV translational energy was aimed at a line of fluorocarbon adsorbates on Cu(110). Sequential 'knock-on' of F-atom products was observed by STM to propagate along the 1D fluorocarbon line. Hot F-atoms travelling along the line in six successive 'to-and-fro' cycles paralleled the rocking of a macroscopic Newton's cradle.

Long-range migration of H-atoms from electron-induced dissociation of HS on Si(111).

The electron-induced dissociation of chemisorbed HS to give recoiling H-atoms was investigated on a Si(111)-7 × 7 surface at 270 K by scanning tunnelling microscopy and modelled by density functional theory. Two different H-atom migratory pathways were identified: 'short-range' (S-R; 37%) and 'long-range' (L-R; 42%). In S-R reaction the H-atom recoiled by only 4 Å whereas in L-R the average H-recoil distance was 17 Å extending up to 72 Å. Chemisorbed H-atoms were not detected in the remaining 22% of dissociative events. Excitation involved three successive events, e-+ HS. Molecular dynamics calculations of S-R and L-R recoil of H-atoms were performed using a model based on electron-induced H ⋅ S repulsion. In S-R the repulsion gave the H-atom sufficient energy to dissociate HS, but not enough to result in capture of the H-atom by the adjacent rest Si-atom. In L-R a higher translational energy of the recoiling H, above 0.2 eV, caused the H-atom to 'bounce' off surface atoms and migrate L-R. The finding that H-atom L-R migration followed the ballistics and 'bounce' mechanism is indicative of the generality of this mode of L-R recoil.

Direct observation of knock-on reaction with umbrella inversion arising from zero-impact-parameter collision at a surface.

In Surface-Aligned-Reactions (SAR), the degrees of freedom of chemical reactions are restricted and therefore the reaction outcome is selected. Using the inherent corrugation of a Cu(110) substrate the adsorbate molecules can be positioned and aligned and the impact parameter, the collision miss-distance, can be chosen. Here, substitution reaction for a zero impact parameter collision gives an outcome which resembles the classic Newton's cradle in which an incident mass 'knocks-on' the same mass in the collision partner, here F + CF3 → (CF3)' + (F)' at a copper surface. The mechanism of knock-on was shown by Scanning Tunnelling Microscopy to involve reversal of the CF3 umbrella as in Walden inversion, with ejection of (F)' product along the continuation of the F-reagent direction of motion, in collinear reaction.

Approaching the forbidden fruit of reaction dynamics: Aiming reagent at selected impact parameters.

Collision geometry is central to reaction dynamics. An important variable in collision geometry is the miss-distance between molecules, known as the "impact parameter." This is averaged in gas-phase molecular beam studies. By aligning molecules on a surface prior to electron-induced dissociation, we select impact parameters in subsequent inelastic collisions. Surface-collimated "projectile" molecules, difluorocarbene (CF2), were aimed at stationary "target" molecules characterized by scanning tunneling microscopy (STM), with the observed scattering interpreted by computational molecular dynamics. Selection of impact parameters showed that head-on collisions favored bimolecular reaction, whereas glancing collisions led only to momentum transfer. These collimated projectiles could be aimed at the wide variety of adsorbed targets identifiable by STM, with the selected impact parameter assisting in the identification of the collision geometry required for reaction.