Chiara Baldacchini

Core-shell photoabsorption and photoelectron spectra of gas-phase pentacene: experiment and theory.

The C K-edge photoabsorption and 1s core-level photoemission of pentacene (C22H14) free molecules are experimentally measured, and calculated by self-consistent-field and static-exchange approximation ab initio methods. Six nonequivalent C atoms present in the molecule contribute to the C 1s photoemission spectrum. The complex near-edge structures of the carbon K-edge absorption spectrum present two main groups of discrete transitions between 283 and 288 eV photon energy, due to absorption to pi* virtual orbitals, and broader structures at higher energy, involving sigma* virtual orbitals. The sharp absorption structures to the pi* empty orbitals lay well below the thresholds for the C 1s ionizations, caused by strong excitonic and localization effects. We can definitely explain the C K-edge absorption spectrum as due to both final (virtual) and initial (core) orbital effects, mainly involving excitations to the two lowest-unoccupied molecular orbitals of pi* symmetry, from the six chemically shifted C 1s core orbitals.

Adsorption of pentacene on filled d-band metal surfaces: Long-range ordering and adsorption energy

The growth of pentacene on suitable metallic templates is studied by means of low-energy electron diffraction and ultraviolet photoelectron spectroscopy. Highly ordered pentacene single layers can be prepared by deposition on filled d-band metal templates kept at 370 K. The presence of the steps for the Cu(119) vicinal surface and of the Au troughs for the Au(110)-(1 x 2) surface allows the formation of commensurate long-range ordered structures with (3 x 7) and (3 x 6) periodicities, respectively. A detailed analysis of the molecular induced electronic states evolution is performed for different growth morphologies. The adsorption energy of the ordered molecular single layers on the Au(110) surface is lower (1.90 eV) than on the Cu vicinal surface (2.36 eV), where the steps enhance the molecule adsorption energy.

Yeast cytochrome c integrated with electronic elements: a nanoscopic and spectroscopic study down to single-molecule level

Various aspects of redox protein integration with nano-electronic elements are addressed by a multi-technique investigation of different yeast cytochrome c (YCC)-based hybrid systems. Three different immobilization strategies on gold via organic linkers are explored, involving either covalent bonding or electrostatic interaction. Specifically, Au surfaces are chemically modified by self-assembled monolayers (SAMs) exposing thiol-reactive groups, or by acid-oxidized single-wall carbon nanotubes (SWNTs). Atomic force microscopy and scanning tunnelling microscopy are employed to characterize the morphology and the electronic properties of single YCC molecules adsorbed on the modified gold surfaces. In each hybrid system, the protein molecules are stably assembled, in a native configuration. A standing-up arrangement of YCC on SAMs is suggested, together with an enhancement of the molecular conduction, as compared to YCC directly assembled on gold. The electrostatic interaction with functionalized SWNTs allows several YCC adsorption geometries, with a preferential high-spin haem configuration, as outlined by Raman spectroscopy. Moreover, the conduction properties of YCC, explored in different YCC nanojunctions by conductive atomic force microscopy, indicate the effectiveness of electrical conduction through the molecule and its dependence on the electrode material. The joint employment of several techniques confirms the key role of a well-designed immobilization strategy, for optimizing biorecognition capabilities and electrical coupling with conductive substrates at the single-molecule level, as a starting point for advanced applications in nano-biotechnology.

Molecular gap and energy level diagram for pentacene adsorbed on filled d-band metal surfaces

The authors present a combined photoemission and scanning-tunneling spectroscopy study of the filled electronic states, the molecular energy gap, and the energy level diagram of highly ordered arrays of pentacene deposited on the Cu(119) vicinal surface. The states localized at the interface are clearly singled out, comparing the results at different pentacene thicknesses and with gas-phase photoemission data. The molecular gap of 2.35eV, the hole injection barrier of 1.05eV, and the electron injection barrier of 1.30eV determine the energy level diagram of the states localized at the pentacene molecules.

Conductive atomic force microscopy investigation of transverse current across metallic and semiconducting single-walled carbon nanotubes

The comprehension of conduction mechanisms in single-walled carbon nanotubes is a crucial task for developing efficient nanodevices. Appealing hybrid architectures could exploit charge transport perpendicular to the main nanotube axis in order to minimize carrier path and phonon scattering effects. Such transverse transport is investigated in metallic and semiconducting nanotubes by means of conductive atomic force microscopy. The transverse current response is interpreted in the framework of a tunneling transport model, and reveals that conduction across metallic nanotubes is either tunneling- or bandlike, depending on the force applied by the tip, while charge carriers always tunnel through the semiconducting nanotubes.

Conductive atomic force microscopy study of single molecule electron transport through the Azurin-gold nanoparticle system

Transduction of biorecognition events into electrical signals through integration of single redox metalloproteins in bioelectronic nanodevices requires both a reliable electrical contact between the biomolecule and the metallic electrode and an efficient overall conduction mechanism. These conditions have been met in the hybrid system obtained by linking gold nanoparticles on top of Azurin proteins, in turn assembled on gold surfaces. Such an assembling strategy, combined with a conductive atomic force microscopy investigation, has allowed us to put into evidence an unprecedented matching between current and topography features and to attribute the intramolecular charge transport to a non-resonant tunnelling mechanism.

Electron tunnelling through single azurin molecules can be on/off switched by voltage pulses

Redox metalloproteins are emerging as promising candidates for future bio-optoelectronic and nano-biomemory devices, and the control of their electron transfer properties through external signals is still a crucial task. Here, we show that a reversible on/off switching of the electron current tunnelling through a single protein can be achieved in azurin protein molecules adsorbed on gold surfaces, by applying appropriate voltage pulses through a scanning tunnelling microscope tip. The observed changes in the hybrid system tunnelling properties are discussed in terms of long-sustained charging of the protein milieu.

Growth of 2-mercaptobenzoxazole on Cu(1 0 0) surface: chemisorbed and physisorbed phases

We present a high-resolution UV photoelectron spectroscopy study of 2-mercaptobenzoxazole (MBO) adsorbed on clean Cu(1 0 0), by sublimation in controlled ultra-high-vacuum conditions, at room temperature and at 100 K. The photoemission data show the formation of an MBO layer chemically interacting with the copper substrate. Saturation coverage is achieved at room temperature with the chemisorbed phase, while a physisorbed multilayer is formed at low temperatures on top of the chemisorbed interfacial layer. 2002 Elsevier Science B.V. All rights reserved.

Excitation of the ligand-to-metal charge transfer band induces electron tunnelling in azurin

Optical excitation of azurin blue copper protein immobilized on indium-tin oxide, in resonance with its ligand-to-metal charge transfer absorption band, resulted in a light-induced current tunnelling within the protein milieu. The related electron transport rate is estimated to be about 105 s−1. A model based on resonant tunnelling through an azurin excited molecular state is proposed. The capability of controlling electron transfer processes through light pulses opens interesting perspectives for implementation of azurin in bio-nano-opto-electronic devices.

Vibrational Changes Induced by Electron Transfer in Surface Bound Azurin Metalloprotein Studied by Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy

The copper protein azurin, due to the peculiar coupling of its optical and vibronic properties with electron transfer (ET) and its biorecognition capabilities, is a very promising candidate for bioelectronic, bio-optoelectronic and biosensor applications. However, a complete understanding of the fundamental processes relating azurin ET and its optical and vibronic characteristics with the charge transport mechanisms occurring in proteins bound to a conductive surface, the typical scenario for a biosensor or bioelectronic component, is still lacking. We studied azurin proteins bound to a gold electrode surface by scanning tunneling microscopy combined with tip-enhanced Raman spectroscopy (STM-TERS). Robust TER spectra were obtained, and the proteins vibronic response under optical excitation in resonance with its ligand-to-metal charge transfer band was found to be affected by the tunneling parameters, indicating a direct involvement of the active site vibrations in the electron transport process.