Thijs Stuyver

Analysis of Aromaticity in Planar Metal Systems using the Linear Response Kernel.

The linear response kernel is used to gain insight into the aromatic behavior of the less classical metal aromatic E4(2-) and CE4(2-) (E = Al, Ga) clusters. The effect of the systematic replacement of the aluminum atoms in Al4(2-) and CAl4(2-) by germanium atoms is studied using, Al3Ge-, Al2Ge2, AlGe3+, Ge4(2+), CAl3Ge-, CAl2Ge2, CAlGe3+, and CGe4(2+). The results are compared with the values of the delocalization index (δ(1,3)) and nucleus independent chemical shifts (NICS(zz)). Unintegrated plots of the linear response, computed for the first time on molecules, are used to analyze the delocalization in these clusters. All aromaticity indices studied, the linear response, δ(1,3), and NICS(zz), predict that the systems with a central carbon are less aromatic than the systems without a central carbon atom. Also, the linear response is more pronounced in the σ-electron density than in the π-density, pointing out that the systems are mainly σ-aromatic.

Dioxygen: What Makes This Triplet Diradical Kinetically Persistent?

Experimental heats of formation and enthalpies obtained from G4 calculations both find that the resonance stabilization of the two unpaired electrons in triplet O2, relative to the unpaired electrons in two hydroxyl radicals, amounts to 100 kcal/mol. The origin of this huge stabilization energy is described within the contexts of both molecular orbital (MO) and valence-bond (VB) theory. Although O2 is a triplet diradical, the thermodynamic unfavorability of both its hydrogen atom abstraction and oligomerization reactions can be attributed to its very large resonance stabilization energy. The unreactivity of O2 toward both these modes of self-destruction maintains its abundance in the ecosphere and thus its availability to support aerobic life. However, despite the resonance stabilization of the π system of triplet O2, the weakness of the O-O σ bond makes reactions of O2, which eventually lead to cleavage of this bond, very favorable thermodynamically.

Conduction of molecular electronic devices: Qualitative insights through atom-atom polarizabilities

The atom-atom polarizability and the transmission probability at the Fermi level, as obtained through the source-and-sink-potential method for every possible configuration of contacts simultaneously, are compared for polycyclic aromatic compounds. This comparison leads to the conjecture that a positive atom-atom polarizability is a necessary condition for transmission to take place in alternant hydrocarbons without non-bonding orbitals and that the relative transmission probability for different configurations of the contacts can be predicted by analyzing the corresponding atom-atom polarizability. A theoretical link between the two considered properties is derived, leading to a mathematical explanation for the observed trends for transmission based on the atom-atom polarizability.

Enhancing the conductivity of molecular electronic devices

We show in this work that conjugated π-electron molecular chains can, in quite specific and understood circumstances, become more conductive the longer they get, in contradiction to what would be expected intuitively. The analysis, done in the framework of the source and sink potential method, and supported by detailed transmission calculations, begins by defining “relative transmission,” an inherent measure of molecular conduction. This, in turn, for conjugated hydrocarbons, is related to a simple molecular orbital expression—the ratio of secular determinants of a molecule and one where the electrode contacts are deleted—and a valence bond idea, since these secular determinants can alternatively be expressed in terms of Kekule structures. A plausible argument is given for relating the relative transmission to the weight of the diradical resonance structures in the resonance hybrid for a molecule. Chemical intuition can then be used to tune the conductivity of molecules by “pushing” them towards more or l...

Conductance Switching in Expanded Porphyrins through Aromaticity and Topology Changes

Expanded porphyrins are flexible enough to switch between different π-conjugation topologies, namely Möbius, Hückel and twisted-Hückel, each with distinct electronic properties and aromaticity. Since these switches can be induced by different external stimuli, expanded porphyrins represent a promising platform to develop a novel type of molecular switch for molecular electronic devices. In this work, the feasibility of conductance switches based on topology and/or aromaticity changes in expanded porphyrins is assessed for the first time. In particular, the electron transport properties of penta-, hexa- and heptaphyrins with different π-conjugation topologies and aromaticity were carefully investigated using the nonequilibrium Greens function formalism in combination with density functional theory for various configurations of the gold contacts. Our results highlight the importance of the macrocyclic aromaticity and connectivity and, to a lesser extent, the molecular topology, in determining the transmission functions and local currents. When the electrodes are connected along the longitudinal axis of the macrocycle, we found that aromaticity of Hückel expanded porphyrins increases single-molecule junction conductance, contrary to the negative relationship between conductance and aromaticity found in single five-membered rings. For this particular connectivity, antiaromatic Hückel structures with [4n] π-electrons exhibit a sharp reduction in transmission near the Fermi level due to destructive quantum interference between the HOMO and LUMO. Belt-shaped Möbius aromatic structures exhibit a lower conductance as compared to the Hückel aromatic structures, and the current flow avoids the molecular twist. Importantly, we show that expanded porphyrins, upon redox and topology interconversions, could act as efficient three-level molecular switches with high ON/OFF ratio, up to 103 at low bias voltage.

Exploring Electrical Currents through Nanographenes: Visualization and Tuning of the Through-Bond Transmission Paths

In this work, electrical currents through nanographenes, a class of alternant hydrocarbons also known as polycyclic aromatic hydrocarbons, in molecular junctions under small bias are explored. We illustrate that when the π-current dominates, that is, when no quantum interference takes place, the current prefers the direction of the shortest bond (the bond with the highest double bond character) upon entering the molecule from the contacts. As such, the idea of electrons propagating through double bonds from contact to contact, originating from the curly arrow drawings used in a previously established selection rule for transmission, seems to be more deeply rooted in the actual physical process of electron transport than previously anticipated. Furthermore, this work confirms that the σ-current behaves completely differently than the π-current. When this type of current becomes important, that is, when quantum interference takes place, the current generally prefers the shortest path from contact to contact, irrespective of the length of the bonds constituting this path, in accordance with the strong distance dependency of the σ-current. Finally, it is demonstrated that keto groups (and cross-conjugating groups in general) can be used to seal off parts of the molecule for the current. No current flows through the sealed off part of the molecule under small bias and it does not influence the transmission spectrum of the considered system.

Diradical Character as a Guiding Principle for the Insightful Design of Molecular Nanowires with an Increasing Conductance with Length

In recent years, a considerable interest has grown in the design of molecular nanowires with an increasing conductance with length. The development of such nanowires is highly desirable because they could play an important role in future molecular-scale circuitry. Whereas the first experimental observation of this nonclassical behavior still has to be realized, a growing number of candidate wires have been proposed theoretically. In this Letter, we point out that all the wires with an anti-Ohmic increasing conductance with length proposed so far share a common characteristic: their diradical character increases with length. The conceptual connection between diradical character and conductance enables a systematic design of such anti-Ohmic wires and explains the difficulty in their syntheses. A strategy is proposed to balance the stability and conductance so that this nonclassical phenomenon can be observed.

Extension of the source-sink potential approach to Hartree-Fock and density functional theory: A new tool to visualize the ballistic current through molecules

The recent source and sink potential approach by Pickup et al. [J. Chem. Phys. 143, 194105 (2015)] is extended to Hartree-Fock and density functional theory, allowing the calculation of the transmission and the visualization of ballistic currents through molecules at these levels of theory. This visualization allows the study of the transmission process in real-space, providing an important tool to better understand the conduction process.