RESUMEN
Precise theoretical calculations of non-adiabatic couplings, which describe the interaction between two Born-Oppenheimer surfaces, are important for the modeling of radiationless decay mechanisms in photochemical processes. Here, we demonstrate that accurate non-adiabatic couplings can be calculated in the framework of linear-response time-dependent density functional theory by using non-empirical, optimally tuned range-separated hybrid (OT-RSH) functionals. We focus on molecular radicals, in which ultrafast non-radiative decay plays a crucial role, to find that the OT-RSH functional compares well to wave-function-based reference data and competes with the accuracy of semi-empirical CAM-B3LYP calculations. Our findings show that the OT-RSH approach yields very accurate non-adiabatic couplings and, therefore, provides a computationally efficient alternative to wave-function-based techniques.
RESUMEN
We present an efficient strategy to modulate tunnelling in molecular junctions by changing the tunnelling decay coefficient, ß, by terminal-atom substitution which avoids altering the molecular backbone. By varying X = H, F, Cl, Br, I in junctions with S(CH2)(10-18)X, current densities (J) increase >4 orders of magnitude, creating molecular conductors via reduction of ß from 0.75 to 0.25 Å-1. Impedance measurements show tripled dielectric constants (εr) with X = I, reduced HOMO-LUMO gaps and tunnelling-barrier heights, and 5-times reduced contact resistance. These effects alone cannot explain the large change in ß. Density-functional theory shows highly localized, X-dependent potential drops at the S(CH2)nX//electrode interface that modifies the tunnelling barrier shape. Commonly-used tunnelling models neglect localized potential drops and changes in εr. Here, we demonstrate experimentally that [Formula: see text], suggesting highly-polarizable terminal-atoms act as charge traps and highlighting the need for new charge transport models that account for dielectric effects in molecular tunnelling junctions.
RESUMEN
The interplay of electronic excitations and structural changes in molecules impacts nonradiative decay and charge transfer in the excited state, thus influencing excited-state lifetimes and photocatalytic reaction rates in optoelectronic and energy devices. To capture such effects requires computational methods providing an accurate description of excited-state potential energy surfaces and geometries. We suggest time-dependent density functional theory using optimally tuned range-separated hybrid (OT-RSH) functionals as an accurate approach to obtain excited-state molecular geometries. We show that OT-RSH provides accurate molecular geometries in excited-state potential energy surfaces that are complex and involve an interplay of local and charge-transfer excitations, for which conventional semilocal and hybrid functionals fail. At the same time, the nonempirical OT-RSH approach maintains the high accuracy of parametrized functionals (e.g., B3LYP) for predicting excited-state geometries of small organic molecules showing valence excited states.
RESUMEN
Predictions about the electrical conductance across molecular junctions based on self-assembled monolayers (SAMs) are often made from the SAM precursor properties. Collective electrostatic effects, however, in a densely packed SAM can override these predictions. We studied, experimentally and theoretically, molecular tunneling junctions based on thiolate SAMs with an aromatic biphenyl backbone and variable, highly polarizable halogen termini X (S-(C6H5)2X; X = H, F, Cl, Br, or I). We found that the halogen-terminated systems show tunneling rates and dielectric behavior that are independent of X despite the large change in the electronegativity of the terminal atom. Using density functional theory, we show that collective electrostatic effects result in modulations of the electrostatic potential that are strongly confined spatially along the direction of charge transport, thereby rendering the role of the halogen atoms insignificant for SAMs with conjugated backbones.
RESUMEN
Electrons in graphene can show diffraction and interference phenomena fully analogous to light thanks to their Dirac-like energy dispersion. However, it is not clear how this optical analogy persists in nanostructured graphene, for example, with pores. Nanoporous graphene (NPG) consisting of linked graphene nanoribbons has recently been fabricated using molecular precursors and bottom-up assembly (Moreno et al. Science 2018, 360, 199). We predict that electrons propagating in NPG exhibit the interference Talbot effect, analogous to photons in coupled waveguides. Our results are obtained by parameter-free atomistic calculations of real-sized NPG samples based on seamlessly integrated density functional theory and tight-binding regions. We link the origins of this interference phenomenon to the band structure of the NPG. Most importantly, we demonstrate how the Talbot effect may be detected experimentally using dual-probe scanning tunneling microscopy. Talbot interference of electron waves in NPG or other related materials may open up new opportunities for future quantum electronics, computing, or sensing.
RESUMEN
Nanosize pores can turn semimetallic graphene into a semiconductor and, from being impermeable, into the most efficient molecular-sieve membrane. However, scaling the pores down to the nanometer, while fulfilling the tight structural constraints imposed by applications, represents an enormous challenge for present top-down strategies. Here we report a bottom-up method to synthesize nanoporous graphene comprising an ordered array of pores separated by ribbons, which can be tuned down to the 1-nanometer range. The size, density, morphology, and chemical composition of the pores are defined with atomic precision by the design of the molecular precursors. Our electronic characterization further reveals a highly anisotropic electronic structure, where orthogonal one-dimensional electronic bands with an energy gap of â¼1 electron volt coexist with confined pore states, making the nanoporous graphene a highly versatile semiconductor for simultaneous sieving and electrical sensing of molecular species.
RESUMEN
We show that the chemical inhomogeneity in ternary three-dimensional topological insulators preserves the topological spin texture of their surface states against a net surface magnetization. The spin texture is that of a Dirac cone with helical spin structure in the reciprocal space, which gives rise to spin-polarized and dissipation-less charge currents. Thanks to the nontrivial topology of the bulk electronic structure, this spin texture is robust against most types of surface defects. However, magnetic perturbations break the time-reversal symmetry, enabling magnetic scattering and loss of spin coherence of the charge carriers. This intrinsic incompatibility precludes the design of magnetoelectronic devices based on the coupling between magnetic materials and topological surface states. We demonstrate that the magnetization coming from individual Co atoms deposited on the surface can disrupt the spin coherence of the carriers in the archetypal topological insulator Bi2Te3, while in Bi2Se2Te the spin texture remains unperturbed. This is concluded from the observation of elastic backscattering events in quasiparticle interference patterns obtained by scanning tunneling spectroscopy. The mechanism responsible for the protection is investigated by energy resolved spectroscopy and ab initio calculations, and it is ascribed to the distorted adsorption geometry of localized magnetic moments due to Se-Te disorder, which suppresses the Co hybridization with the surface states.
RESUMEN
Controlling the nature of the electronic states within organic layers holds the promise of truly molecular electronics. To achieve that we, here, develop a modular concept for a versatile tuning of electronic properties in organic monolayers and their interfaces. The suggested strategy relies on directly exploiting collective electrostatic effects, which emerge naturally in an ensemble of polar molecules. By means of quantum-mechanical modeling we show that in this way monolayer-based quantum-cascades and quantum-well structures can be realized, which allow a precise control of the local electronic structure and the localization of electronic states. Extending that concept, we furthermore discuss strategies for activating spin sensitivity in specific regions of an organic monolayer.