The interplay of adsorption geometry and interface dipoles of the transition-metal complex Ir(ppy)3 on Cu(111) was studied using low-temperature scanning probe microscopy and density-functional-theory calculations. We find that the orientation of the molecule's intrinsic dipole moment with respect to the surface has a strong influence on the total energy of the different configurations, where the most stable one has the molecular dipole moment pointing out of the surface plane along the surface normal. Adsorption-induced redistribution of charges results in an additional dipole moment that also points out of the surface plane for all configurations. Submolecularly resolved maps of the resulting local contact potential difference suggest that any in-plane dipole moment is very effectively screened.
- Publication type
- Journal Article MeSH
Molecular dipoles present important, but underutilized, methods for guiding electron transfer (ET) processes. While dipoles generate fields of Gigavolts per meter in their vicinity, reported differences between rates of ET along versus against dipoles are often small or undetectable. Herein we show unprecedentedly large dipole effects on ET. Depending on their orientation, dipoles either ensure picosecond ET, or turn ET completely off. Furthermore, favorable dipole orientation makes ET possible even in lipophilic medium, which appears counterintuitive for non-charged donor-acceptor systems. Our analysis reveals that dipoles can substantially alter the ET driving force for low solvent polarity, which accounts for these unique trends. This discovery opens doors for guiding forward ET processes while suppressing undesired backward electron transduction, which is one of the holy grails of photophysics and energy science.
The study of magnetic frustration in classical spin systems is motivated by the prediction and discovery of classical spin liquid states. These uncommon magnetic phases are characterized by a massive degeneracy of their ground state implying a finite magnetic entropy at zero temperature. While the classical spin liquid state is originally predicted in the Ising triangular lattice antiferromagnet in 1950, this state has never been experimentally observed in any triangular magnets. The discovery of an electric analogue of classical spin liquids on a triangular lattice of uniaxial electric dipoles in EuAl12O19 is reported here. This new type of frustrated antipolar phase is characterized by a highly-degenerate state at low temperature implying an absence of long-range antiferroelectric order, despite short-range antipolar correlations. Its dynamics are governed by a thermally activated process, slowing down upon cooling toward a complete freezing at zero temperature.
- Keywords
- dielectric relaxation, electric dipoles, frustration, highly degenerate state, structural disorder,
- Publication type
- Journal Article MeSH
We use simple acid-base chemistry to control the valency in self-assembled monolayers of two different carboranedithiol isomers on Au{111}. Monolayer formation proceeds via Au-S bonding, where manipulation of pH prior to or during deposition enables the assembly of dithiolate species, monothiol/monothiolate species, or combination. Scanning tunneling microscopy (STM) images identify two distinct binding modes in each unmodified monolayer, where simultaneous spectroscopic imaging confirms different dipole offsets for each binding mode. Density functional theory calculations and STM image simulations yield detailed understanding of molecular chemisorption modes and their relation with the STM images, including inverted contrast with respect to the geometric differences found for one isomer. Deposition conditions are modified with controlled equivalents of either acid or base, where the coordination of the molecules in the monolayers is controlled by protonating or deprotonating the second thiol/thiolate on each molecule. This control can be exercised during deposition to change the valency of the molecules in the monolayers, a process that we affectionately refer to as the "can-can." This control enables us to vary the density of molecule-substrate bonds by a factor of 2 without changing the molecular density of the monolayer.
The transition dipole coupling model allows to vary systematically many parameters, such as chromophore geometries and transition dipoles. We used it to explore conditions favorable to chirality enhancement observed in many experiments on protein amyloidal precipitates. Stacking of β-sheet planes has been identified as a particularly powerful mechanism of the enhancement.
- Keywords
- Raman optical activity, circular dichroism, enhancement of optical activity, protein spectra, transition dipole coupling,
- MeSH
- Models, Molecular MeSH
- Multiprotein Complexes chemistry MeSH
- Optical Rotation * MeSH
- Stereoisomerism MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Multiprotein Complexes MeSH
Combining proton and phosphorus magnetic resonance spectroscopy offers a unique opportunity to study the oxidative and glycolytic components of metabolism in working muscle. This paper presents a 7 T proton calf coil design that combines dipole and loop elements to achieve the high performance necessary for detecting metabolites with low abundance and restricted visibility, specifically lactate, while including the option of adding a phosphorus array. We investigated the transmit, receive, and parallel imaging performance of three transceiver dipoles with six pair-wise overlap-decoupled standard or twisted pair receive-only coils. With a higher SNR and more efficient transmission decoupling, standard loops outperformed twisted pair coils. The dipoles with standard loops provided a four-fold-higher image SNR than a multinuclear reference coil comprising two proton channels and 32% more than a commercially available 28-channel proton knee coil. The setup enabled up to three-fold acceleration in the right-left direction, with acceptable g-factors and no visible aliasing artefacts. Spectroscopic phantom measurements revealed a higher spectral SNR for lactate with the developed setup than with either reference coil and fewer restrictions in voxel placement due to improved transmit homogeneity. This paper presents a new use case for dipoles and highlights their advantages for the integration in multinuclear calf coils.
- Keywords
- magnetic resonance imaging, magnetic resonance spectroscopy, muscle metabolism, radiofrequency coil, ultra-high field,
- MeSH
- Phantoms, Imaging * MeSH
- Muscle, Skeletal * diagnostic imaging chemistry MeSH
- Lactic Acid chemistry metabolism MeSH
- Humans MeSH
- Magnetic Resonance Spectroscopy methods MeSH
- Magnetic Resonance Imaging * methods MeSH
- Signal-To-Noise Ratio MeSH
- Check Tag
- Humans MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Lactic Acid MeSH
The study is concerned with quantitative mapping of electrocardiographic potentials on the human body surface at various applications of equivalent multipole heart generators. The accuracy or reproduction of the electrical heart field with the application of mobile and immobile dipole and quadrupole generators is compared. The immobile equivalent generator (EG) is fixed in the geometrical centre of the trunk, whereas the mobile EG follows the path of the electrical heart centre during the heart cycle. Four healthy subjects and two patients with permanent postmyocardial ECG changes were examined. On transition from the immobile to the mobile model, in both groups of probands the relative contribution of the quadrupole component to the total potential of the body surface steeply diminished, with consequent substantial increase in accuracy of the dipole heart description. The dipole following the path of the electric heart centre during the heart cycle represents one of the most promising models, and deserves attentive clinical testing.
- MeSH
- Heart Aneurysm diagnosis MeSH
- Electrocardiography * MeSH
- Myocardial Infarction physiopathology MeSH
- Humans MeSH
- Check Tag
- Humans MeSH
- Publication type
- Journal Article MeSH
The emergence of graphene in recent years provides exciting avenues for achieving fast, reliable DNA/RNA sensing and sequencing. Here we explore the possibility of enhancing electronic fingerprints of nucleobases adsorbed on graphene by tuning the surface coverage and modifying molecular dipoles using first-principles calculations. We demonstrate that intermolecular interactions have a strong influence on the adsorption geometry and the electronic structure of the nucleobases, resulting in tilted configurations and a considerable modification of their electronic fingerprints in graphene. Our analysis reveals that the molecular dipole of the nucleobase molecules plays a dominant role in the electronic structure of graphene-nucleobase systems, inducing significant changes in the work functions and energy level alignments at the interface. These results highlight tunable control of the measured molecular signals in graphene by optimizing the surface contact between nucleobases and graphene. Our findings have important implications for identification and understanding of molecular fingerprints of DNA/RNA nucleobases in graphene-based sensing and sequencing methods.
Detailed understanding and control of the intermolecular forces that govern molecular assembly are necessary to engineer structure and function at the nanoscale. Liquid crystal (LC) assembly is exceptionally sensitive to surface properties, capable of transducing nanoscale intermolecular interactions into a macroscopic optical readout. Self-assembled monolayers (SAMs) modify surface interactions and are known to influence LC alignment. Here, we exploit the different dipole magnitudes and orientations of carboranethiol and -dithiol positional isomers to deconvolve the influence of SAM-LC dipolar coupling from variations in molecular geometry, tilt, and order. Director orientations and anchoring energies are measured for LC cells employing various carboranethiol and -dithiol isomer alignment layers. The normal component of the molecular dipole in the SAM, toward or away from the underlying substrate, was found to determine the in-plane LC director orientation relative to the anisotropy axis of the surface. By using LC alignment as a probe of interaction strength, we elucidate the role of dipolar coupling of molecular monolayers to their environment in determining molecular orientations. We apply this understanding to advance the engineering of molecular interactions at the nanoscale.
The electric dipole moments of (H2O)nDCl (n=3-9) clusters have been measured by the beam-deflection method. Reflecting the (dynamical) charge distribution within the system, the dipole moment contributes information about the microscopic structure of nanoscale solvation. The addition of a DCl molecule to a water cluster results in a strongly enhanced susceptibility. There is evidence for a noticeable rise in the dipole moment occurring at n≈5-6. This size is consistent with predictions for the onset of ionic dissociation. Additionally, a molecular-dynamics model suggests that even with a nominally bound impurity an enhanced dipole moment can arise due to the thermal and zero-point motion of the proton and the water molecules. The experimental measurements and the calculations draw attention to the importance of fluctuations in defining the polarity of water-based nanoclusters and generally to the essential role played by motional effects in determining the response of fluxional nanoscale systems under realistic conditions.
- Publication type
- Journal Article MeSH
