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Are surface nanobubbles transient or thermodynamically stable structures? This question remained controversial until recently, when the stability of gas nanobubbles at solid-liquid interfaces was demonstrated from thermodynamic arguments in closed systems, establishing that bubbles with radii of hundreds of nanometers can be stable at modest supersaturations if the gas amount is finite. Here we develop a grand-canonical description of bubble formation that predicts that nanobubbles can nucleate and remain thermodynamically stable in open boundaries at high supersaturations when pinned to hydrophobic supports as small as a few nanometers. While larger bubbles can also be stable at lower supersaturations, the corresponding barriers are orders of magnitude above kT, meaning that their formation cannot proceed via heterogeneous nucleation on a uniform solid interface but must follow some alternative path. Moreover, we conclude that a source of growth-limiting mechanism, such as pinning or gas availability, is necessary for the thermodynamic stabilization of surface bubbles.
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Nanoconfinement effects on water dissociation and reactivity remain controversial, despite their importance to understand the aqueous chemistry at interfaces, pores, or aerosols. The pKw in confined environments has been assessed from experiments and simulations in a few specific cases, leading to dissimilar conclusions. Here, with the use of carefully designed ab initio simulations, we demonstrate that the energetics of bulk water dissociation is conserved intact to unexpectedly small length-scales, down to aggregates of only a dozen molecules or pores of widths below 2â nm. The reason is that most of the free-energy involved in water autoionization comes from breaking the O-H covalent bond, which has a comparable barrier in the bulk liquid, in a small droplet of nanometer size, or in a nanopore in the absence of strong interfacial interactions. Thus, dissociation free-energy profiles in nanoscopic aggregates or in 2D slabs of 1â nm width reproduce the behavior corresponding to the bulk liquid, regardless of whether the corresponding nanophase is delimited by a solid or a gas interface. The present work provides a definite and fundamental description of the mechanism and thermodynamics of water dissociation at different scales with broader implications on reactivity and self-ionization at the air-liquid interface.
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Real time modeling of fluorescence with vibronic resolution entails the representation of the light-matter interaction coupled to a quantum-mechanical description of the phonons and is therefore a challenging problem. In this work, taking advantage of the difference in timescales characterizing internal conversion and radiative relaxation-which allows us to decouple these two phenomena by sequentially modeling one after the other-we simulate the electron dynamics of fluorescence through a master equation derived from the Redfield formalism. Moreover, we explore the use of a recent semiclassical dissipative equation of motion [C. M. Bustamante et al., Phys. Rev. Lett. 126, 087401 (2021)], termed coherent electron electric-field dynamics (CEED), to describe the radiative stage. By comparing the results with those from the full quantum-electrodynamics treatment, we find that the semiclassical model does not reproduce the right amplitudes in the emission spectra when the radiative process involves the de-excitation to a manifold of closely lying states. We argue that this flaw is inherent to any mean-field approach and is the case with CEED. This effect is critical for the study of light-matter interaction, and this work is, to our knowledge, the first one to report this problem. We note that CEED reproduces the correct frequencies in agreement with quantum electrodynamics. This is a major asset of the semiclassical model, since the emission peak positions will be predicted correctly without any prior assumption about the nature of the molecular Hamiltonian. This is not so for the quantum electrodynamics approach, where access to the spectral information relies on knowledge of the Hamiltonian eigenvalues.
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Cooperative optical effects provide a pathway to both the amplification (superradiance) and the suppression (subradiance) of photon emission from electronically excited states. These captivating phenomena offer a rich variety of possibilities for photonic technologies aimed at electromagnetic energy manipulation, including lasers and high-speed emitting devices in the case of superradiance or optical energy storage in that of subradiance. The employment of molecules as the building pieces in these developments requires a precise understanding of the roles of separation, orientation, spatial distribution, and applied fields, which remains challenging for theory and experiments. These questions are addressed here through ab initio quantum dynamics simulations of collective emission on the basis of a novel semiclassical formalism and time-dependent density functional theory. By establishing the configurations leading to decoherence and how the fine-tuning of a pulse can accumulate or release optical energy in H2 arrays, this report provides fundamental insight toward the design of real superradiant and subradiant devices.
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It is well-known that the thermodynamic, kinetic and structural properties of fluids, and in particular of water and its solutions, can be drastically affected in nanospaces. A possible consequence of nanoscale confinement of a solution is the partial segregation of its components. Thereby, confinement in nanoporous materials (NPM) has been proposed as a means for the separation of mixtures. In fact, separation science can take great advantage of NPM due to the tunability of their properties as a function of nanostructure, morphology, pore size, and surface chemistry. Alcohol-water mixtures are in this context among the most relevant systems. However, a quantitative thermodynamic description allowing for the prediction of the segregation capabilities as a function of the material-solution characteristics is missing. In the present study we attempt to fill this vacancy, by contributing a thermodynamic treatment for the calculation of the partition coefficient in confinement. Combining the multilayer adsorption model for binary mixtures with the Young equation, we conclude that the liquid-vapor surface tension and the contact angle of the pure substances can be used to predict the separation ability of a particular material for a given mixture to a semiquantitative extent. Moreover, we develop a Kelvin-type equation that relates the partition coefficient to the radius of the pore, the contact angle, and the liquid-vapor surface tensions of the constituents. To assess the validity of our thermodynamic formulation, coarse grained molecular dynamics simulations were performed on models of alcohol-water mixtures confined in cylindrical pores. To this end, a coarse-grained amphiphilic molecule was parametrized to be used in conjunction with the mW potential for water. This amphiphilic model reproduces some of the properties of methanol such as enthalpy of vaporization and liquid-vapor surface tension, and the minimum of the excess enthalpy for the aqueous solution. The partition coefficient turns out to be highly dependent on the molar fraction, on the interaction between the components and the confining matrix, and on the radius of the pore. A remarkable agreement between the theory and the simulations is found for pores of radius larger than 15 Å.
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The doping mechanisms responsible for elevating the currents up to eleven orders of magnitude in semiconducting polymer films are today well characterized. Doping can also improve the performance of nanoscale devices or single molecule conductors, but the mechanism in this case appears to be different, with theoretical studies suggesting that the dopant affects the electronic properties of the junctions. In the present report, multiscale time-dependent DFT transport simulations help clarify the way in which n-type doping can raise the current flowing through a polymer chain connected to a pair of electrodes, with the focus on polyacetylene. In particular, our multiscale methodology offers control over the magnitude of the chemical coupling between the molecule and the electrodes, which allows us to analyze the effect of doping in low and strong coupling regimes. Interestingly, our results establish that the impact of dopants is the highest in weakly coupled devices, while their presence tends to be irrelevant in low-resistance junctions. Our calculations point out that both the equalization of the frontier orbitals with the Fermi level and a small gap between the HOMO and the LUMO must result from doping in order to observe any significant increase of the currents.
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The dynamical description of the radiative decay of an electronically excited state in realistic many-particle systems is an unresolved challenge. In the present investigation electromagnetic radiation of the charge density is approximated as the power dissipated by a classical dipole, to cast the emission in closed form as a unitary single-electron theory. This results in a formalism of unprecedented efficiency, critical for ab initio modeling, which exhibits at the same time remarkable properties: it quantitatively predicts decay rates, natural broadening, and absorption intensities. Exquisitely accurate excitation lifetimes are obtained from time-dependent DFT simulations for C^{2+}, B^{+}, and Be, of 0.565, 0.831, and 1.97 ns, respectively, in accord with experimental values of 0.57±0.02, 0.86±0.07, and 1.77-2.5 ns. Hence, the present development expands the frontiers of quantum dynamics, bringing within reach first-principles simulations of a wealth of photophysical phenomena, from fluorescence to time-resolved spectroscopies.
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The modeling of coupled electron-ion dynamics including a quantum description of the nuclear degrees of freedom has remained a costly and technically difficult practice. The kinetic model for electron-phonon interaction provides an efficient approach to this problem, for systems evolving with low amplitude fluctuations, in a quasi-stationary state. In this work, we propose an extension of the kinetic model to include the effect of coherences, which are absent in the original approach. The new scheme, referred to as Liouville-von Neumann + Kinetic Equation (or LvN + KE), is implemented here in the context of a tight-binding Hamiltonian and employed to model the broadening, caused by the nuclear vibrations, of the electronic absorption bands of an atomic wire. The results, which show close agreement with the predictions given by Fermi's golden rule (FGR), serve as a validation of the methodology. Thereafter, the method is applied to the electron-phonon interaction in transport simulations, adopting to this end the driven Liouville-von Neumann equation to model open quantum boundaries. In this case, the LvN + KE model qualitatively captures the Joule heating effect and Ohm's law. It, however, exhibits numerical discrepancies with respect to the results based on FGR, attributable to the fact that the quasi-stationary state is defined taking into consideration the eigenstates of the closed system rather than those of the open boundary system. The simplicity and numerical efficiency of this approach and its ability to capture the essential physics of the electron-phonon coupling make it an attractive route to first-principles electron-ion dynamics.
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Gas-producing electrochemical reactions are key to energy conversion and generation technologies. Bubble formation dramatically decreases gas-production rates on nanoelectrodes, by confining the reaction to the electrode boundary. This results in the collapse of the current to a stationary value independent of the potential. Startlingly, these residual currents also appear to be insensitive to the nanoelectrode diameter in the 5 to 500 nm range. These results are counterintuitive, as it may be expected that the current be proportional to the circumference of the electrode, i.e., the length of the three-phase line where the reaction occurs. Here, we use molecular simulations and a kinetic model to elucidate the origin of current insensitivity with respect to the potential and establish its relationship to the size of nanoelectrodes. We provide critical insights for the design and operation of nanoscale electrochemical devices and demonstrate that nanoelectrode arrays maximize conversion rates compared to macroscopic electrodes with same total area.
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In the context of electron dynamics simulations, when the charge density of a molecule is subject to a perturbation in the form of a short electric field pulse, density fluctuations develop in time. In the absence of dissipation, these oscillations continue indefinitely, reflecting the resonances of the electronic system; as a matter of fact, from the Fourier transform of the time dependent dipole arising from them, the absorption spectrum of the molecule can be calculated. Since these oscillations are the result of the electrons moving through the molecular structrure, it seems plausible that they carry information on the transport properties of the system. This is the idea explored in the present article for the case of conjugated polymers. Specifically, we depart from a nonequilibrium state with the charge concentrated on the ends of the molecule, and estimate the currents flowing back and forth during the evolution of electron dynamics simulations. These show that the charge oscillates between the sides of the polymer with the predominance of a frequency that is coincident with one of the main bands in the absorption spectrum, which can be ascribed to a charge transfer transition. Thus, from the charge transfer band frequency appearing in the absorption spectrum, the molecular conductance of a conjugated molecule can be calculated. Also interestingly, we find that, while a perturbation excites all resonances of an electronic system, the form in which this perturbation is applied can be manipulated to determine the relative manifestation of the response. The electric field pulse excites all resonances according to the transition dipole moment and is then appropriate to produce the absorption spectrum. A charge separated initial state, however, specifically stimulates the charge transfer mode and is then suitable to calculate transport properties. This allows us to propose a simple approach to obtain molecular conductances and tunneling decay constants in agreement with results from much more demanding electronic structure techniques.