RESUMEN
A central aim of multiscale modeling is to use results from the Schrödinger equation to predict phenomenology on length scales that far exceed those of typical molecular correlations. In this work, we present a new approach rooted in classical density functional theory (cDFT) that allows us to accurately describe the solvation of apolar solutes across length scales. Our approach builds on the Lum-Chandler-Weeks (LCW) theory of hydrophobicity [K. Lum et al., J. Phys. Chem. B 103, 4570 (1999)] by constructing a free energy functional that uses a slowly varying component of the density field as a reference. From a practical viewpoint, the theory we present is numerically simpler and generalizes to solutes with soft-core repulsion more easily than LCW theory. Furthermore, by assessing the local compressibility and its critical scaling behavior, we demonstrate that our LCW-style cDFT approach contains the physics of critical drying, which has been emphasized as an essential aspect of hydrophobicity by recent theories. As our approach is parameterized on the two-body direct correlation function of the uniform fluid and the liquid-vapor surface tension, it straightforwardly captures the temperature dependence of solvation. Moreover, we use our theory to describe solvation at a first-principles level on length scales that vastly exceed what is accessible to molecular simulations.
RESUMEN
Friction at water-carbon interfaces remains a major puzzle with theories and simulations unable to explain experimental trends in nanoscale waterflow. A recent theoretical frameworkâquantum friction (QF)âproposes to resolve these experimental observations by considering nonadiabatic coupling between dielectric fluctuations in water and graphitic surfaces. Here, using a classical model that enables fine-tuning of the solid's dielectric spectrum, we provide evidence from simulations in general support of QF. In particular, as features in the solid's dielectric spectrum begin to overlap with water's librational and Debye modes, we find an increase in friction in line with that proposed by QF. At the microscopic level, we find that this contribution to friction manifests more distinctly in the dynamics of the solid's charge density than that of water. Our findings suggest that experimental signatures of QF may be more pronounced in the solid's response rather than liquid water's.
RESUMEN
Electrochemical carbon dioxide capture recently emerged as a promising alternative approach to conventional energy-intensive carbon-capture methods. A common electrochemical capture approach is to employ redox-active molecules such as quinones. Upon electrochemical reduction, quinones become activated for the capture of CO2 through a chemical reaction. A key disadvantage of this method is the possibility of side-reactions with oxygen, which is present in almost all gas mixtures of interest for carbon capture. This issue can potentially be mitigated by fine-tuning redox potentials through the introduction of electron-withdrawing groups on the quinone ring. In this article, we investigate the thermodynamics of the electron transfer and chemical steps of CO2 capture in different quinone derivatives with a range of substituents. By combining density functional theory calculations and cyclic voltammetry experiments, we support a previously described trade-off between the redox potential and the strength of CO2 capture. We show that redox potentials can readily be tuned to more positive values to impart stability to oxygen, but significant decreases in CO2 binding free energies are observed as a consequence. Our calculations support this effect for a large series of anthraquinones and benzoquinones. Different trade-off relationships were observed for the two classes of molecules. These trade-offs must be taken into consideration in the design of improved redox-active molecules for electrochemical CO2 capture.