Chemical Physics
Although electrolyte density measurements have been reported for over a century, employing them to obtain accurate partial molar volume (PMV) profiles as a function of salt concentration has remained elusive. Obtaining such curves requires…
Among the possible types of magnetic dipole interactions in molecular systems, couplings between nuclear motion and the nuclear spin have probably received the least attention in molecular spectroscopy. Although very small in comparison to…
In molecular liquids such as water, time-delayed influences between microscopic or mesoscopic variables are typically probed using time-correlation functions, which are symmetric under detailed balance and therefore blind to dynamical…
Attosecond chemistry involves developing strategies to manipulate electronic coherent waves in molecules, which can influence the outcome of photoinduced reactions. While recent progress in this field calls for investigations of…
The geometric phase (GP) is a fundamental quantum effect arising from conical intersections (CIs), with profound consequences for vibronic energy levels. Standard imaginary-time path integral molecular dynamics (PIMD) based on the…
The rapid development of pretrained Machine Learning Interatomic Potentials (MLIPs) that cover a wide range of molecular species has made it challenging to select the best model for a given application. We benchmark 15 pretrained MLIPs,…
Density Functional Theory (DFT) underpins much of modern computational chemistry and materials science. Yet, the reliability of DFT-derived predictions of experimentally measurable properties remains fundamentally limited by the need to…
Low-temperature hydrocarbon autooxidation involves radical intermediates whose reactivity depends not only on the stereochemistry of the intermediates themselves, but also on that of the transient species encountered along the reaction…
The solvation free energy (SFE) of molecules and ions is a fundamental property governing their solvation behavior and solubility. Molecular simulations offer a route to compute SFEs using alchemical free energy methods, such as…
In this work, we develop a theoretical description of the collective behavior of interacting dipolar planar rotors by using time independent perturbation theory and a small angle quadratic approximation. The ground state properties for both…
Density functional theory with plane-wave basis sets is widely employed in computational materials science, including applications to isolated molecular systems. However, the inadequate description of electron correlation remains a…
Tetraphenylpyrazine (TPP) and 2,3,4,5-tetraphenyl-1H-pyrrole (TePP) are closely related heterocycles bearing four phenyl substituents, whose structural similarity makes them a useful pair for comparing how intramolecular flexibility…
There has been a veritable explosion of methods and software to perform machine-learned regression on datasets of electronic energies and forces to develop high-dimensional machine learned potential energy surfaces (ML-PESs). A major, but…
The extension of coherent $\omega$-$2\omega$ control schemes, recently implemented in free-electron lasers (FELs), to molecular systems offers new opportunities to control chemical dynamics on the electronic timescale, potentially allowing…
Signal amplification by reversible exchange (SABRE) is a nuclear spin hyperpolarization technique in which the transient interaction of parahydrogen (pH2) and a target substrate with an iridium complex leads to polarization transfer to the…
Marcus theory famously predicts that electron-transfer rates decrease once the thermodynamic driving force exceeds the reorganization energy. Yet many systems instead exhibit Rehm-Weller kinetics, in which the rate saturates rather than…
A correlation between the symmetry of NMR spectra, including higher-order spectra, and the properties of the spin system has been established. It is shown that for a spectrum to be symmetric about the mid-resonance frequency ({\nu}0), two…
Recent theoretical studies in quantum spectroscopy have emphasized the potential of non-classical correlations in entangled photon pairs for selectively targeting specific nonlinear optical processes in nonlinear optical responses. However,…
Electrochemical nitrate reduction reaction(NO3RR)offers a sustainable route for ambient ammonia synthesis. While metal-nitrogen-carbon (M-N-C) single-atom catalysts have emerged as promising candidates for NO3RR, the structure-activity…
Single-atom catalysts (SACs) with metal-nitrogen-carbon (M-N-C) structures are widely recognized as promising candidates in oxygen reduction reactions (ORR). According to the classical Sabatier principle, optimal 3d metal catalysts, such as…