Participation in a High-Structure General Chemistry Course Increases Student Sense of Belonging and Persistence to Organic Chemistry.

A parallel series of general chemistry courses for Life Science Majors was created in an effort to support students and improve general chemistry outcomes. We created a two-quarter enhanced general chemistry course series that is not remedial, but instead implements several evidence-based teaching practices including Process Oriented Guided Inquiry Learning (POGIL), Peer-Led Team Learning (PLTL), and the Learning Assistant (LA) model. We found that students who took enhanced general chemistry had higher persistence to the subsequent first organic chemistry course, and performed equally well in the organic course compared to their peers who took standard general chemistry. Students in the first enhanced general chemistry course also reported significantly higher belonging, although we were unable to determine if increased belonging was associated with the increased persistence to organic chemistry. Rather we found that the positive association between taking the enhanced general chemistry course and persistence to organic chemistry was mediated by higher grades received in the enhanced general chemistry course. Our findings highlight the responsibility we have as educators to carefully consider the pedagogical practices we use, in addition to how we assign student grades.

Free Energies of Cavity and Noncavity Hydrated Electrons Near the Instantaneous Air/Water Interface.

The properties of the hydrated electron at the air/water interface are computed for both a cavity and a noncavity model using mixed quantum/classical molecular dynamics simulation. We take advantage of our recently developed formalism for umbrella sampling with a restrained quantum expectation value to calculate free-energy profiles of the hydrated electron's position relative to the water surface. We show that it is critical to use an instantaneous description of the air/water interface rather than the Gibbs' dividing surface to obtain accurate potentials of mean force. We find that noncavity electrons, which prefer to encompass several water molecules, avoid the interface where water molecules are scarce. In contrast, cavity models of the hydrated electron, which prefer to expel water, have a local free-energy minimum near the interface. When the cavity electron occupies this minimum, its absorption spectrum is quite red-shifted, its binding energy is significantly lowered, and its dynamics speed up quite a bit compared with the bulk, features that have not been found by experiment. The surface activity of the electron therefore serves as a useful test of cavity versus noncavity electron solvation.

Free Energies of Quantum Particles: The Coupled-Perturbed Quantum Umbrella Sampling Method.

We introduce a new simulation method called Coupled-Perturbed Quantum Umbrella Sampling that extends the classical umbrella sampling approach to reaction coordinates involving quantum mechanical degrees of freedom. The central idea in our method is to solve coupled-perturbed equations to find the response of the quantum system's wave function along a reaction coordinate of interest. This allows for propagation of the system's dynamics under the influence of a quantum biasing umbrella potential and provides a method to rigorously undo the effects of the bias to compute equilibrium ensemble averages. In this way, one can drag electrons into regions of high free energy where they would otherwise not go, thus enabling chemistry by fiat. We demonstrate the applicability of our method for two condensed-phase systems of interest. First, we consider the interaction of a hydrated electron with an aqueous sodium cation, and we calculate a potential of mean force that shows that an e(-):Na(+) contact pair is the thermodynamically favored product starting from either a neutral sodium atom or the separate cation and electron species. Second, we present the first determination of a hydrated electron's free-energy profile relative to an air/water interface. For the particular model parameters used, we find that the hydrated electron is more thermodynamically stable in the bulk rather than at the interface. Our analysis suggests that the primary driving force keeping the electron away from the interface is the long-range electron-solvent polarization interaction rather than the short-range details of the chosen pseudopotential.

To be or not to be in a cavity: the hydrated electron dilemma.

The hydrated electron-the species that results from the addition of a single excess electron to liquid water-has been the focus of much interest both because of its role in radiation chemistry and other chemical reactions, and because it provides for a deceptively simple system that can serve as a means to confront the predictions of quantum molecular dynamics simulations with experiment. Despite all this interest, there is still considerable debate over the molecular structure of the hydrated electron: does it occupy a cavity, have a significant number of interior water molecules, or have a structure somewhere in between? The reason for all this debate is that different computer simulations have produced each of these different structures, yet the predicted properties for these different structures are still in reasonable agreement with experiment. In this Feature Article, we explore the reasons underlying why different structures are produced when different pseudopotentials are used in quantum simulations of the hydrated electron. We also show that essentially all the different models for the hydrated electron, including those from fully ab initio calculations, have relatively little direct overlap of the electron's wave function with the nearby water molecules. Thus, a non-cavity hydrated electron is better thought of as an "inverse plum pudding" model, with interior waters that locally expel the surrounding electron's charge density. Finally, we also explore the agreement between different hydrated electron models and certain key experiments, such as resonance Raman spectroscopy and the temperature dependence and degree of homogeneous broadening of the optical absorption spectrum, in order to distinguish between the different simulated structures. Taken together, we conclude that the hydrated electron likely has a significant number of interior water molecules.

Resonance Raman and temperature-dependent electronic absorption spectra of cavity and noncavity models of the hydrated electron.

Most of what is known about the structure of the hydrated electron comes from mixed quantum/classical simulations, which depend on the pseudopotential that couples the quantum electron to the classical water molecules. These potentials usually are highly repulsive, producing cavity-bound hydrated electrons that break the local water H-bonding structure. However, we recently developed a more attractive potential, which produces a hydrated electron that encompasses a region of enhanced water density. Both our noncavity and the various cavity models predict similar experimental observables. In this paper, we work to distinguish between these models by studying both the temperature dependence of the optical absorption spectrum, which provides insight into the balance of the attractive and repulsive terms in the potential, and the resonance Raman spectrum, which provides a direct measure of the local H-bonding environment near the electron. We find that only our noncavity model can capture the experimental red shift of the hydrated electron's absorption spectrum with increasing temperature at constant density. Cavity models of the hydrated electron predict a solvation structure similar to that of the larger aqueous halides, leading to a Raman O-H stretching band that is blue-shifted and narrower than that of bulk water. In contrast, experiments show the hydrated electron has a broader and red-shifted O-H stretching band compared with bulk water, a feature recovered by our noncavity model. We conclude that although our noncavity model does not provide perfect quantitative agreement with experiment, the hydrated electron must have a significant degree of noncavity character.