Search for: All records

Abstract Hydrogen bonding is a central concept in chemistry and biochemistry, and so it continues to attract intense study. Here, we examine hydrogen bonding in the H₂S dimer, in comparison with the well-studied water dimer, in unprecedented detail. We record a mass-selected IR spectrum of the H₂S dimer in superfluid helium nanodroplets. We are able to resolve a rotational substructure in each of the three distinct bands and, based on it, assign these to vibration-rotation-tunneling transitions of a single intramolecular vibration. With the use of high-level potential and dipole-moment surfaces we compute the vibration-rotation-tunneling dynamics and far-infrared spectrum with rigorous quantum methods. Intramolecular mode Vibrational Self-Consistent-Field and Configuration-Interaction calculations provide the frequencies and intensities of the four SH-stretch modes, with a focus on the most intense, the donor bound SH mode which yields the experimentally observed bands. We show that the intermolecular modes in the H₂S dimer are substantially more delocalized and more strongly mixed than in the water dimer. The less directional nature of the hydrogen bonding can be quantified in terms of weaker electrostatic and more important dispersion interactions. The present study reconciles all previous spectroscopic data, and serves as a sensitive test for the potential and dipole-moment surfaces. 

Abstract Flares produced following the tidal disruption of stars by supermassive black holes can reveal the properties of the otherwise dormant majority of black holes and the physics of accretion. In the past decade, a class of optical-ultraviolet tidal disruption flares has been discovered whose emission properties do not match theoretical predictions. This has led to extensive efforts to model the dynamics and emission mechanisms of optical-ultraviolet tidal disruptions in order to establish them as probes of supermassive black holes. Here we present the optical-ultraviolet tidal disruption event AT 2022dbl, which showed a nearly identical repetition 700 days after the first flare. Ruling out gravitational lensing and two chance unrelated disruptions, we conclude that at least the first flare represents the partial disruption of a star, possibly captured through the Hills mechanism. Since both flares are typical of the optical-ultraviolet class of tidal disruptions in terms of their radiated energy, temperature, luminosity, and spectral features, it follows that either the entire class are partial rather than full stellar disruptions, contrary to the prevalent assumption, or some members of the class are partial disruptions, having nearly the same observational characteristics as full disruptions. Whichever option is true, these findings could require revised models for the emission mechanisms of optical-ultraviolet tidal disruption flares and a reassessment of their expected rates. 

Abstract Laboratory-derived optical constants are essential for identifying ices and measuring their relative abundances on solar system objects. Almost all optical constants of ices important to planetary science come from experiments with transmission geometries. Here we describe our new experimental setup and the modification of an iterative algorithm in the literature to measure the optical constants of ices from experiments with reflectance geometries. We apply our techniques to CH₄ice and H₂O ice samples and find good agreement between our values and those in the literature, except for one CH₄band in the literature that likely suffers from saturation. The work we present here demonstrates that labs with reflectance geometries can generate optical constants essential for the proper analysis of near- and mid-infrared spectra of outer solar system objects such as those obtained with the James Webb Space Telescope. 

In this qualitative, participatory action research study, we examine how six Black women undergraduate students develop, cultivate, and sustain their healthcare career aspirations while examining challenges Black women undergraduate students experience during their pursuit of a healthcare career. Using community cultural wealth to frame our study, we collected two interviews per participant along with participant-generated photographs. We found that student participants experienced multiple forms of oppression, financial challenges, and lack of access to academic resources, but they were able to persist through support from family, faculty, and peers, along with faith-based practices and creative arts. Findings provide insights for higher education leaders, STEM and health sciences faculty, and the healthcare industry to advance equity for Black women pursuing healthcare careers.