Observations on the Electronic Character of Anions and Cations near Water Liquid/Vapor Interfaces.

In recent years, many researchers have become interested in chemical reactions, photon-induced processes, and other events taking place at or near aqueous liquid/vapor or ice/vapor interfaces. Such studies relate to a wide variety of atmospheric, oceanographic, and environmental issues. Near these interfaces, atomic and molecular anions and cations display quite different behaviors than when they are fully solvated in the bulk medium.

Two potential paths for OH radical formation on surfaces of pure water microdroplets.

Experimental findings by others suggest that OH radicals are formed in unexpected abundance on or near surfaces of 1-50 µm microdroplets comprised of pure water, but the mechanism by which these radicals are generated is not yet fully resolved. In this work, we examine two possibilities using ab initio electronic structure methods: (1) electron transfer (ET) from a microdroplet surface-bound OH- anion to a nearby H3O+ cation and (2) proton transfer (PT) from such a H3O+ cation to a nearby OH- anion. Our findings suggest that both processes are possible but only if the droplet's underlying water molecules comprising the microdroplet provide little screening of the Coulomb interaction between the anion and cation once they reach ∼10 Å of one another.

An environmental impact statement for molecular anions.

A molecular anion's (MA's) chemical reactivity and physical behavior can be quite different when it is surrounded by other molecules than when it exists in isolation. This sensitivity to the surrounding environment is especially high for anions because their outermost valence electrons are typically loosely bound and exist in rather spatially diffuse orbitals, allowing even weak intermolecular interactions arising from the environment to have strong effects. This Perspective offers illustrations of such sensitivity for a variety of cases including (i) the effect of solvation on electron binding energies, (ii) how some "well known" anions need to have solvent molecules around to even exist as stable species, (iii) how internal Coulomb repulsions within a multiply charged MA can provide temporary stability toward electron loss, (iv) how MAs arrange themselves spatially near liquid/vapor interfaces in manners that can produce unusual reactivity, (v) how nearby cationic sites can facilitate electron attachment to form a MA site elsewhere, (vi) how internal vibrational or rotational energy can make a MA detach an electron.

Molecular Anions Perspective.

This Perspective attempts to shed light on developments in the theoretical and experimental study of molecular anions highlighting more recent workers in the field. The species I discuss include (i) valence-bound (singly and multiply charged) anions including atmospheric, catalytic, superhalogen, interfacial, and more; (ii) dipole- and correlation-bound anions including their role as doorways to other states and their appearance "in space", and (iii) metastable anions focusing on tools needed for their theoretical treatment. I also briefly discuss angular distributions of photodetached electrons and their growing utilization in experiments and theory.

Why Is Quantum Chemistry So Complicated?

The myriad tools of quantum chemistry are now widely used by a diverse community of chemists, biologists, physicists, and material scientists. The large number of methods (e.g.

Finding Valence Antibonding Levels while Avoiding Rydberg, Pseudo-continuum, and Dipole-Bound Orbitals.

Electronic structure methods are now widely used to assist in the interpretation of many varieties of experimental data. The energies and physical characteristics (e.g.

Do not forget the Rydberg orbitals.

Within any molecule or cluster containing one or more positively charged sites, families of Rydberg orbitals exist. Free electrons can attach directly, and anionic reagents with low electron binding energy can transfer an electron into one of these orbitals to form a neutral Rydberg radical. The possibilities that such a radical could form a covalent bond either to another Rydberg radical or to a radical holding its electron in a conventional valence orbital are considered.

Educator interaction with sexual minority youth.

Sexual minority youth experience a variety of challenges that are further exacerbated by intersectionality and interactions with various educators. Using a directed form of empirical, qualitative research, the authors explored the retrospective school experiences (as part of life stories) of three cohorts of sexual minorities (Stonewall Generation, HIV/AIDS Generation, and Marriage Equality Generation). The aim was to learn how they experienced K-12 education, including interactions with educators.

From Identity to Enaction: Identity Behavior Theory.

The article deals with the meaning of identity in action regulation. A strengths-based action model, Identity Behavior Theory (IBT), is concerned with the role that identity plays in the prediction of behavioral enaction, and implications for education, science, and clinical practice. With this respect the article explores and discusses how enacted behavior, including intention and action, depends on level of subscription to identity as well as on resilience and attitudes that are related to such a behavior.

Analysis of Stabilization and Extrapolation Methods for Determining Energies and Lifetimes of Metastable Electronic States.

Two methods that make use of standard electronic structure tools, the stabilization and extrapolation methods, are discussed with an eye toward pointing out their relative strengths and weaknesses and for improving their applications. In the former, whether to utilize energy data from only one or from both branches of an avoided crossing between the quasi-bound and pseudo-continuum states is one issue that is focused on. Another is the decision of where along the stabilization plot's branches (i.

Experiences of educators who identify as lesbian, gay, and bisexual.

The focus of the phenomenological qualitative study was on the lived experiences of U.S. educators who identified as lesbian, gay, and bisexual (LGB).

School counselor advocacy for gender minority students.

One-thousand-one-hundred-and-ninety-one school counselors completed an online survey regarding advocacy for and with gender minority students comprising transgender and intersex students (school counselor gender minority advocacy competence). School counselors completed a battery of three competency-based assessments to assess their levels of gender identity counselor competence, intersex counselor competence, and school counselor gender minority advocacy competence. They also completed a demographic form so that competency levels could be examined with demographic variables.

Caralumane Superacids of Lewis and Brønsted Character.

Carborane Brønsted superacids have proven to be useful reagents in a variety of organic and inorganic synthetic processes. In this work, analogs in which the icosahedral CB carborane core is replaced by a CAl core are studied using ab initio electronic structure tools. Each so-called caralumane Brønsted acid is formed by adding HF, HCl, or HH to a corresponding caralumane Lewis acid possessing a vacant Al-centered orbital that acts to accept an electron pair from the HF, HCl, or HH.

Ejecting Electrons from Molecular Anions via Shine, Shake/Rattle, and Roll.

The periodically oscillating electromagnetic potential of a photon can, in an electric-dipole transition, "shine" an electron from an anion's bound-state orbital directly into a continuum-state orbital. This occurs in photoelectron and photodetachment spectroscopy, both of which provide much information about the electronic structure of the anion. Alternatively, a molecular anion containing sufficient vibrational energy to "shake/rattle" an electron out of a bound-state orbital can induce electron detachment via a vibration-to-electronic nonadiabatic transition.

Unusual and Conventional Dative Bond Formation by s Lone Pair Donation from Alkaline Earth Metal Atoms to BH, AlH, and GaH.

Using ab initio electronic structure methods with flexible atomic orbital basis sets, we examined the nature of the bonding arising from donation of an ns electron pair on an alkaline earth atom (Mg or Ca) into a vacant n'p orbital on the group 13 atom of BH, AlH, or GaH. We also examined what happens when an excess electron is attached to form corresponding molecular anions. Although the geometries of MgBH, MgAlH, MgGaH, and CaBH are found to be much as one would expect for datively bound molecules, CaAlH and CaGaH were found to have very unusual geometries in that their Al-H or Ga-H bonds are directed toward the Ca atom rather than away, as in the other compounds.

Fate of Dipole-Bound Anion States when Hydrated.

Many strongly polar molecules can form an anion by attaching an electron to either an empty or half-filled valence-bound (VB) orbital or a so-called dipole-bound (DB) orbital. These two families of orbitals can be very different in their radial extent (the former are usually more compact, while the latter are quite diffuse) and in the degree to which they are affected by surrounding solvent molecules. In this study, the effects of hydration (representative of strong solvation) on the DB state of a model polar species are investigated with an eye toward determining whether this state is stabilized or even persists when a few to 100 water molecules surround the polar molecule.

School-Age Coping: Themes Across Three Generations of Sexual Minorities.

Because sexual minorities are an at-risk population, researchers conducted retrospective life story interviews with 191 sexual minority people comprising participants from a marriage equality cohort, an HIV/AIDS epidemic cohort, and a Stonewall rebellion cohort. The participants were located within 80 miles of four major metropolitan areas in the United States. Of the 191 participants interviewed, 90 participants talked about their school-age experiences and how they coped during elementary, middle, and high school.

Concluding remarks for advances in ion spectroscopy Faraday Discussion.

Because the Introductory Lecture of this Faraday Discussion emphasized the recent history and exciting developments in the fields of experimental methods and applications of gaseous ion spectroscopy, these Concluding Remarks are, by design, directed somewhat more toward the roles played by theory. In discussing both the experimental and theoretical studies of gaseous ions, it is important to recognize and appreciate the delicate balance workers in the field are pursuing in terms of methodological/tool development and applications to current-day pressing problems in chemistry, physics, materials science, and biology. Without both components of modern research in this field, progress will not be efficient.

Dissociative electron attachment to HGaF Lewis-Brønsted superacid.

The consequences of an excess electron attachment to HGaF4 (HF/GaF3) superacid are investigated on the basis of theoretical calculations employing ab initio methods. It is found that the dipole potential of HGaF4 plays an important role in the initial formation of a dipole-bound anionic state. Due to the kinetic instability of that initially formed anion, a fragmentation reaction occurs promptly and leads to (GaF4)- and H as the final products.