Non-equilibrium phenomena and molecular reaction dynamics: mode space, energy space and conformer space

status: publishe

Colloquium Overview Statement: What’s New at Gournia? The Gournia Excavation Project 2010–Present.

Abstract of paper read at the 119th Annual Meeting of the Archaeological Institute of America, Boston, Massachusetts, January 7, 2018.Harriet Boyd Hawes conducted the first systematic excavations at Gournia in 1901 and 1903-1904, revealing a palace, a public plateia, some 64 houses, two extramural cemeteries, and a street-network. Hawes was primarily concerned with documenting this small city at its height in the Late Minoan IA (ca. 1600-1480 B.C.E.) period. More recent work at the site and its environs, including a detailed examination of the settlement’s Prepalatial remains, House Tombs and palace (Soles), a reappraisal of the site’s architecture using Hawes’s notebooks (Fotou), a regional survey (Watrous), and an architectural mapping project of the harbor area (Watrous), however, revealed tantalizing clues that the settlement was a thriving Protopalatial (MM IB-II) center and that its Neopalatial (MM IIIA-LM IB) history was far more complex than previously understood. As a result of these studies, Watrous (University at Buffalo, SUNY) initiated a five-year excavation project (2010-2014) with the goal of documenting how and when the settlement was established and how it changed over time. This colloquium includes seven papers, each focusing on key aspects of the built and social environments of Gournia as revealed by five summers of excavation and three study seasons. Taken collectively, these papers shed important new light on how the settlement developed and changed over time. Buell (Concordia University) and McEnroe (Hamilton College) will discuss aspects of their work on the settlement’s architecture, especially as it pertains to the Protopalatial period, its community, and socio-political and economic organization. Gallimore (Wilfred Laurier University) and Glowacki (Texas A&M University) provide an overview of the palace area from its Pre- and Protopalatial remains, to the establishment of the Neopalatial palace in the Middle Minoan IIIA period through to its final destruction at the end of the LM IB period. Smith (Brock University) presents two foundation deposits recovered from palace that mark two crucial events in the life history of the complex, including its early Neopalatial foundation (MM IIIA) and later ashlar refurbishment (LM IB). Barnes (Old Dominion University) and Kunkel (Hunter College) focus on the industrial character of the site in the Late Minoan IA period, presenting, respectively, on a metal foundry and kiln installation in the settlement’s northern sector. Chapin (Brevard College) provides a diachronic overview of the Gournia plasters from both the palace and city. Watrous (University at Buffalo, SUNY) offers an overview of the settlement during its final Neopalatial phase (LM IB), framing his discussion against the broader socio-political developments of the Mirabello region and the northern Isthmus of Ierapetra

Reflections on a Teaching Commons Regarding Diversity and Inclusive Pedagogy

Recently, twenty-one instructors at a Midwestern university participated in a faculty development seminar entitled, “Developing Pedagogies to Enhance Excellence and Diversity.” They designed a pedagogical change for the following academic year based on the workshop. During the following year, we collected data on the workshop participants through surveys and interviews to discover if they had implemented the proposed changes and what they discovered in the process. Thirteen of the twenty-one participants responded to our request for information and nine implemented their proposed changes during our data collection. Reviewing the data, we found three areas where participants made changes: application of pedagogical innovations, equal access to learning and inclusive pedagogy, and assessment of power and position as teacher. Many continued to reflect on how to make these changes more effective and indicated a desire for collegiality to sustain them in their efforts to improve their teaching practices

A parallel multistate framework for atomistic non-equilibrium reaction dynamics of solutes in strongly interacting organic solvents

We describe a parallel linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM. Forces are obtained using the Hellman-Feynmann relationship, giving continuous gradients, and excellent energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to CCSD(T)-F12 electronic structure theory, we built a 64-state MS-EVB model designed to study the F + CD3CN -> DF + CD2CN reaction in CD3CN solvent. This approach allows us to build a reactive potential energy surface (PES) whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We use our PES to run MD simulations, and examine a range of transient observables which follow in the wake of reaction, including transient spectra of the DF vibrational band, time dependent profiles of vibrationally excited DF in CD3CN solvent, and relaxation rates for energy flow from DF into the solvent, all of which agree well with experimental observations. Immediately following deuterium abstraction, the nascent DF is in a non-equilibrium regime in two different respects: (1) it is highly excited, with ~23 kcal mol-1 localized in the stretch; and (2) not yet Hydrogen bonded to the CD3CN solvent, its microsolvation environment is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral blue shift, while relaxation of its microsolvation environment results in a red shift. These two competing effects result in a post-reaction relaxation profile distinct from that observed when DF vibration excitation occurs within an equilibrium microsolvation environment. The parallel software framework presented in this paper should be more broadly applicable to a range of complex reactive systems.Comment: 58 pages and 29 Figure