The states that hide in the shadows: the potential role of conical intersections in the ground state unimolecular decay of a Criegee Intermediate

Author(s):  
Barbara Marchetti ◽  
Vincent John Esposito ◽  
Rachel Bush ◽  
Tolga Karsili

Criegee intermediates (CIs) are of great significance to Earth’s troposphere – implicated in altering the tropospheric oxidation cycle and in forming low volatility products that typically condense to form secondary...

2021 ◽  
Author(s):  
Ignacio Fernández Galván ◽  
Anders Brakestad ◽  
Morgane Vacher

Chemiexcitation, the generation of electronic excited states by a thermal reaction initiated on the ground state, is an essential step in chemiluminescence, and it is mediated by the presence of a conical intersection that allows a nonadiabatic transition from ground state to excited state. Conical intersections classified as sloped favor chemiexcitation over ground state relaxation. The chemiexcitation yield of 1,2-dioxetanes is known to increase upon methylation. In this work we explore to which extent this trend can be attributed to changes in the conical intersection topography or accessibility. Since conical intersections are not isolated points, but continuous seams, we locate regions of the conical intersection seams that are close to the configuration space traversed by the molecules as they react on the ground state. We find that conical intersections are energetically and geometrically accessible from the reaction trajectory, and that topographies favorable to chemiexcitation are found in all three molecules studied. Nevertheless, the results suggest that dynamic effects are more important for explaining the different yields than the static features of the potential energy surfaces.


2019 ◽  
Vol 47 (5) ◽  
pp. 1393-1404 ◽  
Author(s):  
Thomas Brand

Abstract The Popeye domain-containing gene family encodes a novel class of cAMP effector proteins in striated muscle tissue. In this short review, we first introduce the protein family and discuss their structure and function with an emphasis on their role in cyclic AMP signalling. Another focus of this review is the recently discovered role of POPDC genes as striated muscle disease genes, which have been associated with cardiac arrhythmia and muscular dystrophy. The pathological phenotypes observed in patients will be compared with phenotypes present in null and knockin mutations in zebrafish and mouse. A number of protein–protein interaction partners have been discovered and the potential role of POPDC proteins to control the subcellular localization and function of these interacting proteins will be discussed. Finally, we outline several areas, where research is urgently needed.


Author(s):  
Katherine Guérard ◽  
Sébastien Tremblay

In serial memory for spatial information, some studies showed that recall performance suffers when the distance between successive locations increases relatively to the size of the display in which they are presented (the path length effect; e.g., Parmentier et al., 2005) but not when distance is increased by enlarging the size of the display (e.g., Smyth & Scholey, 1994). In the present study, we examined the effect of varying the absolute and relative distance between to-be-remembered items on memory for spatial information. We manipulated path length using small (15″) and large (64″) screens within the same design. In two experiments, we showed that distance was disruptive mainly when it is varied relatively to a fixed reference frame, though increasing the size of the display also had a small deleterious effect on recall. The insertion of a retention interval did not influence these effects, suggesting that rehearsal plays a minor role in mediating the effects of distance on serial spatial memory. We discuss the potential role of perceptual organization in light of the pattern of results.


2014 ◽  
pp. 79-130 ◽  
Author(s):  
Ales Novak

The term ?business model' has recently attracted increased attention in the context of financial reporting and was formally introduced into the IFRS literature when IFRS 9 Financial Instruments was published in November 2009. However, IFRS 9 did not fully define the term ‘business model'. Furthermore, the literature on business models is quite diverse. It has been conducted in largely isolated fashion; therefore, no generally accepted definition of ?business model' has emerged. Therefore, a better understanding of the notion itself should be developed before further investigating its potential role within financial reporting. The aim of this paper is to highlight some of the perceived key themes and to identify other bases for grouping/organizing the literature based on business models. The contributions this paper makes to the literature are twofold: first, it complements previous review papers on business models; second, it contains a clear position on the distinction between the notions of the business model and strategy, which many authors identify as a key element in better explaining and communicating the notion of the business model. In this author's opinion, the term ‘strategy' is a dynamic and forward-looking notion, a sort of directional roadmap for future courses of action, whereas, ‘business model' is a more static notion, reflecting the conceptualisation of the company's underlying core business logic. The conclusion contains the author's thoughts on the role of the business model in financial reporting.


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