Elucidating the Structure of Chiral Molecules by using Amplified Vibrational Circular Dichroism: From Theory to Experimental Realization

Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low‐lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure.     

Capital Accumulation and Embodied Technological Progress

This paper combines technology adoption with capital accumulation taking into account technological progress. We model this as a multi-stage optimal control problem and solve it using the corresponding maximum principle. The model with linear revenue can be solved analytically, while the model with market power is solved numerically. We obtain that investment jumps upwards right at the moment that a new technology is adopted. We find that, if the firm has market power, the firm cuts down on investment before a new technology is adopted. Furthermore, we find that larger firms adopt a new technology later.     

Thermal expansion in 3d-metal Prussian Blue Analogs—A survey study

We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions M^II₃[(M′)^III(CN)₆]₂·nH₂O and M^II₂[Fe^II(CN)₆]·nH₂O, where M^II=Mn, Fe, Co, Ni, Cu and Zn, (M′)^III=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between −150 °C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3?m, F4?3m and Pm3?m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7×¹0⁻⁶ K⁻¹ for Co₃[Co(CN)₆]₂·12H₂O. All of the M^II₃[Co^III(CN)₆]₂·nH₂O compounds show negative thermal expansion behavior, which correlates with the Irving–Williams series for metal complex stability. The thermal expansion behavior for the PBAs of the M^II₃[Fe^III(CN)₆]₂·nH₂O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the M^II₂[Fe^II(CN)₆]·nH₂O compounds show positive thermal expansion behavior.     

Bridge‐Localized HOMO‐Binding Character of Divinylanthracene‐Bridged Dinuclear Ruthenium Carbonyl Complexes: Spectroscopic,Spectroelectrochemical, and Computational Studies

The electronic properties of four divinylanthracene‐bridged diruthenium carbonyl complexes [{RuCl(CO)(PMe₃)₃}₂(μ? CH?CHArCH?CH)] (Ar=9,10‐anthracene ( 1 ), 1,5‐anthracene ( 2 ), 2,6‐anthracene ( 3 ), 1,8‐anthracene ( 4 )) obtained by molecular spectroscopic methods (IR, UV/Vis/near‐IR, and EPR spectroscopy) and DFT calculations are reported. IR spectroelectrochemical studies have revealed that these complexes are first oxidized at the noninnocent bridging ligand, which is in line with the very small ν(C?O) wavenumber shift that accompanies this process and also supported by DFT calculations. Because of poor conjugation in complex 1 , except oxidized 1⁺ , the electronic absorption spectra of complexes 2⁺ , 3⁺ , and 4⁺ all display the characteristic near‐IR band envelopes that have been deconvoluted into three Gaussian sub‐bands. Two of the sub‐bands belong mainly to metal‐to‐ligand charge‐transfer (MLCT) transitions according to results from time‐dependent DFT calculations. EPR spectroscopy of chemically generated 1⁺ – 4⁺ proves largely ligand‐centered spin density, again in accordance with IR spectra and DFT calculations results.     

Routing a mix of conventional,plug-in hybrid,and electric vehicles

We introduce an electric vehicle routing problem combining conventional, plug-in hybrid, and electric vehicles. Electric vehicles are constrained in their service range by their battery capacity, and may require time-consuming recharging operations at some specific locations. Plug-in hybrid vehicles have two engines, an internal combustion engine and an electric engine using a built-in rechargeable battery. These vehicles can avoid visits to recharging stations by switching to fossil fuel. However, this flexibility comes at the price of a generally higher consumption rate and utility cost.To solve this complex problem variant, we design a sophisticated metaheuristic which combines a genetic algorithm with local and large neighborhood search. All route evaluations, within the approach, are based on a layered optimization algorithm which combines labeling techniques and greedy evaluation policies to insert recharging stations visits in a fixed trip and select the fuel types. The metaheuristic is finally hybridized with an integer programming solver, over a set partitioning formulation, so as to recombine high-quality routes from the search history into better solutions. Extensive experimental analyses are conducted, highlighting the good performance of the algorithm and the contribution of each of its main components. Finally, we investigate the impact of fuel and energy cost on fleet composition decisions. Our experiments show that a careful use of a mixed fleet can significantly reduce operational costs in a large variety of price scenarios, in comparison with the use of a fleet composed of a single vehicle class.     

Dynamic programming based metaheuristics for the dial-a-ride problem

The organization of a specialized transportation system to perform transports for elderly and handicapped people is usually modeled as dial-a-ride problem. Users place transportation requests with specified pickup and delivery locations and times. The requests have to be completed under user inconvenience considerations by a specified fleet of vehicles. In the dial-a-ride problem, the aim is to minimize the total travel times respecting the given time windows, the maximum user ride times, and the vehicle restrictions. This paper introduces a dynamic programming algorithm for the dial-a-ride problem and demonstrates its effective application in (hybrid) metaheuristic approaches. Compared to most of the works presented in literature, this approach does not make use of any (commercial) solver. We present an exact dynamic programming algorithm and a dynamic programming based metaheuristic, which restricts the considered solution space. Then, we propose a hybrid metaheuristic algorithm which integrates the dynamic programming based algorithms into a large neighborhood framework. The algorithms are tested on a given set of benchmark instances from the literature and compared to a state-of-the-art hybrid large neighborhood search approach.