Periodic energy decomposition analysis for electronic transport studies as a tool for atomic scale device manufacturing

Atomic scale manufacturing is a necessity of the future to develop atomic scale devices with high precision.A different perspective of the quantum realm,which includes the tunnelling effect,leakage current at the atomic-scale,Coulomb blockade and Kondo effect,is inevitable for the fabrication and hence,the mass production of these devices.For these atomic-scale device development,molecular level devices must be fabricated.Proper theoretical studies could be an aid towards the experimental realities.Electronic transport studies are the basis to realise and interpret the problems happening at this minute scale.Keeping these in mind,we present a periodic energy decomposition analysis(pEDA)of two potential candidates for moletronics:phthalocyanines and porphyrins,by placing them over gold substrate cleaved at the(111)plane to study the adsorption and interaction at the interface and then,to study their application as a channel between two electrodes,thereby,providing a link between pEDA and electronic transport studies.pEDA provides information regarding the bond strength and the contribution of electrostatic energy,Pauli’s energy,orbital energy and the orbital interactions.Combining this analysis with electronic transport studies can provide novel directions for atomic/close-toatomic-scale manufacturing(ACSM).Literature survey shows that this is the first work which establishes a link between pEDA and electronic transport studies and a detailed pEDA study on the above stated molecules.The results show that among the molecules studied,porphyrins are more adsorbable over gold substrate and conducting across a molecular junction than phthalocyanines,even though both molecules show a similarity in adsorption and conduction when a terminal thiol linker is attached.A further observation establishes the importance of attractive terms,which includes interaction,orbital and electrostatic energies,in correlating the pEDA study with the transport properties.By progressing this research,further developments could be possible in atomic-scale manufacturing in the future.

Redesign of a short-chain dehydrogenase/reductase for asymmetric synthesis of ethyl (R)-2-hydroxy-4-phenylbutanoate based on per-residue free energy decomposition and sequence conservatism analysis

As an important building block for the synthesis of angiotensin-converting enzyme inhibitors,ethyl(R)-2-hy-droxyl-4-phenylbutanoate[(R)-HPBE]has attracted increasing attention.The key to industrial biosynthesis of(R)-HPBE is a biocatalyst that efficiently reduces ethyl 2-oxo-4-phenylbutanoate(OPBE)with high R-enantiose-lectivity.This paper proposed a strategy for identifying key residues involved in enantioselectivity control based on per-residue free energy decomposition and sequence conservatism analysis.Using this strategy,4 noncon-servative sites with high energy contribution to binding of OPBE were chosen as engineering targets,generating variant Mu27 with 99%conversion and 98%(R)ee value at substrate loading of up to 500 mmol/L.MD simu-lations suggested the higher stability and formation probability of Mu27-OPBEproR prereaction state as key rea-sons for the excellent R-enantioselectivity of Mu27 towards OPBE.The success in this study provides a viable approach for rational design of alcohol dehydrogenases with high enantioselectivity towards unnatural substrates.

Corrosion Inhibition of Aluminium in Gas and Acid Media by Some Chalcone-Based N-(3-Aminopropyl)Imidazoles: TD-DFT-Based FMO, Conceptual DFT, QTAIM and EDA Studies

The efficacy and mode of action of five chalcone-based imidazole derivatives as corrosion inhibitors of aluminium metal in gas-phase and acidic medium have been investigated herein via quantum chemical calculations. Dispersion-corrected DFT (DFT-D3) and time-dependent DFT (TD-DFT) calculations were performed at PBE0/def2-TZVP//PBEh-3c and CAM-B3LYP/def2- TZVP levels of theory, respectively. Conceptual DFT, the quantum theory of atoms-in-molecules (QTAIM) and local energy decomposition (LED) analyses have been performed. The LED analysis was performed at the coupled-cluster singles and doubles with perturbative triples (CCSD(T))/def2-SVP level of theory. Frontier molecular orbital energy gaps calculated using the TD-DFT method are found to lie in the range 3.574 - 4.444 eV, indicative of good adsorption and corrosion inhibition efficacies of the investigated molecules. The interactions between aluminium and the inhibitor molecules studied are found to be energetically favorable, owing to negative computed interaction energy values. Furthermore, QTAIM analysis revealed metal-carbon, metal-oxygen and metal-nitrogen interactions in the inhibitor-aluminium complexes, which are predominantly electrostatic in character, according to LED analysis results. Calculated proton affinities (PAs) have revealed the anticorrosion potentials of the investigated inhibitors in acidic medium, with a noticeable dependency on temperature within the range 273.15 - 343.15 K.

A Disturbance Source Location Method on the Low Frequency Oscillation With Time-varying Steady-state Points

The low frequency oscillation is a serious threat to security and stability of a power grid.How to locate the disturbance source accurately is an important issue to low frequency oscillation disposal.Existing methods have poor adaptability to the low frequency oscillation with time-varying steady-state points because of the limitations in the location criterion derivation.A disturbance source location method on a low frequency oscillation with good generality is presented in the paper.Firstly,the reasons why the steady-state points are time-varying on a low frequency oscillation are analyzed.Then,based on the energy function construction form,the branch transmission energy is decomposed into state energy,reciprocating energy and dissipation energy by mathematical derivation.The flow direction of the dissipation energy shows the source and destination of the disturbance energy,and the specific location of a disturbance source can be identified according to its flow direction.Meanwhile,to meet the needs of energy calculation,a recognition method on the electrical quantities steady-state points is also presented by using the cubic spline interpolation.Simulation results show the correctness of the derivation and analysis on energy structure in the paper,and the disturbance source can be located accurately according to the dissipation energy.

Condition monitoring and fault diagnosis strategy of railway point machines using vibration signals

Condition monitoring of railway point machines is important for train operation safety and effectiveness.Referring to the fields of mechanical equipment fault detection,this paper proposes a fault detection and identification strategy of railway point machines via vibration signals.A comprehensive feature distilling approach by combining variational mode decomposition(VMD)energy entropy and time-and frequency-domain statistical features is presented,which is more effective than single type of feature.The optimal set of features was selected with ReliefF,which helps improve the diagnosis accuracy.Support vector machine(SVM),which is suitable for a small sample,is adopted to realize diagnosis.The diagnosis accuracy of the proposed method reaches 100%,and its effectiveness is verified by experiment comparisons.In this paper,vibration signals are creatively adopted for fault diagnosis of railway point machines.The presented method can help guide field maintenance staff and also provide reference for fault diagnosis of other equipment.

Structural landscape on a series of rhein:Berberine cocrystal salt solvates:The formation,dissolution elucidation from experimental and theoretical investigations

The specific crystalline form of a compound remarkably affects its physicochemical properties.Therefore,a detailed analysis of the structural features and intermolecular interactions of a multi-component crystal is feasible to understand the relationships among the structure,physicochemical properties and the formation mechanism.In the present study,three novel cocrystal salt solvates of rhein and berberine were reported for the first time.Various solid characterizations and theoretical computations based on density functional theory(DFT)were carried out to demonstrate the intermolecular interactions.The theoretical computation shows that the strongest interaction existed between berberine cation and rhein anion,and the electrostatic interaction play a dominant role.However,no salt bond was observed between them.Further intrinsic dissolution rate analysis in water shows that the monohydrate exhibits 17 times enhancement in comparison with rhein.The rhein and berberine combined in ionic state in cocrystal salt is the main reason for the solubility improvement.This paper suggests that the interactions between the different components can be visualized and qualitatively and quantitatively analyzed by theoretical computation,which is helpful to understand the relationship between stereochemical structure and physicochemical properties of multi-component complex.

A comparative study on the reactivity of cationic niobium clusters with nitrogen and oxygen

We have prepared well-resolved Nb^(+)_(n)(n=1-10)clusters and report here an in-depth study on the es-sentially different reactivity with N_(2)and O_(2),by utilizing a multiple-ion laminar flow tube reactor in tandem with a customized triple quadrupole mass spectrometer(MIFT-TQMS).As results,the Nb^(+)_(n)clus-ters are found to readily react with N_(2)and form adsorption products Nb_(n)N^(+)_(2m);in contrast,the reactions with O_(2)give rise to Nb_(n)O^(+)_(1−4)products,and the odd-oxygen products indicate O-O bond dissociation,as well as increased mass abundance of NbO^(+)pertaining to oxygen-etching reactions.We illustrate how N_(2) prefers a physical adsorption on Nb^(+)_(n)clusters with an end-on orientation for all the products,and allow for size-selective Nb^(+)_(n)clusters to act as electron donor or acceptor in forming Nb_(n)N^(+)_(2m).In contrast to these nitrides,the dioxides Nb_(n)O+2display much larger binding energies,with O_(2)always as an electron acceptor,corresponding to superoxide or peroxide states in the initial reactions.Density-of-states and orbital anal-yses show that the interactions between Nb^(+)_(n)and O_(2)are dominated by strongπ-backdonation indicative of incidental electron transfer;whereas weakπ-backdonation and simultaneousσdonation interactions exist in Nb_(n)N^(+)_(2).Further,reaction dynamics analysis illustrates the different interactions for N_(2)and O_(2) in approaching the Nb^(+)_(n)clusters,showing the energy diagrams for N_(2)adsorption and O-O bond dissoci-ation in producing odd-oxygen products.Fragment analyses with orbital correlation and donor-acceptor charge transfer are also performed,giving rise to full insights into the reactivities and interactions of such transition metal clusters with typical diatomic molecules.

Theoretical Study on the Hydrogen Bonding Interactions in Complexes of 5-Hydroxytryptamine with Water

The energies, geometries and harmonic vibrational frequencies of 1 ： 1 5-hydroxytryptamine-water （5-HT-H20） complexes are studied at the MP2/6-311 ＋ ＋ G（d,p） level. Natural bond orbital （NBO）, quantum theory of atoms in molecules （QTAIM） analyses and the localized molecular orbital energy decomposition analysis （LMO-EDA） were performed to explore the nature of the hydrogen-bonding interactions in these complexes. Various types of hydro- gen bonds （H-bonds） are formed in these 5-HT-H20 complexes. The intermolecular C4H55HT＇＂Ow H-bond in HTW3 is strengthened due to the cooperativity, whereas no such cooperativity is found in the other 5-HT-H20 complexes. H-bond in which nitrogen atom of amino in 5-HT acted as proton donors was stronger than other H-bonds. Our researches show that the hydrogen bonding interaction plays a vital role on the relative stabilities of 5-HT-H20 complexes.