Search results for " function"

DFT calculation of structures and NMR chemical shifts of simple models of small diameter zigzag single wall carbon nanotubes (SWCNTs)

2011

Linearly conjugated benzene rings (acenes), belt-shape molecules (cyclic acenes) and model single wall carbon nanotubes (SWCNTs) were fully optimized at the unrestricted level of density functional theory (UB3LYP/6-31G*). The models of SWCNTs were selected to get some insight into the potential changes of NMR chemical shift upon systematic increase of the molecular size. The theoretical NMR chemical shifts were calculated at the B3LYP/pcS-2 level of theory using benzene as reference. In addition, the change of radial breathing mode (RBM), empirically correlated with SWCNT diameter, was directly related with the radius of cyclic acenes. Both geometrical and NMR parameters were extrapolated t…

Giant Mechanocaloric Effects in Fluorite-Structured Superionic Materials

2016

Mechanocaloric materials experience a change in temperature when a mechanical stress is applied on them adiabatically. Thus, far, only ferroelectrics and superelastic metallic alloys have been considered as potential mechanocaloric compounds to be exploited in solid-state cooling applications. Here we show that giant mechanocaloric effects occur in hitherto overlooked fast ion conductors (FIC), a class of multicomponent materials in which above a critical temperature, Ts, a constituent ionic species undergoes a sudden increase in mobility. Using first-principles and molecular dynamics simulations, we found that the superionic transition in fluorite-structured FIC, which is characterized by …

Chemical modification of carbon nanomaterials (SWCNTs, DWCNTs, MWCNTs and SWCNHs) with diphenyl dichalcogenides

2015

Control over chemical functionalization is a crucial point in the field of nanotechnology. Herein, we present the covalent functionalization of several carbon nanoforms (single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanohorns) by means of diphenyl dichalcogenides. These ones show different reactivity to the nanomaterials and are able to modify their electronic properties depending on the electronegativity of the functionalizing heteroatom. Theoretical calculations were also performed to support the experimental results. All the modified structured nanocarbons were thoroughly characterized by TGA Raman, XPS, UV/Vis/nIR, IR and TEM te…

Short hydrogen bonds enhance nonaromatic protein-related fluorescence

2021

Significance Intrinsic fluorescence of nonaromatic amino acids is a puzzling phenomenon with an enormous potential in biophotonic applications. The physical origins of this effect, however, remain elusive. Herein, we demonstrate how specific hydrogen bond networks can modulate fluorescence. We highlight the key role played by short hydrogen bonds, present in the protein structure, on the ensuing fluorescence. We provide detailed experimental and molecular evidence to explain these unusual nonaromatic optical properties. Our findings should benefit the design of novel optically active biomaterials for applications in biosensing and imaging.

ZrO2 Acting as a Redox Catalyst

2016

Surface defects are discussed and reviewed with regards to the use of ZrO2 in applications involving interactions with CO, H2, CH4, CO2, water and hydrocarbons. Studies of catalytic partial oxidation of methane reveal that part of the surface lattice oxygen in terraces can be removed by methane at high temperatures (e.g. 900 °C). The reaction proceeds via a surface confined redox mechanism. The studies presented here also highlight that defects play a decisive role in the water–gas-shift reaction, since the reaction is likely carried out via OH groups present at defect sites, which are regenerated by dissociating water. Hydroxyl chemistry on ZrO2 is briefly reviewed related to the studies p…

Large-Cavity Coronoids with Different Inner and Outer Edge Structures

2020

Coronoids, polycyclic aromatic hydrocarbons with geometrically defined cavities, are promising model structures of porous graphene. Here, we report the on-surface synthesis of C168 and C140 coronoids, referred to as [6]- and [5]coronoid, respectively, using 5,9-dibromo-14-phenylbenzo[m]tetraphene as the precursor. These coronoids entail large cavities (>1 nm) with inner zigzag edges, distinct from their outer armchair edges. While [6]coronoid is planar, [5]coronoid is not. Low-temperature scanning tunneling microscopy/spectroscopy and noncontact atomic force microscopy unveil structural and electronic properties in accordance with those obtained from density functional theory calculation…

Thermodynamic stability of stoichiometric LaFeO 3 and BiFeO 3 : a hybrid DFT study

2017

BiFeO3 perovskite attracts great attention due to its multiferroic properties and potential use as a parent material for Bi1−xSrxFeO3−δ and Bi1−xSrxFe1−yCoyO3−δ solid solutions in intermediate temperature cathodes of oxide fuel cells. Another iron-based LaFeO3 perovskite is the end member for well-known solid solutions (La1−xSrxFe1−yCoyO3−δ) used for oxide fuel cells and other electrochemical devices. In this study an ab initio hybrid functional approach was used for the study of the thermodynamic stability of both LaFeO3 and BiFeO3 with respect to decompositions to binary oxides and to elements, as a function of temperature and oxygen pressure. The localized (LCAO) basis sets describing th…

Geometric Structure and Torsional Potential of Biisothianaphthene. A Comparative DFT and ab Initio Study

1997

We present a study of the torsional potential of biisothianaphthene and compare it to that of bithiophene. The calculations are performed at the ab initio and semiempirical Hartree−Fock (HF), ab initio post-Hartree−Fock, and density functional theory (DFT) levels. Our study has two major aims:  (i) on the physico-chemical side, to asses the optimal conformation of biisothianaphthene and evaluate the rotational barriers toward coplanar structures and (ii) on the methodological side, to asses the usefulness of DFT approaches. In contrast to previous estimates, the torsional potential of biisothianaphthene is found to differ markedly from that of bithiophene. For biisothianaphthene, strongly r…

2017

The adsorption of molecular acceptors is a viable method for tuning the work function of metal electrodes. This, in turn, enables adjusting charge injection barriers between the electrode and organic semiconductors. Here, we demonstrate the potential of pyrene-tetraone (PyT) and its derivatives dibromopyrene-tetraone (Br-PyT) and dinitropyrene-tetraone (NO2-PyT) for modifying the electronic properties of Au(111) and Ag(111) surfaces. The systems are investigated by complementary theoretical and experimental approaches, including photoelectron spectroscopy, the X-ray standing wave technique, and density functional theory simulations. For some of the investigated interfaces the trends expecte…

Construction of green nanostructured heterogeneous catalysts via non-covalent surface decoration of multi-walled carbon nanotubes with Pd(II) complex…

2017

Abstract Green nanostructured heterogeneous catalysts were prepared via a bottom-up strategy. Designed ligands were synthesized joining covalently an electrondeficient pyrimidine residue and a scorpiand azamacrocycle. The desired molecular properties were easily transferred to nanostructured materials in two steps: first, exploiting their spontaneous chemisorption onto multi-walled carbon nanotubes (MWCNTs) via the pyrimidinic moiety in water at room temperature, then, taking advantage of the easy coordination of Pd(II) to the azamacrocycle in the same conditions. An evenly distribution of catalytic centres was obtained on the MWCNTs surface. Catalytic properties of these materials were ass…