Anisotropic spin transport and photoresponse characteristics detected by tip movement in magnetic single-molecule junction

Orientation-dependent transport properties induced by anisotropic molecules are enticing in single-molecule junctions.Here,using the first-principles method,we theoretically investigate spin transport properties and photoresponse characteristics in trimesic acid magnetic single-molecule junctions with different molecular adsorption orientations and electrode contact sites.The transport calculations indicate that a single-molecule switch and a significant enhancement of spin transport and photoresponse can be achieved when the molecular adsorption orientation changes from planar geometry to upright geometry.The maximum spin polarization of current and photocurrent in upright molecular junctions exceeds 90%.Moreover,as the Ni tip electrode moves,the tunneling magnetoresistance of upright molecular junctions can be increased to 70%.The analysis of the spin-dependent PDOS elucidates that the spinterfaces between organic molecule and ferromagnetic electrodes are modulated by molecular adsorption orientation,where the molecule in upright molecular junctions yields higher spin polarization.Our theoretical work paves the way for designing spintronic devices and optoelectronic devices with anisotropic functionality base on anisotropic molecules.

利用高空间分辨针尖增强拉曼散射识别氮掺杂富勒烯催化的氧还原反应中间体

氮掺杂富勒烯(C_(59)N)催化剂在氢燃料电池的氧还原反应中表现出良好的活性.然而,C_(59)N上发生的氧还原反应路径的中间体和催化活性位点尚未被直接表征,阻碍了对C_(59)N催化剂在氧还原反应中活性增强机制的理解.本文通过在模拟计算中考虑空间限制等离子体的不均匀分布,从理论上提出高空间分辨针尖增强拉曼散射可以有效地识别C_(59)N上氧还原反应的不同中间体构型.通过调整聚焦的空间限制等离子体位置,氧还原反应中与O_(2)-C_(59)N相互作用有关联的振动模式可以被高空间分辨针尖增强拉曼散射光谱直接选择出来,并且得到增强.此外,选择出来的振动模式对应的高空间分辨针尖增强拉曼散射图像在吸附位点周围给出了拉曼热点,提供了氧还原反应在C_(59)N上催化活性位点的原位观测细节。这些发现为今后通过高分辨率高空间分辨针尖增强拉曼散射技术在分子尺度上探索催化系统提供了良好的参考.

Effect of aggregation on thermally activated delayed fluorescence and ultralong organic phosphorescence:QM/MM study

Aggregation-induced thermally activated delayed fluorescence(TADF)phenomena have attracted extensive attention recently.In this paper,several theoretical models including monomer,dimer,and complex are used for the explanation of the luminescent properties of(R)-5-(9H-carbazol-9-yl)-2-(1,2,3,4-tetrahydronaphthalen-1-yl)isoindoline-1,3-dione((R)-ImNCz),which was recently reported[Chemical Engineering Journal 418129167(2021)].The polarizable continuum model(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method are adopted in simulation of the property of the molecule in the gas phase,solvated in acetonitrile and in aggregation states.It is found that large spin–orbit coupling(SOC)constants and a smaller energy gap between the first singlet excited state and the first triplet excited state(△E_(st))in prism-like single crystals(SC_(p)-form)are responsible for the TADF of(R)-lmNCz,while no TADF is found in block-like single crystals(SC_(b)-form)with a larger △E_(st).The multiple ultralong phosphorescence(UOP)peaks in the spectrum are of complex origins,and they are related not only to ImNCz but also to a minor amount of impurities(ImNBd)in the crystal prepared in the laboratory.The dimer has similar phosphorescence emission wavelengths to the(R)-lmNCz-SC_(p) monomers.The complex composed of(R)-lmNCz and(R)-lmNBd contributes to the phosphorescent emission peak at about 600 nm,and the phosphorescent emission peak at about 650 nm is generated by(R)-lmNBd.This indicates that the impurity could also contribute to emission in molecular crystals.The present calculations clarify the relationship between the molecular aggregation and the light-emitting properties of the TADF emitters and will therefore be helpful for the design of potentially more useful TADF emitters.

Density Functional Theory Study on Raman Spectra of Rhodamine Molecules in Different Forms

Rhodamine molecules are one of the most used dyes for applications related to Raman spectroscopy. We have systematically studied Raman spectra of Rhodamine 6G, Rhodamine 123, and Rhodamine B （RhB） molecules using density functional theory. It is found that with BP86 functional the calculated Raman spectra of cationic Rhodamine molecules are in good agreement with corresponding experimental spectra in aqueous solution. It is shown that the involvement of the counter ion, chlorine, and the specific hydrogen bonds has noticeable effects on the Raman spectra of RhB that can partially explain the observed difference between Raman spectra of RhB in solution and on gold surfaces. It also indicates that an accurate description of surface enhanced Raman scattering for Rhodamine molecules on metal surface still requires to take into account the changes induced by the interracial interactions.

Tunneling magnetoresistance in ferromagnet/organic-ferromagnet/metal junctions

Spin-dependent transport in ferromagnet/organic-ferromagnet/metal junctions is investigated theoretically.The results reveal a large tunneling magnetoresistance up to 3230%by controlling the relative magnetization orientation between the ferromagnet and the central organic ferromagnet.The mechanism is explained by distinct efficient spin-resolved tunneling states in the ferromagnet between the parallel and antiparallel spin configurations.The key role of the organic ferromagnet in generating the large magnetoresistance is explored,where the spin selection effect is found to enlarge the difference of the tunneling states between the parallel and antiparallel configurations by comparing with the conventional organic spin valves.The effects of intrinsic interactions in the organic ferromagnet including electron–lattice interaction and spin coupling with radicals on the magnetoresistance are discussed.This work demonstrates a promising potential of organic ferromagnets in the design of high-performance organic spin valves.

Theoretical verification of intermolecular hydrogen bond induced thermally activated delayed fluorescence in SOBF-OMe

Thermally activated delayed fluorescence(TADF)molecules have attracted great attention as high efficient luminescent materials.Most of TADF molecules possess small energy gap between the first singlet excited state(S_(1))and the first triplet excited state(T_(1))to favor the up-conversion from T_(1)to S_(1).In this paper,a new TADF generation mechanism is revealed based on theoretical simulation.By systematic study of the light-emitting properties of SOBF-OMe in both toluene and in aggregation state,we find that the single SOBF-OMe could not realize TADF emission due to large energy gap as well as small up-conversion rates between S_(1)and T_(1).Through analysis of dimers,we find that dimers with intermolecular hydrogen bond(H-bond)are responsible for the generation of TADF,since smaller energy gap between S_(1)and T_(1)is found and the emission wavelength is in good agreement with experimental counterpart.The emission properties of SOBF-H are also studied for comparison,which reflect the important role of H-bond.Our theoretical results agree ith experimental results well and confirm the mechanism of H-bond induced TADF.

Current spin polarization of a platform molecule with compression effect

Using the first-principles method,the spin-dependent transport properties of a novel platform molecule containing a freestanding molecular wire is investigated by simulating the spin-polarized scanning tunneling microscope experiment with Ni tip and Au substrate electrodes.Transport calculations show that the total current increases as the tip gradually approaches to the substrate,which is consistent with the conductance obtained from previous experiment.More interestingly,the spin polarization(SP)of current modulated by compression effect has the completely opposite trend to the total current.Transmission analyses reveal that the reduction of SP of current with compression process originates from the promotion of spin-down electron channel,which is controlled by deforming the molecule wire.In addition,the density of states shows that the SP of current is directly affected by the organic–ferromagnetic spinterface.The weak orbital hybridization between the Ni tip and propynyl of molecule results in high interfacial SP,whereas the breaking of the C≡C triple of propynyl in favor of the Ni–C–C bond induces the strong orbital hybridization and restrains the interfacial SP.This work proposes a new way to control and design the SP of current through organic–ferromagnetic spinterface using functional molecular platform.

Theoretical Analysis on Optical Limiting Properties of Newly Synthesized Graphene Oxide-Porphyrin Composites

Optical limiting （OL） properties and two-photon absorption （TPA） of a series of covalently linked graphene oxide-porphyrin composite materials have been investigated by numerically solving the rate equations and field intensity equation with an iterative predictor-corrector finite-difference time-domain technique in nanosecond time domain. Our results show that graphene oxide-porphyrin composites exhibit enhanced OL behavior and possess larger TPA cross section compared with individual porphyrins. Interestingly~ unlike the previous result that porphyrin with heavier central metal shows better nonlinear abilities than that with- out metal substitute, graphene oxide-metal free porphyrin composite has stronger nonlinear absorption properties compared with graphene oxide-metal porphyrin composite. The com- putational results are in reasonable agreement with the experimental ones. Special attention has been paid to the influence of thickness of the medium and pulse width on TPA cross sections, which presents that larger TPA cross sections are obtained as the medium is thicker or the pulse duration is wider.

Variation of Two-photon Absorption Cross Sections and Optical Limiting of Compounds Induced by Static Electric Field

By numerically solving the Maxwell-Bloch equations using an iterative predictor-corrector finite-difference time-domain technique, we investigate propagating properties of a few-cycle laser pulse in a 4,4＇-bis（di-n-butylamino） stilbene （BDBAS） molecular medium when a static electric field exists. Dynamical two-photon absorption （TPA） cross sections are obtained and optical limiting （OL） behavior is displayed. The results show that when the static electric field intensity increases, the dynamical TPA cross section is enhanced and the OL behavior is improved. Moreover, both even- and odd-order harmonic spectral components are generated with existence of the static electric field because it breaks the inversion symmetry of the BDBAS molecule. This work provides a method to modulate the nonlinear optical properties of the BDBAS compounds.

Protonation Effect on One- and Two-photon Absorption Property of a Newly Synthesized Octupolar Chromophore

The protonation effects on one- and two-photon absorption properties of an octupolar molecule TA with 1,3,5-triazine core and pyrrole electron-donating end-groups have been studied at hybrid density functional theory level. A computational scheme is developed to simulate a proton attached to an atom. The numerical results show that large changes in both one- and two-photon absorption properties are observed when the compound is transformed from neutral to threefold protonated states. When the compound is protonated, more charge transfer states appear and the absorption band has a red-shift. Furthermore, the two-photon absorption cross-section is largely enhanced. The theoretical calculations demonstrate the protonation effect on promoting the intramolecular charge transfer strength. The results present qualitative agreement with the experimental observations. A two-photon absorption switch with the compound TA based on the protonation effect is proposed.

Theoretical design of single-molecule NOR and XNOR logic gates by using transition metal dibenzotetraaza[14]annulenes

The idea of replacing traditional silicon-based electronic components with the ones assembled by organic molecules to further scale down the electric circuits has been attracting extensive research focuses.Among the molecularly assembled components,the design of molecular logic gates with simple structure and high Boolean computing speed remains a great challenge.Here,by using the state-of-the-art nonequilibrium Green’s function theory in conjugation with first-principles method,the spin transport properties of single-molecule junctions comprised of two serially connected transition metal dibenzotetraaza[14]annulenes(TM(DBTAA),TM=Fe,Co)sandwiched between two single-walled carbon nanotube electrodes are theoretically investigated.The numerical results show a close dependence of the spin-resolved current-voltage characteristics on spin configurations between the left and right molecular kernels and the kind of TM atom in TM(DBTAA)molecule.By taking advantage of spin degree of freedom of electrons,NOR or XNOR Boolean logic gates can be realized in Fe(DBTAA)and Co(DBTAA)junctions depending on the definitions of input and output signals.This work proposes a new kind of molecular logic gates and hence is helpful for further miniaturization of the electric circuits.

Tuning the type of charge carriers in N-heterocyclic carbene-based molecular junctions through electrodes

Designing tunable molecular devices with different charge carriers in single-molecule junctions is crucial to the nextgeneration electronic technology.Recently,it has been demonstrated that the type of charge carriers depends on and can be tuned by controlling the molecular length and the number of interfacial covalent bonds.In this study,we show that the type of charge carriers can also be tuned by controlling the material and shape of electrodes.N-heterocyclic carbenes(NHCs)have attracted attention because of their ability to form strong,substitutional inert bonds in a variety of metals.Also,NHCs are more stable than the widely used thiol group.Therefore,we use electrodes to tune the type of charge carriers in a series of NHCs with different side groups.The ab initio calculations based on non-equilibrium Green’s formalism combined with density functional theory show that the dominant charge carrier switches from electrons to holes when gold electrodes are changed into platinum ones.The nature of the charge carriers can be identified by variations in the transport spectra at the Fermi level(EF),which are caused by the side groups.The projections of transport spectra onto the central molecules further validate our inferences.In addition,the transmission coefficient at EF is found to be dependent on the atomic interface structure.In particular,for the NHC without methyl or ethyl side groups,connecting a protruding atom on the electrode surface significantly enhances the transportability of both electrode materials.Overall,this study presents an effective approach to modifying transport properties,which has potential applications in designing functional molecular devices based on NHCs.

Geometric and Electronic Structures of Pyrazine Molecule Chemisorbed on Si(100) Surface by XPS and NEXAFS Spectroscopy

The geometric and electronic structures of several possible adsorption configurations of the pyrazine(C4H4N2)molecule covalently attached to Si(100)surface,which is of vital importance in fabricating functional nano-devices,have been investigated using X-ray spectroscopies.The Carbon K-shell(1s)X-ray photoelectron spectroscopy(XPS)and near-edge X-ray absorption fine structure(NEXAFS)spectroscopy of predicted adsorbed structures have been simulated by density functional theory with cluster model calculations.Both XPS and NEXAFS spectra demonstrate the structural dependence on different adsorption configurations.In contrast to the XPS spectra,it is found that the NEXAFS spectra exhibiting conspicuous dependence on the structures of all the studied pyrazine/Si(100)systems can be well utilized for structural identification.In addition,according to the classification of carbon atoms,the spectral components of carbon atoms in different chemical environments have been investigated in the NEXAFS spectra as well.

Low-Bias Conductance Mechanism of Diarylethene Isomers:a First-Principle Study

The structure-property relationship of diarylethene(DAE)-derivative molecular isomers,which involve ring-closed and ring-open forms,is investigated by employing the nonequilibrium Green’s function formalism combined with density functional theory.Molecular junctions are formed by the isomers connecting to Au(111)electrodes through flanked pyridine groups.The difference in electronic structures caused by different geometry structures for the two isomers,particularly the interatomic alternative single bond and double bond of the ring-closed molecule,contributes to the vastly different low-bias conductance values.The lowest unoccupied molecular orbital(LUMO)of the isomers is the main channel for electron transport.In addition,more electrons transferred to the ring-closed molecular junction in the equilibrium condition,thereby decreasing the LUMO energy to near the Fermi energy,which may contribute to a larger conductance value at the Fermi level.Our findings are helpful for understanding the mechanism of low-bias conductance and are conducive to the design of high-performance molecular switching based on diarylethene or diarylethene-derivative molecules.

Isomerism and coordination mode effects on two-photon absorption of tris(picolyl)amine-based fluorescent probes for zinc ions

One-photon absorption and two-photon absorption（TPA） properties of three tris（picolyl）amine-based zinc ion sensors are investigated by employing the density functional response theory in combination with the polarizable continuum model.The different isomer and coordination geometry of each probe are taken into account. Special emphasis is placed on the effects of isomerism and the coordination mode on the optical properties. The intra-molecular charge transfer（ICT）properties are specified by natural bond orbital charge analysis. It is shown that the isomerism has non-negligible effects on TPA properties of free ligands. It is found that both the TPA wavelength and the cross section are highly dependent on the coordination mode. When the zinc ion connects with the picolyl unit in the middle of a ligand, the zinc complex has a large TPA intensity in a long wavelength range due to the increased ICT mechanism.

Solvent Effects on Two-Photon Absorption of Alkyne and Alkene π-bridging Chromophores

The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption （TPA） processes, for two series of alkyne and alkene π-bridging molecules, within the framework of the polarization continuum model. Particular emphasis was put on the characterization of solvent effects on the molecular geometrical structures and geometric distortion, which were measured by the bond-length-alternation parameter. The π centres in the compounds are seen to play a decisive role in increasing the TPA cross section and nonlinear optical properties. All studied molecules have relatively strong TPA characteristics, while the alkyne π-bridging ones yield larger TPA cross sections.

Effect of crystallographic orientations on transport properties of methylthiol-terminated permethyloligosilane molecular junction

The understanding of the influence of electrode characteristics on charge transport is essential in the field of molecular electronics.In this work,we investigate the electronic transport properties of molecular junctions comprising methylthiolterminated permethyloligosilanes and face-centered crystal Au/Ag electrodes with crystallographic orientations of(111)and(100),based on the ab initio quantum transport simulations.The calculations reveal that the molecular junction conductance is dominated by the electronic coupling between two interfacial metal–S bonding states,which can be tuned by varying the molecular length,metal material of the electrodes,and crystallographic orientation.As the permethyloligosilane backbone elongates,although theσconjugation increases,the decreasing of coupling induced by the increasing number of central Si atoms reduces the junction conductance.The molecular junction conductance of methylthiol-terminated permethyloligosilanes with Au electrodes is higher than that with Ag electrodes with a crystallographic orientation of(111).However,the conductance trend is reversed when the electrode crystallographic orientation varies from(111)to(100),which can be ascribed to the reversal of interfacial coupling between two metal–S interfacial states.These findings are conducive to elucidating the mechanism of molecular junctions and improving the transport properties of molecular devices by adjusting the electrode characteristics.

Bias-induced reconstruction of hybrid interface states in magnetic molecular junctions

Based on first-principles calculations,the bias-induced evolutions of hybrid interface states inπ-conjugated tricene and in insulating octane magnetic molecular junctions are investigated.Obvious bias-induced splitting and energy shift of the spin-resolved hybrid interface states are observed in the two junctions.The recombination of the shifted hybrid interface states from different interfaces makes the spin polarization around the Fermi energy strongly bias-dependent.The transport calculations demonstrate that in theπ-conjugated tricene junction,the bias-dependent hybrid interface states work efficiently for large current,current spin polarization,and distinct tunneling magnetoresistance.But in the insulating octane junction,the spin-dependent transport via the hybrid interface states is inhibited,which is only slightly disturbed by the bias.This work reveals the phenomenon of bias-induced reconstruction of hybrid interface states in molecular spinterface devices,and the underlying role of conjugated molecular orbitals in the transport ability of hybrid interface states.

Perspective for aggregation-induced delayed fluorescence mechanism:A QM/MM study

To enhance the potential application of thermally activated delayed fluorescence(TADF)molecular materials,new functions are gradually cooperated to the TADF molecules.Aggregation induced emission can effectively solve the fluorescence quenching problem for TADF molecules in solid phase,thus aggregation-induced delayed fluorescence(AIDF)molecules were recently focused.Nevertheless,their luminescent mechanisms are not clear enough.In this work,excited state properties of an AIDF molecule DMF-BP-DMAC[reported in Chemistry-An Asian Journal 14828(2019)]are theoretically studied in tetrahydrofuran(THF)and solid phase.For consideration of surrounding environment,the polarizable continuum method(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method were applied for solvent and solid phase,respectively.Due to the increase of the transition dipole moment and decrease of the energy difference between the first single excited state(S1)and the ground state(S0),the radiative rate is increased by about 2 orders of magnitude in solid phase.The energy dissipation of the non-radiative process from S1 to S0 is mainly contributed by low-frequency vibrational modes in solvent,and they can be effectively suppressed in aggregation,which may lead to a slow non-radiation process in solid phase.Both factors would induce enhanced luminescence efficiency of DMF-BP-DMAC in solid phase.Meanwhile,the small energy gap between S1 and triplet excited states results in high reverse intersystem crossing(RISC)rates in both solvent and solid phase.Therefore,TADF is confirmed in both phases.Aggregation significantly influences both the ISC and RISC processes and more RISC channels are involved in solid state.The enhanced delayed fluorescence should be induced by both the enhanced fluorescent efficiency and ISC efficiency.Our calculation provides a reasonable explanation for experimental measurements and helps one to better understand the luminescence mechanism of AIDF molecules.

Optical Properties and Response Mechanism Analysis of Multi-branched Fluorescent Probes Based on Intramolecular Charge Transfer

In this work, the optical properties of fluorescent probes used for detection of biothiol were studied by employing time-dependent density functional theory. By calculating the single photon absorption and emission properties of probe Mol.1, Mol.2 and Mol.3 before and after reaction with cysteine and homocysteine, we have investigated the effect of carboncarbon triple bond and benzene ring on the properties of fluorescent probes. It is found that the oscillator strength of probe molecules increases gradually with the improvement of the structure of the electron donor triphenylamine and the addition of carbon-carbon triple bonds, and better properties of fluorescence probes have also been demonstrated. At the same time, the effect of different number of side branches on the molecular properties of the probe was also studied. The results showed that compared with single-branched molecule Z1 and tribranched probe Mol.3, two side probe molecules Z2 had higher oscillator strength and better detection effect. In addition, the new single-branched probe Mol.4 with the addition of carbon-carbon triple bonds and benzene rings has better probe properties and simpler structure than the tribranched probe Mol.3.