Within a generic model we analyze the Stokes linewidth in surface enhanced Raman scattering (SERS) from molecules embedded as bridges in molecular junctions. We identify four main contributions to the off-resonant Stokes signal and show that under zero voltage bias (a situation pertaining also to standard SERS experiments) and at low bias junctions only one of these contributions is pronounced. The linewidth of this component is determined by the molecular vibrational relaxation rate, which is dominated by interactions with the essentially bosonic thermal environment when the relevant molecular electronic energy is far from the metal(s) Fermi energy(ies). It increases when the molecular electronic level is close to the metal Fermi level so that an additional vibrational relaxation channel due to electron-hole (eh) excition in the molecule opens. Other contributions to the Raman signal, of considerably broader linewidths, can become important at larger junction bias.
Surface enhanced Raman spectra from molecules (bipyridyl ethylene) adsorbed on gold dumbells are observed to become increasingly asymmetric (Fano-like) at higher incident light intensity. The electronic temperature (inferred from the anti-Stokes (AS) electronic Raman signal increases at the same time while no vibrational AS scattering is seen. These observations are analyzed by assuming that the molecule-metal coupling contains an intensity dependent contribution (resulting from light-induced charge transfer transitions as well as renormalization of the molecule metal tunneling barrier). We fi…
We study the role of strong electron confinement in surface-enhanced Raman scattering from molecules adsorbed on small noble-metal particles. We describe a new source of Raman signal enhancement which originates from different behavior of sp-band and d-band electron densities near the particle boundary. In small particles, a spillover of sp-electron wave-functions beyond the classical radius gives rise to a thin layer with diminished population of d-electrons. In this surface layer, the screening of sp-electrons by d-band electron background is reduced. We demonstrate that the interplay betwee…
We study the effects of chemical bonding on Raman scattering from benzenethiol chemisorbed on silver clusters using time-dependent density functional theory (TDDFT). Raman scattering cross sections are computed using a formalism that employs analytical derivatives of frequency-dependent electronic polarizabilities, which treats both off-resonant and resonant enhancement within the same scheme. In the off-resonant regime, Raman scattering into molecular vibrational modes is enhanced by one order of magnitude and shows pronounced dependence on the orientation and the local symmetry of the molecu…
The metal atoms, the alkali ones excepted, might provide the multiple outermost orbitals for the multi-orbital hybridizations with the out-of-plane $π$ bondings on the honeycomb lattice. This will dominate the fundamental properties of Al-, Ti- and Bi-adsorbed graphene nanoribbons, in which they are explored thoroughly by using the first-principles calculations. The principle focuses are the adatom-dependent binding energies, the adatom-carbon lengths, the optimal position, the maximum adatom concentrations, the free electron density transferred per adatom, the adatom-related valence and condu…
Electronic conduction through single molecules is affected by the molecular electronic structure as well as by other information that is extremely difficult to assess, such as bonding geometry and chemical environment. The lack of an independent diagnostic technique has long hampered single-molecule conductance studies. We report simultaneous measurement of the conductance and the Raman spectra of nanoscale junctions used for single-molecule electronic experiments. Blinking and spectral diffusion in the Raman response of both para-mercaptoaniline and a fluorinated oligophenylyne ethynylene cor…
Adsorption-Driven Symmetry Lowering in Single Molecules Revealed by Ångstrom-scale Tip-Enhanced Raman Imaging
Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences（捷克科学院有机化学与生物化学研究所）；Institute of Physics, Czech Academy of Sciences（捷克科学院物理研究所）；Instituto de Ciencia de Materiales de Madrid（马德里材料科学研究所）；Departamento de Química, Universidad Autónoma de Madrid（马德里自治大学化学系）；Faculty of Mathematics and Physics, Charles University（查理大学数学与物理学院）；Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid（马德里自治大学化学高级研究院）
Raman signals from molecules adsorbed on a noble metal surface are enhanced by many orders of magnitude due to the plasmon resonances of the substrate. Additionally, the enhanced spectra are modified compared to the spectra of neat molecules: many vibrational frequencies are shifted and relative intensities undergo significant changes upon attachment to the metal. With the goal of devising an effective scheme for separating the electromagnetic and chemical effects, we explore the origin of the Raman spectra modification of benzenethiol adsorbed on nanostructured gold surfaces. The spectral mod…
We calculate the conductance spectra of a Co atom adsorbed on Cu(111), considering the Co $3d$ orbitals within a correlated multiple configurations model interacting through the substrate band with the Co $4s$ orbital, which is treated in a mean-field like approximation. By symmetry, only the $d_{z^2}$ orbital couples with the $s$ orbital through the Cu bands, and the interference between both conduction channels introduces a zero-bias anomaly in the conductance spectra. We find that, while the Kondo resonance is mainly determined by the interaction of the Co $d$ orbitals with the bulk states …
In this paper we show that the ionic conduction through surface chemisorbed ambient moisture leads to the remarkably high room temperature selective response towards hydrogen gas. The surface adsorbed moisture acts as surface states and shows ionic conduction, as a result of smaller size of ZnO nanoparticles of 20 +/- 5 nm. This response is enhanced remarkably i.e. from 10% to 190% for 1200 ppm H2 gas when p-type NiO quasi-nanowires (width ~50 nm) are mixed with these n-type ZnO nanoparticles to form a homogenous NiO/ZnO nano-bulk p-n heterostructure. The maximum response is obtained for about…
A tight binding model for scanning tunneling microscopy images of a molecule adsorbed on a metal surface is described. The model is similar in spirit to that used to analyze conduction along molecular wires connecting two metal leads and makes it possible to relate these two measurements and the information that may be gleaned from the corresponding results. In particular, the dependence of molecular conduction properties along and across a molecular chain on the chain length, intersite electronic coupling strength and on thermal and disorder effects are discussed and contrasted. It is noted t…
The transfer of electrons between a solid surface and adsorbed atomic or molecular species is fundamental in natural and synthetic processes, being at the heart of most catalytic reactions and many sensors. In special cases, metallic conduction can be induced at the surface of, for example, Si-terminated SiC1, or mixed-terminated ZnO2, in the presence of a hydrogen adlayer. Generally, only the surface atoms are significantly affected by adsorbates. However, remotely changing electronic states far from the adsorbed layer is possible if these states are electrostatically coupled to the surface. …
Photo-Induced Enhanced Raman Spectroscopy (PIERS) is a new surface enhanced Raman spectroscopy (SERS) modality with an order-of-magnitude Raman signal enhancement of adsorbed analytes over that of typical SERS substrates. Despite the impressive PIERS enhancement factors and explosion in recent demonstrations of its utility, the detailed enhancement mechanism remains undetermined. Using a range of optical and X-ray spectroscopies, supported by density functional theory calculations, we elucidate the chemical and atomic-scale mechanism behind the PIERS enhancement. Stable PIERS substrates with e…
We report on a theoretical study of magnetic transitions induced by tunnelling electrons in individual adsorbed M-Phthalocyanine (M-Pc) molecules where M is a metal atom: Fe-Pc on a Cu(110)(2$\times$1)-O surface and Co-Pc layers on Pb(111) islands. The magnetic transitions correspond to the change of orientation of the spin angular momentum of the metal ion with respect to the surroundings and possibly an applied magnetic field. The adsorbed Fe-Pc system is studied with a Density Functional Theory (DFT) transport approach showing that i) the magnetic structure of the Fe atom in the adsorbed Fe…
The surface conductivity for conduction electrons with a fixed chirality in a topological insulator with impurities scattering is considered. The surface excitations are described by the Weyl Hamiltonian. For a finite chemical potential one projects out the hole band and one obtains a single electronic band with a fixed chirality. One obtains a model of spinless electrons which experience a half vortex when they return to the origin. As a result the conductivity is equivalent to a spinless problem with correlated noise which gives rise to anti-localization. We compute conductivity as a functio…
The theory of Raman scattering in half-metals by optical phonons interacting with conduction electrons is developed. We evaluate the effect of electron-phonon interactions at ferromagnetic ordering in terms of the Boltzmann equation for carriers. The chemical potential is found to decrease with temperature decreasing. Both the linewidth and frequency shift exhibit a dependence on temperature.
Under the local plasmonic excitation, the Raman images of a single molecule can now reach sub-nanometer resolution. We report here a theoretical description of the interaction between a molecule and a highly confined plasmonic field. It is shown that when the spatial distribution of the plasmonic field is comparable with the size of the molecule, the optical transition matrix of the molecule becomes to be dependent on the position and the spatial distribution of the plasmonic field, resulting in spatially resolved Raman image of a molecule. It is found that the resonant Raman image reflects th…
We present a microscopic model for surface-enhanced Raman scattering (SERS) from molecules adsorbed on small noble-metal nanoparticles. In the absence of direct overlap of molecular orbitals and electronic states in the metal, the main enhancement source is the strong electric field of the surface plasmon resonance in a nanoparticle acting on a molecule near the surface. In small particles, the electromagnetic enhancement is strongly modified by quantum-size effects. We show that, in nanometer-sized particles, SERS magnitude is determined by a competition between several quantum-size effects s…
We study the effects of the exchange interaction between an adsorbed magnetic atom with easy-axis magnetic anisotropy and the conduction-band electrons from the substrate. We model the system using an anisotropic Kondo model and we compute the impurity spectral function which is related to the differential conductance (dI/dV) spectra measured using a scanning tunneling microscope. To make contact with the known experimental results for iron atoms on the CuN/Cu(100) surface [Hirjibehedin et al., Science {\bf 317}, 1199 (2007)], we calculated the spectral functions in the presence of an external…
The band structure of type-I (In,Al)As/AlAs quantum dots with band gap energy exceeding 1.63 eV is indirect in momentum space, leading to long-lived exciton states with potential applications in quantum information. Optical access to these excitons is provided by mixing of the $Γ$- and X-conduction band valleys, from which control of their spin states can be gained. This access is used here for studying the exciton spin-level structure by resonant spin-flip Raman scattering, allowing us to accurately measure the anisotropic hole and isotropic electron $g$ factors. The spin-flip mechanisms for …
This is a preliminary acount of a theory for Raman scattering by current-carrying molecular junctions. The approach combines a non-equilibrium Green's function (NEGF) description of the non-equilibrium junction with a generalized scattering theory formulation for evaluating the light scattering signal. This generalizes our previous study (Phys. Rev. Lett. 95, 206802 (2005); J. Chem. Phys. 124, 234709 (2006)) of junction spectroscopy by including molecular vibrations and developing machinery for calculation of state-to-state (Raman scattering) fluxes within the NEGF formalism. For large enough …
Hybridisation of electronic bands of two-dimensional materials, assembled into twistronic heterostructures, enables one to tune their optoelectronic properties by selecting conditions for resonant interlayer hybridisation. Resonant interlayer hybridisation qualitatively modifies the excitons in such heterostructures, transforming these optically active modes into superposition states of interlayer and intralayer excitons. For MoSe$_2$/WSe$_2$ heterostructures, strong hybridization occurs between the holes in the spin-split valence band of WSe$_2$ and in the top valence band of MoSe$_2$, especi…
In this paper, we review recent development in the theory of resonant inelastic light (Raman) scattering in one-dimensional electron systems. The particular systems we have in mind are electron doped GaAs based semiconductor quantum wire nanostructures, although the theory can be easily modified to apply to other one-dimensional systems. We compare the traditional conduction-band-based non-resonant theories with the full resonant theories including the effects of interband transitions. We find that resonance is essential in explaining the experimental data in which the single particle excitati…
We report on the resonant coupling between localized surface plasmon resonances (LSPRs) in nanostructured Ag films, and an adsorbed monolayer of Rhodamine 6G dye. Hybridization of the plasmons and molecular excitons creates new coupled polaritonic modes, which have been tuned by varying the LSPR wavelength. The resulting polariton dispersion curve shows an anticrossing behavior which is very well fit by a simple coupled-oscillator Hamiltonian, giving a giant Rabi-splitting energy of ~400 meV. The strength of this coupling is shown to be proportional to the square root of the molecular density.…
We used Raman scattering for study the phonon modes of self-organized Ge/Si quantum dots, grown by a molecular-beam epitaxy method. It is revealed, that Ge-Ge and Si-Ge vibrational modes considerably intensify at excitation of exciton between the {Lambda}3 valence and {Lanbda}1 conduction bands (transitions E1 and E1+{Delta}1), that allows to observe Raman scattering spectrum from extremely small volumes of Ge, even from one layer of quantum dots with the layer thickness of ~ 10 A. It is shown that Si diffuses into the Ge quantum dots from the Si spacer layers forming Ge_xSi_{1-x} solid soluti…
Graphdiynes (GDYs) represent a class of 2D carbon materials based on sp-sp$^2$ hybridization with appealing properties and potential applications. Recent advances have demonstrated the experimental self-assembly of GDYs on metal substrates. Here we focus on $α$- and $β$-GDYs on Au(111) and Pt(111), and investigate how their electronic and vibrational properties are affected by the interaction with a metal substrate. We adopt hydrogenated GDY, previously characterized experimentally, as a benchmark for density functional theory simulations, that we apply to show that Au and Pt substrates impose…
Metal nanostructures act as powerful optical antennas[1, 2] because collective modes of the electron fluid in the metal are excited when light strikes the surface of the nanostructure. These excitations, known as plasmons, can have evanescent electromagnetic fields that are orders of magnitude larger than the incident electromagnetic field. The largest field enhancements often occur in nanogaps between plasmonically active nanostructures[3, 4], but it is extremely challenging to measure the fields in such gaps directly. These enhanced fields have applications in surface-enhanced spectroscopies…
We measure the temperature distribution in a biased single-layer graphene transistor using Raman scattering microscopy of the 2D-phonon band. Peak operating temperatures of 1050 K are reached in the middle of the graphene sheet at 210 KW cm^(-2) of dissipated electric power. The metallic contacts act as heat sinks, but not in a dominant fashion. To explain the observed temperature profile and heating rate, we have to include heat-flow from the graphene to the gate oxide underneath, especially at elevated temperatures, where the graphene thermal conductivity is lowered due to umklapp scattering…
The observation of helical surface states in Bi-based three-dimensional topological insulators has been a challenge since their theoretical prediction. The main issue raises when the Fermi level shifts deep into the bulk conduction band due to the unintentional doping. This results in a metallic conduction of the bulk which dominates the transport measurements and hinders the probing of the surface states in these experiments. In this study, we investigate various strategies to reduce the residual doping in Bi-based topological insulators. Flakes of Bi$_2$Se$_3$ and Bi$_{1.5}$Sb$_{0.5}$Te$_{1.…
