K-point longitudinal acoustic phonons are responsible for ultrafast intervalley scattering in monolayer MoSe2.

In transition metal dichalcogenides, valley depolarization through intervalley carrier scattering by zone-edge phonons is often unavoidable. Although valley depolarization processes related to various acoustic phonons have been suggested, their optical verification is still vague due to nearly degenerate phonon frequencies on acoustic phonon branches at zone-edge momentums. Here we report an unambiguous phonon momentum determination of the longitudinal acoustic (LA) phonons at the K point, which are responsible for the ultrafast valley depolarization in monolayer MoSe2. Using sub-10-fs-resolution pump-probe spectroscopy, we observed coherent phonons signals at both even and odd-orders of zone-edge LA mode involved in intervalley carrier scattering process. Our phonon-symmetry analysis and first-principles calculations reveal that only the LA phonon at the K point, as opposed to the M point, can produce experimental odd-order LA phonon signals from its nonlinear optical modulation. This work will provide momentum-resolved descriptions of phonon-carrier intervalley scattering processes in valleytronic materials.

Reply to Correspondence on "Core Electron Topologies in Chemical Compounds: Case Study of Carbon versus Silicon".

In their Correspondence, von Szentpály, Schwarz, Stoll, and Werner claim that the main conclusions of our Communication previously published in this journal are based on computational artifacts and oversimplified models. We clarify the justification of our simple one-electron model to describe one-electron physics, and refute their criticism based on what they call "computational artifacts." We remind that our main conclusion on the crucial role of qualitative changes in core electron wavefunctions is evidenced not only by wavefunction topologies the complainants cling to, but also by several other physical observables, which remain unrefuted. Hence, the conclusions of our original Communication stand.

Core Electron Topologies in Chemical Compounds: Case Study of Carbon versus Silicon.

The similarities and differences between carbon and silicon have attracted the curiosity of chemists for centuries. Similarities and analogies can be found in their saturated compounds, but carbon exhibits a cornucopia of unsaturated compounds that silicon (and most other elements) cannot replicate. While this qualitative difference is empirically well known, quantum chemistry has previously only described quantitative differences related to orbital overlap, steric effects, or orbital energies. We study C2 and Si2 and their hydrides X2 H2n (X=C, Si; n=1, 2, 3) by first-principles quantum chemical calculation, and find a qualitative difference in the topologies of the core electrons: carbon has the propensity to alter its core electron topology when forming unsaturated compounds, and silicon has not. We draw a connection between the core electron topologies and ionization energies, and identify other elements we expect to have similarly flexible core topologies as carbon.

Clusterization modes of Ti on TiO2(1 1 0)-1 × 1 due to stablization by catalytic suboxide formation.

The electronic states of individual clusters formed from Ti deposition on a TiO(2)(1 1 0)-1 × 1 surface were measured using scanning tunneling spectroscopy (STS). The results of scanning tunneling microscopy (STM) suggests that as the amount of deposited Ti increased, at a critical height of 1.4 nm, the cluster growth changes from vertical oxide formation to lateral growth. Based on the STS spectra, the relation between the band-gap and cluster size was revealed. In the first oxide-formation mode, the band gaps decreased smoothly in response to the increase of the cluster size, while a band-gap-free (metallic) phase appears when the clusters are thicker than ∼1.4 nm. This result indicates that Ti adatoms initially diffuse on the oxide surface and are stabilized by oxygen atoms from the substrate to form a suboxide interfacial layer. This catalytic suboxide formation promotes the vertical granular growth of the deposited Ti atoms.

Terahertz-field-induced nonlinear electron delocalization in Au nanostructures.

Improved control over the electromagnetic properties of metal nanostructures is indispensable for the development of next-generation integrated nanocircuits and plasmonic devices. The use of terahertz (THz)-field-induced nonlinearity is a promising approach to controlling local electromagnetic properties. Here, we demonstrate how intense THz electric fields can be used to modulate electron delocalization in percolated gold (Au) nanostructures on a picosecond time scale. We prepared both isolated and percolated Au nanostructures deposited on high resistivity Si(100) substrates. With increasing the applied THz electric fields, large opacity in the THz transmission spectra takes place in the percolated nanostructures; the maximum THz-field-induced transmittance difference, 50% more, is reached just above the percolation threshold thickness. Fitting the experimental data to a Drude-Smith model, we found furthermore that the localization parameter and the damping constant strongly depend on the applied THz-field strength. These results show that ultrafast nonlinear electron delocalization proceeds via strong electric field of THz pulses; the intense THz electric field modulates the backscattering rate of localized electrons and induces electron tunneling between Au nanostructures across the narrow insulating bridges without any material breakdown.

Local electronic properties at organic-metal interfaces: thiophene derivatives on Pt(111).

The valence electronic states of thiophene (TP), 2-thiophenethiol (TT), 2,2'-bithiophene (BTP), and 2,2'-bithiophene-5-thiol (BTT) on Pt(111) were measured by ultraviolet photoemission spectroscopy (UPS) and metastable atom electron spectroscopy (MAES) to elucidate how the local electronic properties at the organic-metal interface are altered by the extent of π-conjugation and substituent effects. First-principles calculations using density functional theory (DFT) were used to assign the observed spectra. TP and BTP chemisorb weakly on Pt(111), whereas TT and BTT are strongly bound to Pt(111) through the S atom with the cleavage of the S-H bond, forming a thiolate. In the MAES spectra, weak emission just below the Fermi level (E(F)) was attributed to a chemisorption-induced gap state (CIGS) produced by orbital mixing between the organic species and Pt(111). The formation of CIGS is responsible for a metallic structure at the organic-metal interface. The relative intensities of CIGSs at E(F) were in the order of TP (flat-lying configuration) > TT > TP (inclined configuration), indicating that the spatial distribution of CIGSs is drastically altered by the strength of the organic-metal bond and the adsorption geometry. In other words, TP (flat-lying geometry) and TT serve as good mediators of the extension of the metal wave function at E(F), which would be closely related to charge transport at organic-metal interfaces.

Ultrafast dynamics of surface-enhanced Raman scattering due to Au nanostructures.

Ultrafast dynamics of surface-enhanced Raman scattering (SERS) was investigated at cleaved graphite surfaces bearing deposited gold (Au) nanostructures (∼10 nm in diameter) by using sensitive pump-probe reflectivity spectroscopy with ultrashort (7.5 fs) laser pulses. We observed enhancement of phonon amplitudes (C═C stretching modes) in the femtosecond time domain, considered to be due to the enhanced electromagnetic (EM) field around the Au nanostructures. Finite-difference time-domain (FDTD) calculations confirmed the EM enhancement. The enhancement causes drastic increase of coherent D-mode (40 THz) phonon amplitude and nanostructure-dependent changes in the amplitude and dephasing time of coherent G-mode (47 THz) phonons. This methodology should be suitable to study the basic mechanism of SERS and may also find application in nanofabrication.