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An exciton–polariton condensate is a hybrid light–matter state in the quantum fluid phase. The photonic component endows it with characters of spin, as represented by circular polarization. Spin-polarization can form stochastically for quasi-equilibrium exciton–polariton condensates at parallel momentum vector k|| ∼ 0 from bifurcation or deterministically for propagating condensates at k|| > 0 from the optical spin-Hall effect (OSHE). Here, we report deterministic spin-polarization in exciton–polariton condensates at k|| ∼ 0 in microcavities containing methylammonium lead bromide perovskite (CH3NH3PbBr3) single crystals under non-resonant and linearly polarized excitation. We observe two energetically split condensates with opposite circular polarizations and attribute this observation to the presence of strong birefringence, which introduces a large OSHE at k|| ∼ 0 and pins the condensates in a particular spin state. Such spin-polarized exciton–polariton condensates may serve not only as circularly polarized laser sources but also as effective alternatives to ultracold atom Bose–Einstein condensates in quantum simulators of many-body spin–orbit coupling processes. [ABSTRACT FROM AUTHOR]

The fragmentation dynamics of two isomers of C3H6, cyclopropane and propene, induced by 4 keV/u Ar8+ are investigated employing a reaction microscope. Four two-body and two three-body dissociation channels of C 3 H 6 2 + dications are identified for each isomer, among which the channels involving CC bond breaking are found to be much more favored than H 3 + and H 2 + formation channels. The observation of the CH 3 + or H 3 + formation channels from cyclopropane are direct evidence of the proton migration within the carbon skeleton before dissociation. Obvious isomer effects are revealed by comparing the relative branching ratios of different channels of the two isomers. Moreover, it was shown that a sequential dissociation mechanism with H elimination prior to CC bond cleavage may be dominant for the two three-body dissociation channels for both isomers. [ABSTRACT FROM AUTHOR]

The optical spectra of transition metal dichalcogenide monolayers are dominated by excitons and trions. Here, we establish the dependence of these optical transitions on the disorder from hyperspectral imaging of h-BN encapsulated monolayer MoSe2. While both exciton and trion energies vary spatially, these two quantities are almost perfectly correlated, with spatial variation in the trion binding energy of only ∼0.18 meV. In contrast, variation in the energy splitting between the two lowest energy exciton states is one order of magnitude larger at ∼1.7 meV. Statistical analysis and theoretical modeling reveal that disorder results from dielectric and bandgap fluctuations, not electrostatic fluctuations. Our results shed light on disorder in high quality TMDC monolayers, its impact on optical transitions, and the many-body nature of excitons and trions. [ABSTRACT FROM AUTHOR]

The ultrafast optical Kerr effect (OKE) is widely used to investigate the structural dynamics and interactions of liquids, solutions, and solids by observing their intrinsic nonlinear temporal responses through nearly collinear four-wave mixing. Non-degenerate mixing schemes allow for background free detection and can provide information on the interplay between a material's internal degrees of freedom. Here, we show a source of temporal dynamics in the OKE signal that is not reflective of the internal degrees of freedom but arises from a group index and momentum mismatch. It is observed in two-color experiments on condensed media with sizable spectral dispersion, a common property near an optical resonance. In particular, birefringence in crystalline solids is able to entirely change the character of the OKE signal via the off-diagonal tensor elements of the nonlinear susceptibility. We develop a detailed description of the phase-mismatched ultrafast OKE and show how to extract quantitative information on the spectrally resolved birefringence and group index from time-resolved experiments in one and two dimensions. [ABSTRACT FROM AUTHOR]

We investigate crystallization of Lennard-Jones liquids on substrates under dynamic compression with large-scale molecular dynamics simulations. The substrates examined include single crystals and bicrystals with different crystallographic orientations, and the loading paths include shock and quasi-isentropic loading. Microstructure is characterized with simulated x-ray diffraction and orientation mapping. For shock loading, only heterogeneous nucleation occurs at the simulation scales. Quasi-isentropic loading induces less heating and larger supercooling; as a result, heterogeneous nucleation occurs at low loading strengths, and both heterogeneous and homogeneous nucleation occur at high loading strengths, despite the crystalline substrates. Crystallization depends on the substrate structure (crystal orientation and grain boundary) and loading characteristics. Deformation may induce grain structure change (e.g., reorientation and twinning) of substrates and affect subsequent crystallization. Crystallization rate is anisotropic, inversely proportional to the cosine of the dihedral angle between the substrate plane and a main f111g growth plane. [ABSTRACT FROM AUTHOR]

Previous experimental work has shown that a phase transition in C60 multifragmentation induced by nanosecond laser occurs at almost constant temperature covering a wide range of laser fluency. Here the relative yields of ionic fragments (IFs) Cn+ (n = 1-20) resulting from the multifragmentation are measured within the phase transition region. By excluding two small IFs and magic IFs due to their abnormal behavior, the data for residual IFs are used to estimate the size distributions of primary intermediate-mass IFs in the multifragmentation regime. The distributions are found to obey power laws n- T . Furthermore, the exponent T values have sensitive dependence on lower laser fluency and converge to a constant of about 2.4 ± 0.2 for larger fluencies. These observations are in good agreement with an explanation based on the Fisher droplet model, offering the tantalizing possibility of a liquid-to-gas phase transition in C60 systems. [ABSTRACT FROM AUTHOR]

Surface states play essential roles in condensed matter physics, e.g., as model two-dimensional (2D) electron gases and as the basis for topological insulators. Here, we demonstrate quantum interference in the optical excitation of 2D surface states using the model system of C60/Au(111). These surface states are transiently populated and probed in a femtosecond time- and angle-resolved two-photon photoemission experiment. We observe quantum interference within the excited populations of these surface states as a function of parallel momentum vector. Such quantum interference in momentum space may allow one to control 2D transport properties by optical fields. [ABSTRACT FROM AUTHOR]

We have studied the excitation and dissociation processes of the molecule W(CO)6 in collisions with low kinetic energy (3 keV) protons, monocharged fluorine, and chlorine ions using double charge transfer spectroscopy. By analyzing the kinetic energy loss of the projectile anions, we measured the excitation energy distribution of the produced transient dications W(CO)62+. By coincidence measurements between the anions and the stable or fragments of W(CO)62+, we determined the energy distribution for each dissociation channel. Based on the experimental data, the emission of the first CO was tentatively attributed to a nonstatistical direct dissociation process and the emission of the second or more CO ligands was attributed to the statistical dissociation processes. The dissociation energies for the successive breaking of the W-CO bond were estimated using a cascade model. The ratio between charge separation and evaporation (by the loss of CO+ and CO, respectively) channels was estimated to be 6% in the case of Cl+ impact. [ABSTRACT FROM AUTHOR]

The binding energies and lifetimes of the n=1 image resonance on Au(111) are measured as a function of n-heptane layer thickness by femtosecond time-resolved two-photon photoemission (TR-2PPE) spectroscopy. The lifetime of the image resonance dramatically increases from ∼4 fs on clean Au(111) to 1.6 ps with three layers of n-heptane. Because the image resonance is above the L1 band edge of Au, this increase in lifetime is attributed to the tunneling barrier presented by the σ-σ* band gap of the n-heptane film. We use the one-dimensional dielectric continuum model (DCM) to approximate the surface potential and to determine the binding energies and the lifetimes of the image resonances. The exact solution of the DCM potential is determined in two ways: the first by wave-packet propagation and the second by using a tight-binding Green’s function approach. The first approach allows band-edge effects to be treated. The latter approach is particularly useful in illustrating the similarity between TR-2PPE and conductance measurements. [ABSTRACT FROM AUTHOR]

Ab initio all-electron molecular-orbital calculations are carried out to study the structures and relative stability of low-energy silicon clusters (Sin = 12-20). Selected geometric isomers include those predicted by Ho et al. [Nature (London) 392, 582 (1998)] based on an unbiased search with tight-binding/genetic algorithm, as well as those found by Rata et at [Phys. Rev. Lett. 85, 546 (2000)] based on density-functional tight-binding/single-parent evolution algorithm. These geometric isomers are optimized at the Møller-Plesset (MP2) MP2/6-31G(d) level. The single-point energy at the coupled-cluster single and double substitutions (including triple excitations) [CCSD(T)] CCSD(T)/6-31G(d) level for several low-lying isomers are further computed. Harmonic vibrational frequency analysis at the MP2/6-31G(d) level of theory is also undertaken to assure that the optimized geometries are stable. For Si12-Si17 and Si19 the isomer with the lowest-energy at the CCSD(T)/6-31G(d) level is the same as that predicted by Ho et al., whereas for Si18 and Si20, the same as predicted by Rata et at However, for Si14 and Si15, the vibrational frequency analysis indicates that the isomer with the lowest CCSD(T)/6-31G(d) single-point energy gives rise to imaginary frequencies. Small structural perturbation onto the Si14 and Si15 isomers can remove the imaginary frequencies and results in new isomers with slightly lower MP2/6-31G(d) energy; however the new isomers have a higher single-point energy at the CCSD(T)/6-31G(d) level. For most Sin, (n = 12-18,20) the low-lying isomers are prolate in shape, whereas thr Si19 a spherical-like isomer is slightly lower in energy at the CCSD(T)/6-31G(d) level than low-lying prolate isomers. [ABSTRACT FROM AUTHOR]

Ab initio all-electron molecular-orbital calculations are carried out to study the structures and relative stability of low-energy silicon clusters (Sin = 12-20). Selected geometric isomers include those predicted by Ho et al. [Nature (London) 392, 582 (1998)] based on an unbiased search with tight-binding/genetic algorithm, as well as those found by Rata et at [Phys. Rev. Lett. 85, 546 (2000)] based on density-functional tight-binding/single-parent evolution algorithm. These geometric isomers are optimized at the Møller-Plesset (MP2) MP2/6-31G(d) level. The single-point energy at the coupled-cluster single and double substitutions (including triple excitations) [CCSD(T)] CCSD(T)/6-31G(d) level for several low-lying isomers are further computed. Harmonic vibrational frequency analysis at the MP2/6-31G(d) level of theory is also undertaken to assure that the optimized geometries are stable. For Si12-Si17 and Si19 the isomer with the lowest-energy at the CCSD(T)/6-31G(d) level is the same as that predicted by Ho et al., whereas for Si18 and Si20, the same as predicted by Rata et at However, for Si14 and Si15, the vibrational frequency analysis indicates that the isomer with the lowest CCSD(T)/6-31G(d) single-point energy gives rise to imaginary frequencies. Small structural perturbation onto the Si14 and Si15 isomers can remove the imaginary frequencies and results in new isomers with slightly lower MP2/6-31G(d) energy; however the new isomers have a higher single-point energy at the CCSD(T)/6-31G(d) level. For most Sin, (n = 12-18,20) the low-lying isomers are prolate in shape, whereas thr Si19 a spherical-like isomer is slightly lower in energy at the CCSD(T)/6-31G(d) level than low-lying prolate isomers. [ABSTRACT FROM AUTHOR]

Image-potential states on Cu(111) surfaces covered by thin films of C[SUB60] fullerene have been characterized by angle-resolved two-photon photoemission spectroscopy. Metal-to-molecule electron transfer within the first layer creates a 4x4 superlattice of surface dipoles. We show that such a surface dipole lattice provides lateral confinement of image-electron wave functions. Measurements of parallel dispersion indicate that the n51 image state is localized in the presence of one monolayer of C[SUB60] but becomes delocalized by the addition of a second layer. Quantum mechanical calculations explain this in terms of the screening of the dipole potential, thus, restoring the free-electron behavior parallel to the surface. These results show that a surface dipole lattice can effectively control the interfacial electronic structure. [ABSTRACT FROM AUTHOR]

Potential energy curves and spectroscopic constants for 37 low-lying electronic states of Mo[sub 2] and the ground state of Mo[sup +][sub 2] have been computed using the complete active space multiconfiguration self-consistent field followed by the multireference singles+doubles configuration interaction calculations that included up to 19 million configurations. We compute equilibrium distances (r[sub e]), vibrational frequencies (ω[sub e]), and energy separations (T[sub e]). We have suggested tentative assignments for the spectra of Mo[sub 2] including the recent work on resonance Raman and fluorescence spectra of Mo[sub 2]. Our work supports the ground state with ω[sub e] near 450-486 cm[sup -1], and we suggest that the 394.5 cm[sup -1] line in the resonance Raman spectrum of Lombardi and co-workers is for the a ³Σ[sup +][sub u] state of Mo[sub 2]. Our computations are consistent with the recently observed near-infrared spectrum of Mo[sub 2] by Bondybey and co-workers. We have computed a number of spectroscopic systems for Mo[sub 2], which are yet to be observed. Our computed adiabatic ionization energy of Mo[sub 2] is in excellent agreement with Simard and co-workers. We have computed the D[sub e]'s of Mo[sup +][sub 2] and Mo[sub 2]. [ABSTRACT FROM AUTHOR]

We report the unstable surface feature in nanometer-scale of diamondlike carbon (DLC) films deposited through C[sub 60] evaporation with simultaneous bombardment of 1.5 keV Ne[sup +] ions. The periodical ripples, commonly appearing in postprocessing of the deposited films, form directly at 550°C and 700°C, which is qualitatively consistent with the theoretical model based on sputtering yield variation with surface curvature. A dramatic transition from ripple surface to mounding roughening occurs at 400°C. The graphitization with increasing temperature induces the different dominant smoothening mechanisms, which is responsible for the morphological change observed. Further, the calculations of height-height correlation function show that the roughness exponents are around 0.8 at 200°C and 400°C, implying self-affinity of roughened surfaces. This study exhibits a potential of ion beam assisted deposition to tune DLC morphologies by controlling the deposition parameters to drive the competition between ion erosion and film deposition. [ABSTRACT FROM AUTHOR]

Vibrational population up to v″=3 in the umbrella mode of CD3 thermally desorbed from GaAs(100) has been determined by resonance enhanced multiphoton ionization (REMPI) spectroscopy. The population ratios are superthermal. The methyl radical must desorb promptly with a transition state geometry significantly different from the planar gas phase geometry. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The translational, rotational, and vibrational state distributions of CO (g) resulting from the single photon photodissociation of Cl2CO in the condensed phase at ∼90 K have been determined by time-of-flight (TOF) distribution measurement and resonance-enhanced multiphoton ionization (REMPI) spectroscopy. The TOF distribution of CO (g) is bimodal. Internal state characterization of the slow channel reveals a completely thermalized origin, with a rotational temperature of Trot=88±5 K, which is equal to the translational temperature as well as the substrate temperature. We believe these slow CO molecules originate from photodissociation below the topmost surface of the molecular film and achieve thermal equilibrium with the substrate before escaping into the gas phase. Internal state characterization of the fast channel shows, on the other hand, an energetic origin: at hν=5.0 eV, the rotational distribution, with an overall flux-weighted mean rotational energy of =0.12±0.01 eV, is non-Boltzmann and can be approximated by a bimodal distribution with rotational temperatures of 210±40 K at low J″(s) and 2200±300 K at high J″(s); the relative vibrational population is Nν=1/Nν=0=0.33±0.05. Both rotational and translational distributions of fast CO show positive correlation with photon energy. These CO molecules must be promptly ejected into the gas phase, carrying nascent energetic information from the photodissociation reaction on the surface of the molecular film. For electronic excitation events that result in photodissociation, 74% of the excess excitation energy is distributed in the translational and internal motions of products (CO and Cl); only 26% of the available energy is converted to motions of surrounding molecules. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Understanding photochemistry and energy transfer mechanisms in molecular solid films is of interest to many scientific issues, ranging from matrix-assisted laser desorption ionization mass spectrometry to photochemical processes on polar stratospheric cloud particles. We present a study of a model system: the photochemistry (hν=1.2–6.4 eV) of a molecular Cl2CO solid film at low laser power density, 10 μJ–1 mJ/cm2 for ∼10 ns pulses. At hν≥3.5 eV, photon absorption by Cl2CO leads to a major photodissociation channel resulting in CO (g) and Cl (g) and a minor molecular Cl2CO ejection channel. Both photodissociation and molecular ejection are observed at the lowest laser power density and their yields depend linearly on pulse energy. This result establishes a single photon photoexcitation mechanism. The electronically excited Cl2CO in the surface region of the solid film can either dissociate or convert its electronic energy to translational motion in Cl2CO. The translational energy distribution of CO (g) from the photodissociation channel is bimodal: the flux-weighted mean translational energy of the fast channel is photon energy dependent (=210, 135, and ∼90 meV at hν=6.4, 5.0, and 3.5 eV, respectively), while the slow channel is independent of photon energy and corresponds to completely thermalized CO molecules (=84±3 K). The mean translational energy of photoejected Cl2CO is =220±20 meV. In addition to photoejection, there is also a distinctively different thermal desorption channel due to transient laser heating. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

State resolved characterization of nascent gas phase products is used as probe for the dynamics of an energetic surface reaction. This is achieved in the photodissociation of monolayer phosgene adsorbed on Ag(110). Irradiation of adsorbed Cl2CO in a broad photon energy range (hν=1.9–6.4 eV) leads to dissociation, with Cl retained on the surface and CO desorbing into the gas phase. The translational energy of product CO (g), =0.26 eV, is independent of hν, even at the threshold photon energy (1.9 eV). This result establishes a dissociative electron attachment mechanism involving a reactive intermediate, ClCO, whose prompt dissociation serves as a probe to surface dissociation dynamics. Consistent with translation, internal state distribution of product CO (g) also shows an energetic origin: The rotational distribution, with an overall flux-weighted mean rotational energy of =0.17 eV, can be approximated by a bimodal Boltzmann distribution with rotational temperatures of 700 K at low J(s) and 7000 K at high J(s); the relative vibrational population is Nν=1/Nν=0=0.30. Contrary to common expectation based on quenching rates, both translational and rotational energies of CO (g) from monolayer photodissociation are much higher than those from the direct photodissociation in multilayers. This is taken as evidence for concerted reaction dynamics on the surface: The high exothermicity in the Cl–Ag bond formation on the surface exerts part of the energy to the Cl–CO coordinate, leading to higher energies in CO (g). © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Excitation and de-excitation of the electronic states of an adsorbed molecule on a solid surface result in intramolecular vibrational excitation. The internal vibrational energy can couple to the adsorbate–substrate bond and lead to molecular desorption. In this mechanism, the isotope effect in molecular desorption is determined not by the mass ratio of the leaving particles, but by that in the internal coordinate. This process is modeled within the context of semiclassical wave packet dynamics, which, in the short-time-limit harmonic approximation, allows analytical solution. Results are obtained for the ammonia/GaAs(100) system and are compared with experimental observations. [ABSTRACT FROM AUTHOR]

UV laser irradiation of ammonia adsorbed on GaAs(100) leads to molecular desorption and dissociation. A nitride passivation layer can be formed on the GaAs surface at 100 K by simultaneous exposure to ammonia and uv photons in a UHV environment. The nitride layer consists of a mixture of Ga and As nitrides. While the dominating GaN surface species is thermally stable, AsN desorbs below 800 K. Surface NH2 is identified as an intermediate. The implication of this study for selective area passivation and GaN growth is discussed. [ABSTRACT FROM AUTHOR]

UV laser irradiation of ammonia adsorbed on GaAs(100) leads to molecular desorption, with a mean translational temperature of =300 K, independent of photon energy and isotope substitution. However, the photodesorption cross section depends strongly on isotope substitution: σNH3/σND3=4.1 at hν=6.4 eV. This isotope effect is too large to be accounted for by the mass difference in the leaving particles (NH3 vs ND3), but can be successfully explained in terms of an isotope effect in the internal N–H(D) coordinates. We take this as evidence for uv-driven photodesorption from electronically quenched, but vibrationally hot ground state ammonia. [ABSTRACT FROM AUTHOR]

Molecular AsH3, adsorbed on Ga-rich GaAs(100) at 115 K, dissociates readily upon uv irradiation with 193, 248, and 351 nm excimer laser light. In the initial photodissociation step one As–H bond cleaves, leaving all the AsH2, and a large fraction of the H, adsorbed to As. The AsH2 further photodissociates to give As–H and Ga–H. The final steps, photochemical removal of hydrogen from Ga–H and As–H, lead to As deposition. The photodissociation cross section decreases sharply with the extent of photolysis. The wavelength dependence, compared to the gas-phase absorption cross section, extends to much lower photon energies and indicates that substrate-mediated excitation dominates the observed chemistry. There are strong isotope effects in all the cross sections; these are related to mass-dependent substrate-mediated quenching of the excited states. Implications for photon-assisted organometallic chemical vapor deposition are discussed. [ABSTRACT FROM AUTHOR]

The photodissociation rate of phosgene (Cl2CO) adsorbed on Pt(111) has been measured as a function of photon energy at normal incidence and as a function of incident angle using p-polarized light. Compared to the gas phase, the wavelength dependence of the initial photolysis cross section on the surface is redshifted. The angular response to p-polarized light is wavelength dependent. Above 315 nm, the angular dependence correlates with calculated metal absorption. At 280 nm, the angular dependence is much too strong to be accounted for solely by substrate excitation. A combination of substrate and direct excitation is adequate. This is the first direct evidence, for monolayers on metals, that both direct and substrate excitation contribute to surface photochemistry but dominate at different wavelengths. [ABSTRACT FROM AUTHOR]

A Pt(111) surface saturated with molecular oxygen was irradiated by UV light from a mercury arc lamp with various cutoff filters. High-resolution electron energy-loss spectroscopy (HREELS) and temperature programmed desorption mass spectroscopy (TPD) were used to characterize the products retained on the surface. Upon UV irradiation at 95 K, chemisorbed O2 (peroxo) undergoes dissociation, desorption and rearrangement. Different wavelength dependences were observed for the three processes: dissociation was not observed at wavelengths longer than 295 nm, in agreement with gas phase photodissociation of the O–O bond in hydrogen peroxide; desorption and rearrangement became negligible at wavelengths longer than 420 nm, in agreement with the photolysis of an organometallic peroxoplatinum complex. For wavelengths between 230 and 315 nm, the average cross sections of dissociation and desorption were estimated to be 5.7×10-20 and 1.2×10-19 cm2 , respectively. The possible origins of the three processes are discussed. [ABSTRACT FROM AUTHOR]

We report evidence for the coexistence of direct and precursor dynamics in the dissociative chemisorption of H2 on Ni(l00). Hydrogen and deuterium uptakes on Ni(l00) were measured at various surface temperatures by following the secondary ion ratios, Ni2 H+/Ni+ and Ni2 D+/Ni+ , which are proportional to surface hydrogen and deuterium coverage on both clean and carbon-covered Ni(100). Between 100 and 200 K on clean Ni(l00), the initial sticking coefficient of hydrogen decreases, but only slightly, as the surface temperature increases. The decrease is more pronounced both in the presence of predosed carbon and for deuterium adsorption on Ni(100). This is interpreted as due to the involvement at low temperatures of a molecular precursor which mediates dissociative adsorption at low temperatures. The precursor probably involves surface defects and sites formed in the presence of carbon. In addition to the precursor channel, a direct dissociation channel also operates, and dominates for T≥200 K. [ABSTRACT FROM AUTHOR]

Homodyne depolarized photon-correlation functions of 1,3,5-tri-α-naphthyl benzene (TαNB) have been measured at the 90° scattering angle in the temperature range of 75–110 °C. The correlation functions are analyzed in terms of a fractional exponential function and a modified constrained regularization method originally developed by Provencher. The results from both methods of data analysis are in agreement. The temperature dependence of the mean orientational relaxation time when fitted to the Arrhenius equation, gives an apparent activation energy E=85.3 kcal/mol. The Antoine–WLF equation provides a better fit of the mean reorientational relaxation time data. It is also found that orientational time τ is linearly proportional to η/T, indicating that the Debye–Stokes–Einstein equation is applicable to describe molecular reorientation in the supercooled TαNB liquid. [ABSTRACT FROM AUTHOR]

We report the vibrational and electronic spectra for pyridine and benzene adsorbed on the Rh(111) crystal surface obtained by high-resolution electron energy loss spectroscopy (HREELS). Low-energy electron diffraction (LEED), thermal desorption spectroscopy (TDS), and optical second harmonic generation (SHG) have also been used to provide complementary information. Pyridine adsorption on Rh(111) was studied over the 77–450 K temperature range. At 77 K, multilayers of pyridine are observed with a vibrational spectrum similar to that of liquid pyridine. Between 185 and 230 K, HREELS and TDS indicate that both physisorbed and chemisorbed pyridine species are present on the surface. The physisorbed species desorbs at 295 K, while the chemisorbed species is stable until it decomposes on the surface at 400 K. We propose that the chemisorbed species is an α-pyridyl complex as thermal desorption spectroscopy indicates partial dehydrogenation of this pyridine surface species. Electronic energy loss spectra for both benzene and pyridine adsorbed at 310 K show only a weak transition centered at ∼4 eV. The absence of prominent π→π* transitions, which are readily observed for multilayers of benzene adsorbed on Rh(111), implies that the π orbitals are strongly involved in the chemisorption bond of these molecules with the Rh(111) surface. [ABSTRACT FROM AUTHOR]

The photon-driven (2.5 to 6.4 eV) desorption of SO2 (coverages up to 2.7 monolayers) on Ag(111) has been studied by time-of-flight mass spectrometry in combination with temperature programmed desorption and Auger electron spectroscopy. The photodesorption yields per incident photon increase with photon energy. Consistent with substrate-mediated excitation, the mean translational energy trans/2k> is constant (650 K) for photon energies between 3.5 and 6.4 eV, but decreases at longer wavelengths (480 K at 2.5 eV). The decrease is attributed to changes in the energy distribution of the hot substrate carriers responsible for desorption. The photodesorption yields vary with the initial coverage, the method of preparing the initial coverage, and the extent of photolysis. These variations are attributed, in part, to changes in the SO2 orientation on the surface. Even at 6.4 eV, where unimolecular photodissociation occurs in the gas phase and multilayer, there is no photodissociation in monolayers. This effect is attributed to strong substrate quenching. [ABSTRACT FROM AUTHOR]

We probe the electronic structure of alkanethiolate self-assembled monolayers (SAMs) on Au(111) using two-photon photoemission spectroscopy. We observe a dispersive unoccupied resonance close to the vacuum level with a lifetime shorter than 30 fs. The short lifetime and the insensitivity of the energy level and dispersion to molecular length (and thus layer thickness) suggest that the probability density of the electron wave function is concentrated inside the molecular layer close to the SAM/Au interface. Such an interfacial resonance results from the image like potential at the SAM/Au interface. [ABSTRACT FROM AUTHOR]

We propose an approach to determine the excitation energy distribution due to multiphoton absorption in the case of excited systems following decays to produce different ion species. This approach is based on the measurement of the time-resolved photoion position spectrum by using velocity map imaging spectrometry and an unfocused laser beam with a low fluence and homogeneous profile. Such a measurement allows us to identify the species and the origin of each ion detected and to depict the energy distribution using a pure Poisson’s equation involving only one variable which is proportional to the absolute photon absorption cross section. A cascade decay model is used to build direct connections between the energy distribution and the probability to detect each ionic species. Comparison between experiments and simulations permits the energy distribution and accordingly the absolute photon absorption cross section to be determined. This approach is illustrated using C60 as an example. It may therefore be extended to a wide variety of molecules and clusters having decay mechanisms similar to those of fullerene molecules. [ABSTRACT FROM AUTHOR]

We demonstrate that surface plasmon oscillations excited at an adsorbate covered metal–vacuum interface can effectively couple to the electronic system of the adsorbed molecule. Using p-polarized light (hν=3.5 eV) incident at the surface plasmon resonant angle in Kretschmann’s attenuated-total-reflection (ATR) configuration, we observe a strong enhancement of the photodissociation rate of Mo(CO)6 from a 180 Å Al film, evaporated on a quartz prism in UHV. [ABSTRACT FROM AUTHOR]

The rates of photodissociation and photodesorption of dioxygen adsorbed on Ag (110) under ultraviolet irradiation have been measured as a function of polarization at normal incidence. No dependence of the rate was found on the angle between the O2 bond axis and the electric vector of the incident light. This result supports a mechanism for surface photochemistry in which substrate excitation is the dominant process. [ABSTRACT FROM AUTHOR]

The optical spectra of transition metal dichalcogenide monolayers are dominated by excitons and trions. Here, we establish the dependence of these optical transitions on the disorder from hyperspectral imaging of h-BN encapsulated monolayer MoSe2. While both exciton and trion energies vary spatially, these two quantities are almost perfectly correlated, with spatial variation in the trion binding energy of only ∼0.18 meV. In contrast, variation in the energy splitting between the two lowest energy exciton states is one order of magnitude larger at ∼1.7 meV. Statistical analysis and theoretical modeling reveal that disorder results from dielectric and bandgap fluctuations, not electrostatic fluctuations. Our results shed light on disorder in high quality TMDC monolayers, its impact on optical transitions, and the many-body nature of excitons and trions. [ABSTRACT FROM AUTHOR]

In recent years, the exploration of solar absorbers has grown in favor due to the scarcity of energy. Here, we propose an absorber with an array of a circular ring surrounding disk (RSD) for solar energy capture. The novel structure keeps above 93.5% absorption with an average absorption of 96.95% in wavelengths from 300 to 4000 nm. Meanwhile, the proposed absorber is advantageous in that the structure is generalizable to other metals and dielectric materials. Furthermore, the data results show that the absorber has polarization-independent properties as well as maintaining >90% absorption in the considered wavelength range up to an incidence angle of 52° and >95% absorption at large process tolerances. Finally, the excellent absorption under the AM1.5 solar spectrum demonstrates the RSD absorber's ability to capture solar energy. These results show the potential of the absorber for applications in electromagnetic invisibility cloaking, thermal emitters, and solar energy capture and conversion., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The direct conversion of methane to methanol has attracted increasing interest due to abundant and low-cost natural gas resources. Herein, by anchoring Cr-oxo/-oxyhydroxides on UiO-66 metal-organic frameworks, we demonstrate that reactive anionic oxyl radicals can be formed by controlling the coordination environment based on the results of density functional theory calculations. The anionic oxyl radicals produced at the completely oxidized CrVI site acted as the active species for facile methane activation. The thermodynamically stable CrVI-oxo/-oxyhydroxides with the anionic oxyl radicals catalyze the activation of the methane C-H bond through a homolytic mechanism. An analysis of the results showed that the catalytic performance of the active oxyl species correlates with the reaction energy of methane activation and H adsorption energies. Following methanol formation, N2O can regenerate the active sites on the most stable CrVI oxyhydroxides, i.e., the Cr(O)4Hf species. The present study demonstrated that the anionic oxyl radicals formed on the anchored CrVI oxyhydroxides by tuning the coordination environment enabled facile methane activation and facilitated methanol production., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Freezing of water under nanoconfinement exhibits physical peculiarities with respect to the bulk water. However, experimental observations are extremely challenging at this scale, which limits our understanding of the effect of confinement on water properties upon freezing. In this study, we use molecular dynamic simulations to investigate how confinement affects the kinetics of growth of ice and the thermodynamic equilibrium of ice-liquid coexistence. TIP4P/Ice water model and CSH-FF model were applied to simulate ice crystallization in a confined cement system at temperatures down to 220 K. We adapted an interface detection algorithm and reparameterized the CHILL/CHILL+ algorithm to capture ice growth. The confinement leads to a shift of the maximum growth rate of ice to a higher temperature than for bulk water. Both the confinement and surface impurities contribute to slowing down the ice growth. For the ice-liquid coexistence at equilibrium, we derive a formulation of Thomson's equation adapted to statistical physics quantities accessible by molecular simulation, and we show that this adapted equation predicts accurately the melting line of bulk and confined ice Ih as a function of pressure. The confinement decreases systematically the melting temperature of ice of about 5 K compared with bulk ice Ih. A premelted water film about 1 nm thick is observed between the solid wall and ice, and its thickness is found to decrease continuously as temperature is lowered. We note that the surface impurities are key to the formation of the premelted water nanofilm when the temperature is lower than 250 K., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Many-Body eXpansion (MBX) is a C++ library that implements many-body potential energy functions (PEFs) within the "many-body energy" (MB-nrg) formalism. MB-nrg PEFs integrate an underlying polarizable model with explicit machine-learned representations of many-body interactions to achieve chemical accuracy from the gas to the condensed phases. MBX can be employed either as a stand-alone package or as an energy/force engine that can be integrated with generic software for molecular dynamics and Monte Carlo simulations. MBX is parallelized internally using Open Multi-Processing and can utilize Message Passing Interface when available in interfaced molecular simulation software. MBX enables classical and quantum molecular simulations with MB-nrg PEFs, as well as hybrid simulations that combine conventional force fields and MB-nrg PEFs, for diverse systems ranging from small gas-phase clusters to aqueous solutions and molecular fluids to biomolecular systems and metal-organic frameworks., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

In this paper, a broadband metamaterial absorber consisting of the doped silicon substrate and the square array of doped silicon covered by a SU-8 layer is presented. The target structure achieves an average absorption of 94.42% in the studied frequency range (0.5-8 THz). In particular, the structure exceeds 90% absorption in the frequency range of 1.44-8 THz, which is a significant increase in bandwidth relative to reported devices of the same type. Next, the near-perfect absorption of the target structure is verified by the impedance matching principle. Furthermore, through the analysis of the electric field distribution inside the structure, the physical mechanism of its broadband absorption is investigated and explained. Finally, the impact of fluctuations in the incident angle, polarization angle, and structural parameters on the absorption efficiency is examined at length. The analysis shows that the structure has characteristics, such as polarization insensitivity, wide-angle absorption, and good process tolerance. The proposed structure is advantageous for applications in THz shielding, cloaking, sensing, and energy harvesting., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Integration of hexagonal boron nitride (h-BN) with plasmonic nanostructures that possess nanoscale field confinement will enable unusual properties; hence, the manipulation and understanding of the light interactions are highly desirable. Here, we demonstrate the surface plasmonic coupling of Au nanoparticles (ANPs) with ultrathin h-BN nanosheets (BNNS) in nonspecific nanocomposites leading to a great enhancement of the Raman signal of E2g in both experimental and theoretical manner. The nanocomposites were fabricated from liquid-exfoliated atomically thin BNNS and diblock copolymer-based ANPs with excellent dispersion through a self-assembly approach. By precisely varying the size of ANPs from 3 to 9 nm, the Raman signal of BNNS was improved from 1.7 to 71. In addition, the underlying mechanism has been explored from the aspects of electromagnetic field coupling strength between the localized surface plasmons excited from ANPs and the surrounding dielectric h-BN layers, as well as the charge transfer at the BNNS/ANPs interfaces. Moreover, we also demonstrate its capability to detect dye molecules as a surface enhanced Raman scattering (SERS) substrate. This work provides a basis for the self-assembly of BNNS hierarchical nanocomposites allowing for plasmon-mediated modulation of their optoelectronic properties, thereby showing the great potential not only in the field of SERS but also in large-scale h-BN-based plasmonic devices., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Understanding structural transformation and phase transition accompanying reactions in a solid as a catalyst or oxygen carrier is important to the design and optimization of many catalytic or chemical looping reaction processes. Herein, we combined density functional theory calculation with the stochastic surface walking global optimization approach to track the structural transformation accompanying the reduction of CuO upon releasing oxygen. We then used machine learning (ML) methods to correlate the structural properties of CuO x with varying x. By decomposing a reduction step into oxygen detachment and structural reconstruction, we identified two types of pathways: (1) uniform reduction with minimal structural changes; (2) segregated reduction with significant reconstruction. The results of ML analysis showed that the most important feature is the radial distribution functions of Cu-O at a percentage of oxygen vacancy [C(O V )] < 50% and Cu-Cu at C(O V ) > 50% for CuO x formation. These features reflect the underlying physicochemical origin, i.e., Cu-O breaking and Cu-Cu formation in the respective stage of reduction. Phase diagram analysis indicates that CuO will be reduced to Cu 2 O under a typical oxygen uncoupling condition. This work demonstrates the complexity of solid structural transformation and the potential of ML methods in studying solid state materials involved in many chemical processes.

The optical spectra of transition metal dichalcogenide monolayers are dominated by excitons and trions. Here, we establish the dependence of these optical transitions on the disorder from hyperspectral imaging of h-BN encapsulated monolayer MoSe 2 . While both exciton and trion energies vary spatially, these two quantities are almost perfectly correlated, with spatial variation in the trion binding energy of only ∼0.18 meV. In contrast, variation in the energy splitting between the two lowest energy exciton states is one order of magnitude larger at ∼1.7 meV. Statistical analysis and theoretical modeling reveal that disorder results from dielectric and bandgap fluctuations, not electrostatic fluctuations. Our results shed light on disorder in high quality TMDC monolayers, its impact on optical transitions, and the many-body nature of excitons and trions.

The fragmentation dynamics of two isomers of C 3 H 6 , cyclopropane and propene, induced by 4 keV/u Ar 8+ are investigated employing a reaction microscope. Four two-body and two three-body dissociation channels of C 3 H 6 2+ dications are identified for each isomer, among which the channels involving CC bond breaking are found to be much more favored than H 3 + and H 2 + formation channels. The observation of the CH 3 + or H 3 + formation channels from cyclopropane are direct evidence of the proton migration within the carbon skeleton before dissociation. Obvious isomer effects are revealed by comparing the relative branching ratios of different channels of the two isomers. Moreover, it was shown that a sequential dissociation mechanism with H elimination prior to CC bond cleavage may be dominant for the two three-body dissociation channels for both isomers.

High-level quantum chemical computations have provided significant insight into the fundamental physical nature of non-covalent interactions. These studies have focused primarily on gas-phase computations of small van der Waals dimers; however, these interactions frequently take place in complex chemical environments, such as proteins, solutions, or solids. To better understand how the chemical environment affects non-covalent interactions, we have undertaken a quantum chemical study of π-π interactions in an aqueous solution, as exemplified by T-shaped benzene dimers surrounded by 28 or 50 explicit water molecules. We report interaction energies (IEs) using second-order Møller-Plesset perturbation theory, and we apply the intramolecular and functional-group partitioning extensions of symmetry-adapted perturbation theory (ISAPT and F-SAPT, respectively) to analyze how the solvent molecules tune the π-π interactions of the solute. For complexes containing neutral monomers, even 50 explicit waters (constituting a first and partial second solvation shell) change total SAPT IEs between the two solute molecules by only tenths of a kcal mol -1 , while significant changes of up to 3 kcal mol -1 of the electrostatic component are seen for the cationic pyridinium-benzene dimer. This difference between charged and neutral solutes is attributed to large non-additive three-body interactions within solvated ion-containing complexes. Overall, except for charged solutes, our quantum computations indicate that nearby solvent molecules cause very little "tuning" of the direct solute-solute interactions. This indicates that differences in binding energies between the gas phase and solution phase are primarily indirect effects of the competition between solute-solute and solute-solvent interactions.

The wetting state of surfaces can be rendered to a highly hydrophobic state by the deposition of hydrophilic gas phase synthesized Ag nanoparticles (NPs). The aging of Ag NPs leads to an increase in their size, which is also associated with the presence of Ag adatoms on the surface between the NPs that have a strong effect on the wetting processes. Furthermore, surface airborne hydrocarbons were removed by UV-ozone treatment, providing deeper insight into the apparent mobility of the NPs on different surfaces and their subsequent ripening and aging. In addition, the UV-ozone treatment revealed the presence of adatoms during the magnetron sputtering process. This surface treatment lowers the initial contact angle of the substrates and facilitates the mobility of Ag NPs and adatoms on the surface of substrates. Adatoms co-deposited on clean high surface energy substrates will nucleate on Ag NPs that will remain closely spherical and preserve the pinning effect due to the water nanomeniscus. If the adatoms are co-deposited on a UV-ozone cleaned low surface energy substrate, their mobility is restricted, and they will nucleate in two-dimensional islands and/or nanoclusters on the surface instead of connecting to existing Ag NPs. This growth results in a rough surface without overhangs, where the wetting state is reversed from hydrophobic to hydrophilic. Finally, different material surfaces of transmission electron microscopy grids revealed strong differences in the sticking coefficient for the Ag NPs, suggesting another factor that can strongly affect their wetting properties.

Atomistic modeling of energy and charge transfer at the heterojunction of organic solar cells is an active field with many remaining outstanding questions owing, in part, to the difficulties in performing reliable photodynamics calculations on very large systems. One approach to being able to overcome these difficulties is to design and apply an appropriate simplified method. Density-functional tight binding (DFTB) has become a popular form of approximate density-functional theory based on a minimal valence basis set and neglect of all but two center integrals. We report the results of our tests of a recent long-range correction (lc) [A. Humeniuk and R. Mitrić, J. Chem. Phys. 143, 134120 (2015)] for time-dependent (TD) lc-DFTB by carrying out TD-lc-DFTB fewest switches surface hopping calculations of energy and charge transfer times using the relatively new DFTBABY [A. Humeniuk and R. Mitrić, Comput. Phys. Commun. 221, 174 (2017)] program. An advantage of this method is the ability to run enough trajectories to get meaningful ensemble averages. Our interest in the present work is less in determining exact energy and charge transfer rates than in understanding how the results of these calculations vary with the value of the range-separation parameter (R lc = 1/μ) for a model organic solar cell heterojunction consisting of a gas-phase van der Waals complex P/F made up of a single pentacene (P) molecule together with a single buckminsterfullerene (F) molecule. The default value of R lc = 3.03 a 0 is found to be much too small as neither energy nor charge transfer is observed until R lc ≈ 10 a 0 . Tests at a single geometry show that the best agreement with high-quality ab initio spectra is obtained in the limit of no lc (i.e., very large R lc ). A plot of energy and charge transfer rates as a function of R lc is provided, which suggests that a value of R lc ≈ 15 a 0 yields the typical literature (condensed-phase) charge transfer time of about 100 fs. However, energy and charge transfer times become as high as ∼300 fs for R lc ≈ 25 a 0 . A closer examination of the charge transfer process P * /F → P + /F - shows that the initial electron transfer is accompanied by a partial delocalization of the P hole onto F, which then relocalizes back onto P, consistent with a polaron-like picture in which the nuclei relax to stabilize the resultant redistribution of charges.