Emergent photophenomena in three dimensional van der Waals heterostructures

We report on the fabrication and observation of emergent opto-electronic phenomena in three dimensional, micron-sized van der Waals heterostructures self-assembled from atomic layers of graphene and hexagonal boron nitride in varying ratios.

Morphological Stability of Epitaxial Thin Elastic Films by Van Der Waals Force

The morphological stability of epitaxial thin elastic films on a substrate by van der Waals force is discussed. It is found that only van der Waals force with negative Hamaker constant (A < 0) tends to stabilize the film, and the lower bound for the Hamaker constant is also obtained for the stability of thin film. The critical value of the undulation wavelength is found to be a function of both film thickness and external stress. The charateristic time-scale for surface mass diffusion scales to the fourth power to the wavelength of the perturbation.

Combined effect of surface tension, gravity and van der Waals force induced by a non-contact probe tip on the shape of liquid surface

Aiming at understanding how a liquid film on a substrate affects the atomic force microscopic image in experiments, we present an analytical representation of the shape of liquid surface under van der Waals interaction induced by a non-contact probe tip. The analytical expression shows good consistence with the corresponding numerical results. According to the expression, we find that the vertical scale of the liquid dome is mainly governed by a combination of van der Waals force, surface tension and probe tip radius, and is weekly related to gravity. However, its horizontal extension is determined by the capillary length.

Dynamic Stability of Electrostatic Torsional Actuators with van Der Waals Effect

electrostatic torsional nano-electro-mechanical systems (NEMS) actuators is analyzed in the paper. The dependence of the critical tilting angle and voltage is investigated on the sizes of structure with the consideration of vdW effects. The pull-in phenomenon without the electrostatic torque is studied, and a critical pull-in gap is derived. A dimensionless equation of motion is presented, and the qualitative analysis of it shows that the equilibrium points of the corresponding autonomous system include center points, stable focus points, and unstable saddle points. The Hopf bifurcation points and fork bifurcation points also exist in the system. The phase portraits connecting these equilibrium points exhibit periodic orbits, heteroclinic orbits, as well as homoclinic orbits.

Precursor adsorption on copper surfaces as the first step during the deposition of copper: a density functional study with van der Waals correction

Copper dimethylamino-2-propoxide [Cu(dmap)2] is used as a precursor for low-temperature atomic layer deposition (ALD) of copper thin films. Chemisorption of the precursor is the necessary first step of ALD, but it is not known in this case whether there is selectivity for adsorption sites, defects, or islands on the substrate. Therefore, we study the adsorption of the Cu(dmap)2 molecule on the different sites on flat and rough Cu surfaces using PBE, PBE-D3, optB88-vdW, and vdW-DF2 methods. We found the relative order of adsorption energies for Cu(dmap)2 on Cu surfaces is Eads (PBE-D3) > Eads (optB88-vdW) > Eads (vdW-DF2) > Eads (PBE). The PBE and vdW-DF2 methods predict one chemisorption structure, while optB88-vdW predicts three chemisorption structures for Cu(dmap)2 adsorption among four possible adsorption configurations, whereas PBE-D3 predicts a chemisorbed structure for all the adsorption sites on Cu(111). All the methods with and without van der Waals corrections yield a chemisorbed molecule on the Cu(332) step and Cu(643) kink because of less steric hindrance on the vicinal surfaces. Strong distortion of the molecule and significant elongation of Cu–N bonds are predicted in the chemisorbed structures, indicating that the ligand–Cu bonds break during the ALD of Cu from Cu(dmap)2. The molecule loses its initial square-planar structure and gains linear O–Cu–O bonding as these atoms attach to the surface. As a result, the ligands become unstable and the precursor becomes more reactive to the coreagent. Charge redistribution mainly occurs between the adsorbate O–Cu–O bond and the surface. Bader charge analysis shows that electrons are donated from the surface to the molecule in the chemisorbed structures, so that the Cu center in the molecule is partially reduced.

Observation of the C2H2-N2O van der Waals complex in the overtone range using CW-CRDS

A slit nozzle supersonic expansion containing C2H2 (246 sccm) and N2O (355 sccm) seeded into Ar (1260 sccm) is investigated using CW cavity ring-down spectroscopy, in the 1.5 μm range. The C2H2-N2O van der Waals complex is observed around the 2CH acetylenic band. Despite strong perturbations, 117 b-type lines are assigned. Their combined fit with published microwave data leads to new upper state and improved lower state rotational constants. The Lorentzian width of the assigned line profiles sets the mean lifetime to 1.6 ns. The rotational temperature is estimated to be 15 K from the comparison between observed and simulated spectra. © 2008 Elsevier B.V. All rights reserved.

Ab initio investigation of C2H2/X Van der Waals complexes (X=Noble gas, CO2, N2O)

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The Fantasio set-up: High resolution overtone spectroscopy of acetylene containing van der Waals dimers

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The C2H2-Ar van der Waals complex

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Investigation of acetylene-containing van der Waals complexes by cavity ring-down spectroscopy and ab initio calculations

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12C2H2-Ar van der Waals complex

New theoretical and experimental results on the acetylene-Ar van der Waals complex are presented and the literature is reviewed. New ab initio calculations at the MP2 level were performed using large basis sets with diffuse functions and taking into account the basis set superposition error. It was found that the structure of acetylene is not significantly altered by the complexation and that its vibrational frequencies are only slightly lowered. Finally, it was observed that the calculated properties of the complex (structure, vibrational spectrum, bond dissociation energy) are not sensitive to the structure imposed on acetylene. Experimentally, acetylene-Ar was produced in a supersonic expansion under experimental conditions corresponding to 9 K rotational temperature. Thanks to the performances of CW-CRDS detection, the Ka = 0 ← 1, 1 ← 0, and 2 ← 1 sub- bands of the v1 + v3 band could be recorded and resolved and most of their lines assigned. Upper-state rotational constants were fitted, however not including the upper Ka = 2 state, which shows K-doubling the opposite of the expected. The Lorentzian width of most line profiles sets the mean lifetime to some 7.5 ns. Local perturbations affecting line positions and/or line widths are demonstrated. Additional series of lines tentatively attributed to acetylene-Ar are discussed.© 2009 American Chemical Society.

Accurate ground-state potential energy surfaces of the C2H2–Kr and C2H2–Xe van der Waals complexes

Accurate ab initio intermolecular potential energy surfaces (IPES) have been obtained for the first time for the ground electronic state of the C 2H2-Kr and C2H2-Xe van der Waals complexes. Extensive tests, including complete basis set and all-electron scalar relativistic results, support their calculation at the CCSD(T) level of theory, using small-core relativistic pseudopotentials for the rare-gas atoms and aug-cc-pVQZ basis sets extended with a set of 3s3p2d1f1g mid-bond functions. All results are corrected for the basis set superposition error. The importance of the scalar relativistic and rare-gas outer-core (n.1)d correlation effects is investigated. The calculated IPES, adjusted to analytical functions, are characterized by global minima corresponding to skew T-shaped geometries, in which the Jacobi vector positioning the rare-gas atom with respect to the center of mass of the C2H2 moiety corresponds to distances of 4.064 and 4.229Å, and angles of 65.22° and 68.67° for C 2H2-Kr and C2H2-Xe, respectively. The interaction energy of both complexes is estimated to be -151.88 (1.817 kJ mol-1) and -182.76 cm-1 (2.186 kJ mol-1), respectively. The evolution of the topology of the IPES as a function of the rare-gas atom, from He to Xe, is also discussed. © 2012 Taylor and Francis.

Delocalization of a hole in van der Waals clusters: Ionization potential of rare-gas and small Hg_n clusters

The size dependence of the ionization potential I_p(n) of van der Waals (vdW) bound clusters has been calculated by using a model Hamiltonian, which includes electron hopping, vdW interactions, and charge-dipole interactions. The charge-density and dipole-density distributions for both neutral and ionized n-atom clusters are determined self-consistently. The competition between the polarization energy of the neutral atoms surrounding a partially localized hole and the tendency toward hole delocalization in the ionized clusters is found to dominate the size dependence of I_p(n). To test our theory, we culculate I_p(Xe_n) and I_p(Kr_n) for n \le 300. Good quantitative agreement with experiment is obtained. The theory is also applied to calculate I_p(Hg_n). Comparison with experiments suggests that in Hg_n^+ clusters with n \le 20 the positive charge is mainly distributed within a trimer which is situated at the center of the cluster and which polarizes the n - 3 surrounding neutral atoms.

Slave-boson approach to the size-dependent transition from van der Waals to covalent bonding in Hg_n clusters

We use a microscopic theory to describe the dynamics of the valence electrons in divalent-metal clusters. The theory is based on a many-body model Harniltonian H which takes into account, on the same electronic level, the van der Waals and the covalent bonding. In order to study the ground-state properties of H we have developed an extended slave-boson method. We have studied the bonding character and the degree of electronic delocalization in Hg_n clusters as a function of cluster size. Results show that, for increasing cluster size, an abrupt change occurs in the bond character from van der Waals to covalent bonding at a critical cluster size n_c ~ 10-20. This change also involves a transition from localized to delocalized valence electrons, as a consequence of the competition between both bonding mechanisms.