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Van der Waals clusters composed of He and aromatic molecules provide fundamental information about intermolecular interactions in weakly bound systems. In this study, phenol–helium clusters (PhOH–Hen with n ≤ 2) are characterized for the first time by UV and IR spectroscopies. The S1 ← S0 origin and ionization energy both show small but additive shifts, suggesting π-bound structures of these clusters, a conclusion supported by rotational contour analyses of the S1 origin bands. The OH stretching vibrations of the PhOH moiety in the clusters match with those of bare PhOH in both the S0 and D0 states, illustrating the negligible perturbation of the He atoms on the molecular vibration. Matrix shifts induced by He attachment are discussed based on the observed band positions with the help of complementary quantum chemical calculations. For comparison, the UV and ionization spectra of PhOH–Ne are reported as well. [ABSTRACT FROM AUTHOR]

We present the observation of the N2–H2O van der Waals complex in the 2OH stretch overtone region. The high-resolution jet cooled spectra were measured using a sensitive continuous wave cavity ringdown spectrometer. Several bands were observed and vibrationally assigned in terms of ν1, ν2, and ν3, the vibrational quantum numbers of the isolated H2O molecule, as ( ν 1 ′ ν 2 ′ ν 3 ′ ) ← ( ν 1 ″ ν 2 ″ ν 3 ″ ) = (200) ← (000) and (101) ← (000). A combination band involving the excitation of the in-plane bending motion of N2 and the (101) vibration of water is also reported. The spectra were analyzed using a set of four asymmetric top rotors, each associated with a nuclear spin isomer. Several local perturbations of the (101) vibrational state were observed. These perturbations were assigned to the presence of the nearby (200) vibrational state and to the combination of (200) with intermolecular modes. [ABSTRACT FROM AUTHOR]

Measurements of the 0–0 hyperfine resonant frequencies of ground-state 85Rb atoms show a nonlinear dependence on the pressure of the buffer gases Ar, Kr, and Xe. The nonlinearities are similar to those previously observed with 87Rb and 133Cs and presumed to come from alkali-metal–noble-gas van der Waals molecules. However, the shape of the nonlinearity observed for Xe conflicts with previous theory, and the nonlinearities for Ar and Kr disagree with the expected isotopic scaling of previous 87Rb results. Improving the modeling alleviates most of these discrepancies by treating rotation quantum mechanically and considering additional spin interactions in the molecules. Including the dipolar-hyperfine interaction allows simultaneous fitting of the linear and nonlinear shifts of both 85Rb and 87Rb in either Ar, Kr, or Xe buffer gases with a minimal set of shared, isotope-independent parameters. To the limit of experimental accuracy, the shifts in He and N2 were linear with pressure. The results are of practical interest to vapor-cell atomic clocks and related devices. [ABSTRACT FROM AUTHOR]

We experimentally studied the three-body fragmentation dynamics of a noble gas cluster (ArKr2) upon its multiple ionization by an intense femtosecond laser pulse. The three-dimensional momentum vectors of correlated fragmental ions were measured in coincidence for each fragmentation event. A novel comet-like structure was observed in the Newton diagram of the quadruple-ionization-induced breakup channel of ArKr 2 4 + → Ar+ + Kr+ + Kr2+. The concentrated head part of the structure mainly originates from the direct Coulomb explosion process, while the broader tail part of the structure stems from a three-body fragmentation process involving electron transfer between the distant Kr+ and Kr2+ ion fragments. Due to the field-driven electron transfer, the Coulomb repulsive force of the Kr2+ and Kr+ ions with respect to the Ar+ ion undergoes exchange, leading to changes in the ion emission geometry in the Newton plot. An energy sharing among the separating Kr2+ and Kr+ entities was observed. Our study indicates a promising approach for investigating the strong-field-driven intersystem electron transfer dynamics by using the Coulomb explosion imaging of an isosceles triangle van der Waals cluster system. [ABSTRACT FROM AUTHOR]

We report a joint spectroscopic and theoretical study probing spin-orbit coupling (SOC) in a variety of molecular complexes between an iodine atom and a ligand (L) with L ranging from Ar, HF to formic/acetic acids, and glycine/N-methylated glycine derivatives. Cryogenic photoelectron spectroscopy of L·I- (L=HCOOH, CH3COOH) reveals three distinct peaks, identified as three SOC states, denoted as X(1/2), A(3/2), and B(l/2) for the corresponding neutrals. The X and A separation ΔEXA is measured to be 0.10 eV for both, whereas the X and B gap ΔEXB is 0.98 and 0.97 eV for formic and acetic acid, respectively. These new ΔEXA values are compared with the previously reported values for the molecular complexes L·I· with L=Ar, HF, glycine, and A-methylated glycines. All together these complexes encompass a diversity of intermolecular interactions, from van der Waals to weak and strong hydrogen bonding. While the ΔEXB remains similar, the ΔEXA is shown to be extremely sensitive to the type of ligands and interactions, spanning from 5 meV to 150 meV. High-level relativistic quantum calculations including explicit SOC formulism nicely reproduce all experimental SOC splitting. A direct correlation between the magnitude of ΔEXA with the intermolecular interaction strength or bond distance of the neutral complexes—the stronger interaction (shorter bond length), the greater splitting, is established. [ABSTRACT FROM AUTHOR]

The fine structure excitation of the interstellar CCS radical induced by collisions with He is investigated. The first potential energy surface (PES) for the CCS–He van der Waals complex is presented. It was obtained from a highly correlated spin unrestricted coupled cluster approach with single double and perturbative triple excitations. The PES presents two shallow minima of 31.85 and 37.12 cm−1 for the linear (He facing S) and the nearly T-shaped geometries, respectively. The dissociation energy of the complex was calculated and found to be D0 = 14.183 cm−1. Inelastic scattering calculations were performed using the close-coupling approach. Cross-sections for transitions between the 61 first fine structure levels of CCS were obtained for energy up to 600 cm−1 and rate coefficients for the 5–50 K temperature range were derived. This set of collisional data can be used to model CCS emission spectra in dark molecular interstellar clouds and circumstellar envelopes and enable an accurate determination of CCS abundance in these astrophysical media. [ABSTRACT FROM AUTHOR]

This paper presents the experimental and theoretical analyses of ArICl(IP,vIP,nIP) states' population and decay at energies lower than the ArICl(E,vE = 0,nE) dissociation limit (IP = E0+, D′2, β1), vIP = 0, 1, and nIP are the quantum numbers of the van der Waals (vdW) modes. We have measured the excitation spectra of the ArICl(E,vE = 0,1,nE → X,vX,nX) and ArICl(β,0,nβ → A and/or D ′ , v D ′ , n D ′ → A ′ luminescence as well as luminescence spectra themselves. To construct potential energy surfaces (PESs) for valence (A1, A′2) and ion-pair (E, β, and D′) electronic states of the complex, we utilized the intermolecular diatomic-in-molecule perturbation theory first order method. The experimental and calculated spectroscopic characteristics of the T-shaped ArICl valence and E, β states agree well. The ArICl(D′) state PES has no vdW levels in the T-shaped configuration, and collinear ArICl(D′) binding energy is larger than that of the T-shaped ArICl(β) state. We calculated vibrational state energies and the ArICl(IP → valence states) luminescence excitation spectra, as well as luminescence spectra themselves, by using the Heidelberg MCTDH code. The comparison of the experimental and calculated excitation spectra shows that the latter describe their principal features. The bound–bound ArICl(E,0,nE → X and β,0,nβ → A) parts of experimental luminescence spectra are described adequately by the calculated spectra, whereas bound-free ArICl(E,0,nE → X, D′, 0, nD′ → A′) parts are not described since the bound-free transitions occur in repulsive parts of the ArICl(X, A ′ PESs, which we cannot describe accurately. [ABSTRACT FROM AUTHOR]

Due to the lack of specific collisional data, the abundance of NS+ in cold dense interstellar clouds was determined using collisional rate coefficients of CS as a substitute. To better understand the chemistry of sulfur in the interstellar medium, further abundance modeling using the actual NS+ collisional rate coefficients is needed. For this purpose, we have computed the first full 4D potential energy surface of the NS+–H2 van der Waals complex using the explicitly correlated coupled cluster approach with single, double, and non-iterative triple excitation in conjunction with the augmented-correlation consistent-polarized valence triple zeta basis set. The potential energy surface exhibits a global minimum of 848.24 cm−1 for a planar configuration of the complex. The long-range interaction energy, described using multipolar moments, is sensitive to the orientation of H2 up to radial distances of ∼50 a0. From this new interaction potential, we derived excitation cross sections, induced by collision with ortho- and para-H2, for the 15 low-lying rotational levels of NS+ using the quantum mechanical close-coupling approach. By thermally averaging these data, we determined downward rate coefficients for temperatures up to 50 K. By comparing them with the previous NS+–H2 data, we demonstrated that reduced dimensional approaches are not suited for this system. In addition, we found that the CS collisional data underestimate our results by up to an order of magnitude. The differences clearly indicate that the abundance of NS+, in cold dense clouds retrieved from observational spectra, must be reassessed using these new collisional rate coefficients. [ABSTRACT FROM AUTHOR]

In this work, the Li ordering and its influence on Li intercalation and plating on graphite, bilayer, and single-layer graphene are investigated by first-principles calculation with two-dimensional cluster expansion and van der Waals corrections. The results show that Li intercalation has a multistage feature for graphite and bilayer graphene at Li concentrations from C2 to LiC6. Beyond LiC6, Li atoms are crowded in graphite and bilayer graphene, resulting in a negative discharge voltage. The calculated overpotential indicates Li plating easily happens on graphite but is unlikely on bilayer graphene. For single-layer graphene, Li atoms uniformly cover the graphene surface from C2 to LiC4 with the presence of voltage stages, while forming an atomic island at a higher Li concentration. Our findings not only give a good recount on recent Li plating phenomena in Li-ion batteries but also provide a rationale for circumventing those side reactions on graphene and its variants. [ABSTRACT FROM AUTHOR]

The CO2 molecule is of great interest for astrophysical studies since it can be found in a large variety of astrophysical media where it interacts with the dominant neutral species, such as He, H2, or H2O. The CO2–He collisional system was intensively studied over the last two decades. However, collisional data appear to be very sensitive to the potential energy surface (PES) quality. Thus, we provide, in this study, a new PES of the CO2–He van der Waals complex calculated with the coupled-cluster method and a complete basis set extrapolation in order to provide rotational rate coefficients that are as accurate as possible. The PES accuracy was tested through the calculations of bound state transition frequencies and pressure broadening coefficients that were compared to experimental data. An excellent agreement was globally found. Then, revised collisional data were provided for the 10–300 K temperature range. Rate coefficients were compared to previously computed ones and are found to be up to 50% greater than previously provided ones. These differences can induce non-negligible consequences for the modeling of CO2 abundance in astrophysical media. [ABSTRACT FROM AUTHOR]

We present quantum five-dimensional bound-state calculations of the fully coupled intermolecular rovibrational states of H2O–CO2 and D2O–CO2 van der Waals (vdW) complexes in the rigid-monomer approximation for the total angular momentum J values of 0, 1, and 2. A rigid-monomer version of the recent ab initio full-dimensional (12D) potential energy surface of H2O–CO2 [Q. Wang and J. M. Bowman, J. Chem. Phys. 147, 161714 (2017)] is employed. This treatment provides for the first time a rigorous and comprehensive description of the intermolecular rovibrational level structure of the two isotopologues that includes the internal-rotation tunneling splittings and their considerable sensitivity to rotational and intermolecular vibrational excitations, as well as the rotational constants of the two vdW complexes. Two approaches are used in the calculations, which differ in the definition of the dimer-fixed (DF) frame and the coordinates associated with them. We demonstrate that with the approach introduced in this work, where the DF frame is fixed to the CO2 moiety, highly accurate results are obtained using significantly smaller basis sets in comparison to those for the alternative approach. In addition, the resulting wavefunctions tend to lend themselves better to physical interpretation and assignment. The H2O–CO2 ground-state internal-rotation tunneling splittings, the rotational transition frequencies, and the rotational constants of both vdW complexes are in excellent agreement with the experimental results. The calculated intermolecular vibrational fundamentals agree well with the scant terahertz spectroscopy data for these complexes in cryogenic neon matrices. [ABSTRACT FROM AUTHOR]

We consider the origin of nonlinear collision shifts for the 0–0 hyperfine transition in alkali/noble-gas systems due to van der Waals molecule formation. Developing a semi-empirical model, we describe the shift as arising from three fundamental interactions: (1) a fractional change in the alkali's valence electron density at the alkali nucleus, η, which affects the hyperfine contact term; (2) a mixing of p-wavefunction character into the alkali ground state (characterized by the probability for p-state character appearing in the perturbed wavefunction ξ12), which gives rise to an electric quadrupole term in the ground-state hyperfine splitting; and (3) an interaction of the alkali's valence electron with the magnetic field produced by molecular rotation, characterized by a magnetic field strength BvdW. In addition to these molecular parameters, the model also depends on the formation rate of van der Waals molecules, kfP2, and the breakup rate of the molecules, kbP, where P is the noble-gas pressure. Fitting the model to the 85Rb/Xe and 87Rb/Xe experimental data of McGuyer and co-workers (and taking previously measured values for kf and BvdW), we find that η = 9 × 10−3, ξ12 = 5 × 10−3, and kb = 2.9×107 s−1/Torr. [ABSTRACT FROM AUTHOR]

This study proposes a new approach for constructing intermolecular potential energy surfaces (PESs) of van der Waals (vdW) complexes using neural networks. The descriptors utilized in this neural network model are split into two parts: radial parts representing the intermolecular stretching vibrations between monomers and angular parts describing the relative orientation of these molecules. Specifically, the parity-adapted rotational basis functions used in the bound state calculation are taken as the angular descriptors, which ensure the correct symmetry of the PES. The number of orthogonal rotational basis functions is controlled by the maximum value of the angular momentum quantum number. In addition, the symmetry of monomer molecules is achieved by restricting the quantum number of the rotational basis function. The descriptors for five types of van der Waals complexes, including atom-linear, atom-nonlinear, linear-linear, linear-nonlinear and nonlinear-nonlinear molecules complexes, have been derived in this work. The neural network models with these newly developed descriptors were then applied to construct PESs of two van der Waals complexes, Ar-NaCl and N2-OCS. The root-mean-square error values between the fitted and ab initio energies are found to be 0.11 cm−1 and 0.26 cm−1 for Ar-NaCl and N2-OCS, respectively. These results indicate that this method is accurate and effective for constructing high-precision PESs of vdW complexes. [ABSTRACT FROM AUTHOR]

Collisional data for the excitation of NH by H2 are key to accurately derive the NH abundance in astrophysical media. We present a new four-dimensional potential energy surface (PES) for the NH–H2 van der Waals complex. The ab initio calculations of the PES were carried out using the explicitly correlated partially spin-restricted coupled cluster method with single, double, and perturbative triple excitations [RCCSD(T)-F12a] with the augmented correlation-consistent polarized valence triple zeta basis set. The PES was represented by an angular expansion in terms of coupled spherical harmonics. The global minimum corresponds to the linear structure with a well depth De = 149.10 cm−1. The calculated dissociation energy D0 is found to be 30.55 and 22.11 cm−1 for ortho-H2 and para-H2 complexes, respectively. These results are in agreement with the experimental values. Then, we perform quantum close-coupling calculations of the fine structure resolved excitation cross sections of NH induced by collisions with ortho-H2 and para-H2 for collisional energies up to 500 cm−1. We find strong differences between collisions induced by ortho-H2 and para-H2. Propensity rules are discussed. The cross sections are larger for fine structure conserving transitions than for fine structure changing ones, as predicted by theory. These new results should help in interpreting NH interstellar spectra and better constrain the abundance of NH in interstellar molecular clouds. [ABSTRACT FROM AUTHOR]

Photodissociation of the van der Waals complex Ar–I2 after excitation into the Rydberg states of I2 has been investigated with velocity map imaging of photofragments. Formation of the translationally hot ions of argon Ar+ with three modes in kinetic energy distribution has been revealed. The measured dependence of the kinetic energy of Ar+ on the pumping photon energy indicates the appearance of Ar+ from three channels of the photodissociation of the linear intermediate Ar+–I–I− containing chemically bound argon. These channels are (1) dissociation into Ar++ I2−; (2) three-body dissociation into (Ar+)* + I* + I−, with (Ar+)* and I* being the 2P1/2 states of the species; and (3) two-body electron photodetachment, giving rise to Ar+ + I2 + e. Three indicated channels are similar to those established for the photodissociation of trihalide anions. This similarity confirms the conclusion on the formation of the Ar+–I–I− intermediate, which is isoelectronic to the trihalide anion Cl–I–I−. The mechanism of the Ar+–I–I− formation involves two-photon excitation of the complex Ar–I2 into the Rydberg state of I2 converted into the ion-pair state and further electron transfer from Ar to I+ of the ion-pair state. The self-assembling of the structure making the formation of the Ar+–I–I− intermediate energetically accessible is confirmed by modeling the dynamics in the excited linear complex Ar–I2. Photoexcitation of the van der Waals complexes of noble gases with halogens into the ion-pair states of halogen is supposed to be a promising approach for generating the new chemical compounds of noble gas atoms. [ABSTRACT FROM AUTHOR]

Photodissociation of the van der Waals complex Ar–I2 after excitation into the Rydberg states of I2 has been investigated with velocity map imaging of photofragments. Formation of the translationally hot ions of argon Ar+ with three modes in kinetic energy distribution has been revealed. The measured dependence of the kinetic energy of Ar+ on the pumping photon energy indicates the appearance of Ar+ from three channels of the photodissociation of the linear intermediate Ar+–I–I− containing chemically bound argon. These channels are (1) dissociation into Ar++ I2−; (2) three-body dissociation into (Ar+)* + I* + I−, with (Ar+)* and I* being the 2P1/2 states of the species; and (3) two-body electron photodetachment, giving rise to Ar+ + I2 + e. Three indicated channels are similar to those established for the photodissociation of trihalide anions. This similarity confirms the conclusion on the formation of the Ar+–I–I− intermediate, which is isoelectronic to the trihalide anion Cl–I–I−. The mechanism of the Ar+–I–I− formation involves two-photon excitation of the complex Ar–I2 into the Rydberg state of I2 converted into the ion-pair state and further electron transfer from Ar to I+ of the ion-pair state. The self-assembling of the structure making the formation of the Ar+–I–I− intermediate energetically accessible is confirmed by modeling the dynamics in the excited linear complex Ar–I2. Photoexcitation of the van der Waals complexes of noble gases with halogens into the ion-pair states of halogen is supposed to be a promising approach for generating the new chemical compounds of noble gas atoms. [ABSTRACT FROM AUTHOR]

We study the role of pairwise long-range interactions in the formation of van der Waals molecules through direct three-body recombination processes A + B + B → AB + B, based on a classical trajectory method in hyperspherical coordinates developed in our earlier works [J. Pérez-Ríos et al., J. Chem. Phys. 140, 044307 (2014); M. Mirahmadi and J. Pérez-Ríos, J. Chem. Phys. 154, 034305 (2021)]. In particular, we find the effective long-range potential in hyperspherical coordinates with an exact expression in terms of dispersion coefficients of pairwise potentials. Exploiting this relation, we derive a classical threshold law for the total cross section and the three-body recombination rate yielding an analytical expression for the three-body recombination rate as a function of the pairwise long-range coefficients of the involved partners. [ABSTRACT FROM AUTHOR]

We present a full-dimensional ab initio intermolecular potential energy surface (IPES) for the OC–HF van der Waals complex. 3167 ab initio points were computed at the frozen-core (FC) explicitly correlated coupled cluster [FC-CCSD(T)-F12b] level, with the augmented correlation-consistent polarized valence quadruple-zeta basis set plus bond functions. Basis set superposition error correction was also considered by the full counterpoise procedure. Gaussian process regression (GPR) was used to map out the potential energy surface, while a multipole expansion method was employed to smooth the ab initio noise of intermolecular potential in the long range. The global minimum of −1248.364 cm−1 was located at the linear configuration with the C atom pointing toward the H atom of the HF molecule. In addition, a local minimum of −602.026 cm−1 was found at another linear configuration with the O atom pointing toward the H atom of the HF molecule. The eigenstates were calculated on the vibrational averaged four-dimensional IPESs with the mixed radial discrete variable representation/angular finite basis representation method and Lanczos propagation algorithm. The dissociation energy D0 was calculated to be 701.827 cm−1, well reproducing the experimental value of 732 ± 2 cm−1. The dipole moment surfaces were also fitted by GPR from 3132 ab initio points calculated using the coupled cluster method [CCSD(T)] with AVTZ basis set plus bond functions. The frequencies and relative line intensities of rovibrational transitions in the HF (DF) and CO stretching bands were further calculated and compared well with the experimental results. These results indicate the high fidelity of the new IPES. [ABSTRACT FROM AUTHOR]

Recent studies of the weakly bound anisole⋯CH4 complex found a dual mode of binding, featuring both C/H⋯π and C/H⋯O noncovalent interactions. In this work, we examine the dissociation energies of related aniline⋯(CH4)n (n = 1, 2) van der Waals clusters, where both C/H⋯π and C/H⋯N interactions are possible. Using a combination of theory and experiments that include mass-selected two-color resonant two-photon ionization spectroscopy, two-color appearance potential (2CAP) measurements, and velocity-mapped ion imaging (VMI), we derive the dissociation energies of both complexes in the ground (S0), excited (S1), and cation radical (D0) states. As the amide group is non-planar in the ground state, the optimized ground state geometry of the aniline⋯CH4 1:1 complex shows two isomers, each with the methane positioned above the aniline ring. The observed redshift of the electronic origin from the aniline monomer is consistent with TDDFT calculations for the more stable isomer, where the methane sits on the same face as the amino hydrogens. The dissociation energies of the 1:1 complex, obtained from 2CAP measurements, are in good agreement with the calculated theoretical values from selected density functional theory methods. VMI data for the 1:1 complex gave a binding energy value overestimated by ∼179 cm−1 when compared to the 2CAP results, indicating that dissociative ionization selectively populates an excited vibrational level of the aniline cation radical. Given that the electron donating ability of aromatic substituents trends as –NH2 > –OCH3 > –CH3, it is noteworthy that the strength of methane binding also trends in this order, as found by experiment (dissociation energies in kJ/mol: 6.6 > 5.8 > 4.5) and predicted by theory (PBE0-D3/def2-QZVPPD, in kJ/mol: 6.9 > 6.0 > 5.0). For the 1:2 complex of aniline and methane, calculations predict that the more stable conformer is the one where the two methane molecules lie on opposite faces of the ring, consistent with the observed redshift of the electronic origin. Unlike the anisole–methane 1:2 complex, which shows an enhanced dissociation energy for the loss of one methane in comparison with the 1:1 complex, here, we find that the energy required to remove one methane from the ground state aniline–methane 1:2 complex is smaller than that of the 1:1 complex, consistent with theoretical expectations. [ABSTRACT FROM AUTHOR]

The vibration behaviors of van der Waals (vdW) heterostructures are studied based on molecular dynamics (MD) simulations and continuum mechanics modelling in this paper. Graphene/hexagonal boron nitride and graphene/silicene systems are considered as two typical examples of heterostructures studied here. Our MD results show that the resonance frequency of vdW heterostructures grows as their layer number increases and tends to be saturated when the layer number is relatively large. These findings deviate from results of the conventional composite beam (CB) model of vdW heterostructures. By abandoning the assumptions in the CB model, we propose a novel multiple beam (MB) model giving a result that agrees well with MD results. We find from the MB model that compared to other factors the interlayer shearing effect plays the key role in determining the resonance behaviors of vdW heterostructures. Considering this fact, we further simplify the MB model to a much simpler form which gives a simple but precise description of the vibration behaviors of vdW heterostructures. This simplified MB model suggests that the resonance frequency of vdW heterostructures can be optimized by changing their total mass, the sum of bending stiffness of their component layers, and the sum of interlayer shear modulus of their vdW layers. [ABSTRACT FROM AUTHOR]

We propose a tubular van der Waals heterostructure by rolling up graphene and MoS2 atomic layers into a tubular form. We show that the interlayer space of this heterostructure can be varied in a specific range. This specific range is related to the interlayer van der Waals force, the ultrahigh in-plane stiffness and small bending modulus of graphene, and the brittle characteristic properties of MoS2. This variability of the interlayer space can be utilized to efficiently tune the mechanical properties of the tubular van der Waals heterostructure. More specifically, we demonstrate that the Poisson's ratio of the tubular van der Waals heterostructure can be manipulated by a factor of two by varying the interlayer space in the range 1.44–4.44 Å. This work provides a basis for applications of a new member of the van der Waals heterostructure family with a tunable Poisson's ratio. [ABSTRACT FROM AUTHOR]

We derive the effective Flory-Huggins parameter in polarizable polymeric systems, within a recently introduced polarizable field theory framework. The incorporation of bead polarizabilities in the model self-consistently embeds dielectric response, as well as van der Waals interactions. The latter generate a χ parameter (denoted χ ̃ ) between any two species with polarizability contrast. Using one-loop perturbation theory, we compute corrections to the structure factor S k and the dielectric function ϵ ^ ( k ) for a polarizable binary homopolymer blend in the one-phase region of the phase diagram. The electrostatic corrections to S(k) can be entirely accounted for by a renormalization of the excluded volume parameter B into three van der Waals-corrected parameters BAA, BAB, and BBB, which then determine χ ̃ . The one-loop theory not only enables the quantitative prediction of χ ̃ but also provides useful insight into the dependence of χ ̃ on the electrostatic environment (for example, its sensitivity to electrostatic screening). The unapproximated polarizable field theory is amenable to direct simulation via complex Langevin sampling, which we employ here to test the validity of the one-loop results. From simulations of S(k) and ϵ ^ ( k ) for a system of polarizable homopolymers, we find that the one-loop theory is best suited to high concentrations, where it performs very well. Finally, we measure χ ̃ N in simulations of a polarizable diblock copolymer melt and obtain excellent agreement with the one-loop theory. These constitute the first fully fluctuating simulations conducted within the polarizable field theory framework. [ABSTRACT FROM AUTHOR]

In this work, we present a new endstation for the AMOLine of the ASTRID2 synchrotron at Aarhus University, which combines a cluster and nanodroplet beam source with a velocity map imaging and time-of-flight spectrometer for coincidence imaging spectroscopy. Extreme-ultraviolet spectroscopy of free nanoparticles is a powerful tool for studying the photophysics and photochemistry of resonantly excited or ionized nanometer-sized condensed-phase systems. Here, we demonstrate this capability by performing photoelectron–photoion coincidence experiments with pure and doped superfluid helium nanodroplets. Different doping options and beam sources provide a versatile platform to generate various van der Waals clusters as well as He nanodroplets. We present a detailed characterization of the new setup and show examples of its use for measuring high-resolution yield spectra of charged particles, time-of-flight ion mass spectra, anion–cation coincidence spectra, multi-coincidence electron spectra, and angular distributions. A particular focus of the research with this new endstation is on intermolecular charge and energy-transfer processes in heterogeneous nanosystems induced by valence-shell excitation and ionization. [ABSTRACT FROM AUTHOR]

Using the van der Waals density functional theory method (DFT-D2), we have investigated thickness dependent energy band gaps and effective masses of multilayer BN/graphene/BN structures by changing the stacking order. The band gap is substantially dependent on the stacking order. For instance, the calculated band gap in ABA stacking is about 150 meV, whereas it becomes 31 meV in ABC stacking. No significant thickness dependent band gap is observed in both ABA and ABC stackings although the band gap is gradually increasing with the BN thickness in ABA stacking. In addition, the effective mass is found to be strongly dependent on the stacking order. The effective mass in ABA stacking is much larger than that found in ABC stacking. On the other hand, the effective mass along K-M direction is smaller than that along K-Γ direction in ABA stacking. However, it is independent on the band direction in ABC stacking. We have found that the inclusion of van der Waals interaction alters thickness dependent band gap and effective mass of BN/graphene/BN multilayer systems compared with those found with standard density functional theory. [ABSTRACT FROM AUTHOR]

Electron correlations in molecules can be divided in short range dynamical correlations, long range Van der Waals type interactions, and near degeneracy static correlations. In this work, we analyze for a one-dimensional model of a two-electron system how these three types of correlations can be incorporated in a simple wave function of restricted functional form consisting of an orbital product multiplied by a single correlation function f (r12) depending on the interelectronic distance r12. Since the three types of correlations mentioned lead to different signatures in terms of the natural orbital (NO) amplitudes in two-electron systems, we make an analysis of the wave function in terms of the NO amplitudes for a model system of a diatomic molecule. In our numerical implementation, we fully optimize the orbitals and the correlation function on a spatial grid without restrictions on their functional form. Due to this particular form of the wave function, we can prove that none of the amplitudes vanishes and moreover that it displays a distinct sign pattern and a series of avoided crossings as a function of the bond distance in agreement with the exact solution. This shows that the wave function ansatz correctly incorporates the long range Van der Waals interactions. We further show that the approximate wave function gives an excellent binding curve and is able to describe static correlations. We show that in order to do this the correlation function f (r12) needs to diverge for large r12 at large internuclear distances while for shorter bond distances it increases as a function of r12 to a maximum value after which it decays exponentially. We further give a physical interpretation of this behavior. [ABSTRACT FROM AUTHOR]

Standard density functionals without van der Waals interactions yield an unsatisfactory description of ice phases, specifically, high density phases occurring under pressure are too unstable compared to the common low density phase Ih observed at ambient conditions. Although the description is improved by using functionals that include van der Waals interactions, the errors in relative volumes remain sizable. Here we assess the random phase approximation (RPA) for the correlation energy and compare our results to experimental data as well as diffusion Monte Carlo data for ice. The RPA yields a very balanced description for all considered phases, approaching the accuracy of diffusion Monte Carlo in relative energies and volumes. This opens a route towards a concise description of molecular water phases on surfaces and in cavities. [ABSTRACT FROM AUTHOR]

Quantum devices made from van der Waals (vdW) heterostructures of two dimensional (2D) materials may herald a new frontier in designer materials that exhibit novel electronic properties and unusual electronic phases. However, due to the complexity of layered atomic structures and the physics that emerges, experimental realization of devices with tailored physical properties will require comprehensive measurements across a large domain of material and device parameters. Such multi-parameter measurements require new strategies that combine data-intensive techniques—often applied in astronomy and high energy physics—with the experimental tools of solid state physics and materials science. We discuss the challenges of comprehensive experimental science and present a technique, called Multi-Parameter Dynamic Photoresponse Microscopy (MPDPM), which utilizes ultrafast lasers, diffraction limited scanning beam optics, and hardware automation to characterize the photoresponse of 2D heterostructures in a time efficient manner. Using comprehensive methods on vdW heterostructures results in large and complicated data sets; in the case of MPDPM, we measure a large set of images requiring advanced image analysis to extract the underlying physics. We discuss how to approach such data sets in general and in the specific case of a graphene–boron nitride–graphite heterostructure photocell. [ABSTRACT FROM AUTHOR]

van der Waals solids have been recognized as highly photosensitive materials that compete conventional Si and compound semiconductor based devices. While 2-dimensional nanosheets of single and multiple layers and 1-dimensional nanowires of molybdenum and tungsten chalcogenides have been studied, their nanostructured derivatives with complex morphologies are not explored yet. Here, we report on the electrical and photosensitive properties of WS2 nanowire-nanoflake hybrid materials we developed lately. We probe individual hybrid nanostructured particles along the structure using focused ion beam deposited Pt contacts. Further, we use conductive atomic force microscopy to analyze electrical behavior across the nanostructure in the transverse direction. The electrical measurements are complemented by in situ laser beam illumination to explore the photoresponse of the nanohybrids in the visible optical spectrum. Photodetectors with responsivity up to ∼0.4 AW−1 are demonstrated outperforming graphene as well as most of the other transition metal dichalcogenide based devices. [ABSTRACT FROM AUTHOR]

Hexagonal Boron Nitride (hBN) is a layered van der Waals material able to sustain hyperbolic phonon-polaritons within its mid-infrared reststrahlen bands. We study the effect of a metallic substrate adjacent to hBN flakes on the polariton dispersion and on the standing wave patterns in nanostructures by means of mid-infrared nanospectroscopy and nanoimaging. We exploit the gold-coated tip apex for atomic force microscopy to launch polaritons in thin hBN flakes. The photo-thermal induced mechanical resonance is used to detect the amplitude profile of polariton standing waves with a lateral resolution of 30 nm. We observe the polariton excitation spectra on hBN flakes as thin as 4 nm, thanks to the infrared field enhancement in the nanogap between the gold-coated tip apex and an ultraflat gold substrate. The data indicate no major effect of remote screening of the free electrons in gold on the phonon-polariton excitation that appears robust also against geometrical imperfections. [ABSTRACT FROM AUTHOR]

The structure and electronic properties of the MoS2/SiC van der Waals (vdW) heterostructures under an influence of normal strain and an external electric field have been investigated by the first-principles method. Our results reveal that the compressive strain has much influence on the band gap of the vdW heterostructures and the band gap monotonically increases from 0.955 to 1.343 eV. The results also imply that electrons are likely to transfer from MoS2 to SiC monolayer due to the deeper potential of SiC monolayer. Interestingly, by applying a vertical external electric field, the results present a parabola-like relationship between the band gap and the strength. As the E-field changes from -0.55 to +0.18 V/Å, the band gap first increases from zero to a maximum of about 1.76 eV and then decreases to zero. The significant variations of band gap are owing to different states of Mo, S, Si, and C atoms in conduction band and valence band. The predicted electric field tunable band gap of the MoS2/SiC vdW heterostructures is very promising for its potential use in nanodevices. [ABSTRACT FROM AUTHOR]

Graphene pseudohalides are natural candidates for use in molecular sensing due to their greater chemical activity as compared to both graphene halides and pristine graphene. Though their study is still in its infancy, being hindered until recently by the unavailability of both selective and efficient procedures for their synthesis, they promise to considerably widen the application potential of chemically modified graphenes. Herein, we employ van der Waals density functional theory to study the structural and electronic properties of two selected graphene pseudohalides, namely, cyanographone and isocyanographone and investigate the potential use of the latter as a chemical sensor via electron transport calculations. [ABSTRACT FROM AUTHOR]

The fragmentation of doubly and triply charged mercury clusters is theoretically studied to analyze an experiment performed by Katakuse’s group at Osaka University [T. Satoh et al., J. Mass Spectrom. Soc. Jpn. 51, 391 (2003)]. The fission barrier is calculated using a liquid-drop model proposed by Echt et al. In the decay of doubly charged clusters, the barrier height is found to take the minimum value for nearly symmetric fission. On the other hand, in the decay of triply charged clusters, the barrier is the lowest for strongly asymmetric fission. These results well explain the product size distribution observed in the experiment. The appearance size for multiply charged clusters measured in the experiment is found to be the size where the fission barrier is equal to the monomer evaporation energy. These findings provide evidence that small mercury clusters behave like van der Waals clusters in the process of fragmentation. [ABSTRACT FROM AUTHOR]

We investigated the release of a stuck carbon nanotube (CNT) cantilever beam in nanorelay applications using a nano-manipulator. Even with strong adhesion induced by electrostatic attraction that is 100 times stronger than the van der Waals interaction, successful release of a nanotube arm from a stuck state was realized by the application of a resonant vibration to the stuck CNT arm. Furthermore, nonvolatile operation of the nanotube nanorelay was demonstrated by the application of the resonant vibration to the stuck CNT arm. [ABSTRACT FROM AUTHOR]

A system-specific but very accurate density functional theory (DFT) correction scheme is proposed for precise calculations of adsorbent-adsorbate interactions by combining the non-empirical van der Waals density functional (vdW-DF) method and the empirical DFT/CC correction scheme to reach accuracy of the coupled clusters method with single, double and perturbative triple excitations (CCSD(T)). The new approach is applied to small molecules (CH4, CO2, H2, H2O, N2) interacting with silica surfaces and purely siliceous microporous solids. The vdW-DF/CC results for a perfectly reconstructed α-quartz surface are consistent with other dispersion-corrected DFT methods. Corrected for ZPVE, the vdW-DF/CC enthalpies of adsorption in pure-silica zeolite LTA (ΔHads(0 K)) of 3.6 and 5.2 kcal/mol for methane and carbon dioxide, respectively, are in excellent agreement with experimental values of 3.6 and 5.0 kcal/mol. The very high accuracy of the new scheme and its relatively easy use and numerical stability as compared to the earlier DFT/CC scheme offer a straightforward solution for obtaining reliable predictions of adsorption energies. [ABSTRACT FROM AUTHOR]

We report experimental results for the ionization and fragmentation of weakly bound van der Waals clusters of n C60 molecules following collisions with Ar2 +, He2 +, and Xe20 + at laboratory kinetic energies of 13 keV, 22.5 keV, and 300 keV, respectively. Intact singly charged C60 monomers are the dominant reaction products in all three cases and this is accounted for by means of Monte Carlo calculations of energy transfer processes and a simple Arrhenius-type [C60]n+ → C60++(n-1)C60 evaporation model. Excitation energies in the range of only ∼0.7 eV per C60 molecule in a [C60]13+ cluster are sufficient for complete evaporation and such low energies correspond to ion trajectories far outside the clusters. Still we observe singly and even doubly charged intact cluster ions which stem from even more distant collisions. For penetrating collisions the clusters become multiply charged and some of the individual molecules may be promptly fragmented in direct knock-out processes leading to efficient formations of new covalent systems. For Ar2 + and He2 + collisions, we observe very efficient C119+ and C118+ formation and molecular dynamics simulations suggest that they are covalent dumb-bell systems due to bonding between C59+ or C58+ and C60 during cluster fragmentation. In the Ar2 + case, it is possible to form even smaller C120-2m+ molecules (m = 2-7), while no molecular fusion reactions are observed for the present Xe20 + collisions. [ABSTRACT FROM AUTHOR]