van der Waals Interactions in Bimolecular Reactions

The van der Waals (vdW) interaction is very important in fields of physics, biology and chemistry, and its role in reaction dynamics is an issue of great interest. In this review, we focus on the recent progresses in the theoretical and experimental studies on the vdW interaction in bimolecular reactions. In particular, we review those studies that have advanced our understanding of how the vdW interaction can strongly influence the dynamics in both direct activated and complex-forming reactions, and further extend the discussion to the polyatomic reactions involving more atoms and those occurring at cold and ultracold temperatures. We indicate that an accurate description of the delicate vdW structure and long-range potential remains a challenge nowadays in either ab initio calculations or the fitting of the potential energy surfaces. We also present an explanation on the concept of vdW saddle proposed by us recently which may have general importance.

Electronic structure and phase transition engineering in NbS2: Crucial role of van der Waals interactions

Based on first-principles simulations,we revisit the crystal structures,electronic structures,and structural stability of the layered transition metal dichalcogenides(TMDCs)NbS2,and shed more light on the crucial roles of the van der Waals(vdW)interactions.Theoretically calculated results imply that the vdW corrections are important to reproduce the layered crystal structure,which is significant to correctly describe the electronic structure of NbS2.More interestingly,under hydrostatic pressure or tensile strain in ab plane,an isostructural phase transition from two-dimensional layered structure to three-dimensional bulk in the I4/mmm phase has been uncovered.The abnormal structural transition is closely related to the electronic structure instability and interlayer bonding effects.The interlayer Nb-S distances collapse and the interlayer vdW interactions disappear,concomitant with new covalent bond emerging and increasing coordination number.Present work highlights the significance of the vdW interactions,and provides new insights on the unconventional structural transitions in NbS2,which will attract wide audience working in the hectic field of TMDCs.

Phonon resonance modulation in weak van der Waals heterostructures:Controlling thermal transport in graphene-silicon nanoparticle systems

The drive for efficient thermal management has intensified with the miniaturization of electronic devices.This study explores the modulation of phonon transport within graphene by introducing silicon nanoparticles influenced by van der Waals forces.Our approach involves the application of non-equilibrium molecular dynamics to assess thermal conductivity while varying the interaction strength,leading to a noteworthy reduction in thermal conductivity.Furthermore,we observe a distinct attenuation in length-dependent behavior within the graphene-nanoparticles system.Our exploration combines wave packet simulations with phonon transmission calculations,aligning with a comprehensive analysis of the phonon transport regime to unveil the underlying physical mechanisms at play.Lastly,we conduct transient molecular dynamics simulations to investigate interfacial thermal conductance between the nanoparticles and the graphene,revealing an enhanced thermal boundary conductance.This research not only contributes to our understanding of phonon transport but also opens a new degree of freedom for utilizing van der Waals nanoparticle-induced resonance,offering promising avenues for the modulation of thermal properties in advanced materials and enhancing their performance in various technological applications.

Direct observation of Pt nanocrystal coalescence induced by electron-excitation-enhanced van der Waals interactions

Nanocrystal coalescence has attracted paramount attention in nanostructure fabrication in the past decades. Tremendous endeavor and progress have been made in understanding its mechanisms, benefiting from the development of transmission electron microscopy. However, many mechanisms still remain unclear, especially for nanocrystals that lack a permanent dipole moment standing on a solid substrate. Here, we report an in situ coalescence of Pt nanocrystals on an amorphous carbon substrate induced by electron-excitation- enhanced van der Waals interactions studied by transmission electron microscopy and first principles calculations. It is found that the electron-beam-induced excitation can significantly enhance the van der Waals interaction between Pt nanocrystals and reduce the binding energy between Pt nanocrystals and the carbon substrate, both of which promote the coalescence. This work extends our understanding of the nanocrystal coalescence observed in a transmission electron microscope and sheds light on a potential pathway toward practical electron- beam-controlled nanofabrication.

Superradiance of ultracold cesium Rydberg |65D_(5/2)> → |66P_(3/2)>

We investigate Rydberg |65D_(5/2)> → |66P_(3/2)> superradiance in dense ultracold cesium atoms,where the ground atoms are excited to |65D_(5/2)> Rydberg states via two-photon excitation in a standard magneto-optical trap.The superradiant spectrum of |65D_(5/2)> → |66P_(3/2)> is obtained using the state-selective field ionization technique.We observe its dynamic evolution process by varying the delay time of ionization field td.The results show that the evolution process of |65D_(5/2)> →|66P_(3/2)> is much shorter than its radiation lifetime at room temperature,which verifies the superradiance effect.The dependence of the superradiance process on Rydberg atoms number N_(e) and principal quantum number n is investigated.The results show that the superradiance becomes faster with increasing N_(e),while it is suppressed for stronger van der Waals(vdW) interactions.Superradiance has potential applications in quantum technologies,and the Rydberg atom is an ideal medium for superradiance.Our system is effective for studying the strong two-body interaction between Rydberg atoms.

Alloy-buffer-controlled van der Waals epitaxial growth of aligned tellurene

Group-VI elemental two-dimensional(2D)materials(e.g.,tellurene(Te))have unique crystalline structures and extraordinarily physical properties.However,it still remains a great challenge to controllably grow 2D Te with good repeatability,uniformity,and highly aligned orientation using vapor growth method.Here,we design a Cu foil-assisted alloy-buffer-controlled growth method to epitaxially grow aligned single-crystalline 2D Te on an insulating mica substrate.The in-situ formation of Cu-Te alloy plays a key role on 2D Te growth,alleviating the spatial and temporal non-uniformity of precursor in conventional vapor deposition process.Through transmission electron microscopy(TEM)analysis combined with theoretical calculations,we unveil that the alignment growth of Te in the[110]direction is along the[600]direction of mica,owing to the small lattice mismatch(0.15%)and strong binding strength.This work presents a method to grow aligned high-quality 2D Te in a controllable manner.

Theoretical calculations of thermophysical properties of single-wall carbon nanotube bundles

Carbon nanotube bundles are promising thermal interfacial materials due to their excellent thermal and mechanical characteristics. In this study, the phonon dispersion relations and density of states of the single-wall carbon nanotube bundles are calculated by using the force constant model. The calculation results show that the inter-tube interaction leads to a significant frequency raise of the low frequency modes. To verify the applied calculation method, the specific heat of a single single-wall carbon nanotube is calculated first based on the obtained phonon dispersion relations and the results coincide well with the experimental data. Moreover, the specific heat of the bundles is calculated and exhibits a slight reduction at low temperatures in comparison with that of the single tube. The thermal conductivity of the bundles at low temperatures is calculated by using the ballistic transport model. The calculation results indicate that the inter-tube interaction, i.e. van der Waals interaction, hinders heat transfer and cannot be neglected at extremely low temperatures. For （5, 5） bundles, the relative difference of the thermal conductivity caused by ignoring inter-tube effect reaches the maximum value of 26% around 17 K, which indicates the significant inter-tube interaction effect on the thermal conductivity at low temperatures.

Ring Polymer Molecular Dynamics of the C(^(1)D)+H_(2) Reaction on the Most Recent Potential Energy Surfaces

Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.

Modeling Frequency- and Temperature-Invariant Dissipative Behaviors of Randomly Entangled Carbon Nanotube Networks under Cyclic Loading

Recent experiments have shown that entangled networks of carbon nanotubes exhibit temperature- and frequency-invariant dissipative behaviors under cyclic loading. We have performed coarse-grained molecular dynamics simulations which show that these intriguing phenomena can be attributed to the unstable attachments/detachments between individual carbon nanotubes induced by van der Waals interactions. We show that this behavior can be described by a triboelastic constitutive model. This study highlights the promise of carbon nanomaterials for energy absorption and dissipation under extreme conditions.

Quantum thermal field fluctuation induced corrections to the interaction between two ground-state atoms

We generalize the formalism proposed by Dalibard, Dupont-Roc, and Cohen-Tannoudji(the DDC formalism) in the fourth order for two atoms in interaction with scalar fields in vacuum to a thermal bath at finite temperature T, and then calculate the interatomic interaction energy of two ground-state atoms separately in terms of the contributions of thermal fluctuations and the radiation reaction of the atoms and analyze in detail the thermal corrections to the van der Waals and Casimir–Polder interactions. We discover a particular region, i.e. 4(λ3β)(1/2) ■ L■λwith L, β and λ denoting the interatomic separation, the wavelength of thermal photons and the transition wavelength of the atoms respectively, where the thermal corrections remarkably render the van der Waals force, which is usually attractive, repulsive, leading to an interesting crossover phenomenon of the interatomic interaction from attractive to repulsive as the temperature increases. We also find that the thermal corrections cause significant changes to the Casimir–Polder force when the temperature is sufficiently high, resulting in an attractive force proportional to TL-3in the λ ■ β ■ L region, and a force that can be either attractive or repulsive and even vanishing in the β ■ λ ■ L region depending on the interatomic separation.

Transformation optics from macroscopic to nanoscale regimes:a review

Transformation optics is a mathematical method that is based on the geometric interpretation of Maxwell’s equations.This technique enables a direct link between a desired electromagnetic(EM)phenomenon and the material response required for its occurrence,providing a powerful and intuitive design tool for the control of EM fields on all length scales.With the unprecedented design flexibility offered by transformation optics(TO),researchers have demonstrated a host of interesting devices,such as invisibility cloaks,field concentrators,and optical illusion devices.Recently,the applications of TO have been extended to the subwavelength scale to study surface plasmon-assisted phenomena,where a general strategy has been suggested to design and study analytically various plasmonic devices and investigate the associated phenomena,such as nonlocal effects,Casimir interactions,and compact dimensions.We review the basic concept of TO and its advances from macroscopic to the nanoscale regimes.

In-situ liquid cell TEM investigation on assembly and symmetry transformation of Pt superlattice

Two dimensional(2D)nanocrystal functional superlattices with a well controlled structure are of significant importance in photonic,plasmonic and optoelectronic applications and have been well studied,but it remains challenging to understand the formation mechanism and development pathway of the superlattice.In this study,we employed in-situ liquid cell transmission electron microscopy to study the formation of 2D superlattice and its local phase transition from hexagonal-to-square nanocrystal ordering.When colloidal nanocrystals flowed in the solution,long-range ordered hexagonal superlattice could be formed either through shrinking and rearrangement of nanocrystal aggregates or via nanocrystal attachment.As the nanocrystals’shape transformed from truncated octahedral to cube,the local superlattice rearranged to square geometry.Moreover,our observations and quantitative analyses reveal that the phase transition from hexagonal to square mainly originates from the strong van der Waals interactions between the vertical(100)facets.The tracking of 2D cube superlattice formation in real-time could provide unique insights on the governing force of superlattice assembling and stabilization.

Radial deformation and adhesion of carbon nanotube

The van der Waals(vdW) interactions of carbon nanotube(CNT)–substrate and CNT–CNT can cause strong adhesion. The adhesion can lead to radial deformation of CNTs, which is shown in both experiments and theoretical analysis. A scaling approach is used to predict the mechanical properties, vdW adhesion, and the elastic deformation of CNTs. It is found that the indentation of CNT is proportional to R7/4 and h3/2 in nanotube–substrate system and two same CNT system. Here, R and h are the radius and the wall thickness of CNT, respectively. The indentation ratio H1/H2 for CNT–CNT is proportional to(R1/R2)3/2 and(h2/h1)3/2.

Thermal Transport across Polyethylene Chains

In polymers,heat could transfer efficiently along the long polymer chains;however due to the finite length of polymer chains,such heat eventually has to pass across the chain-chain boundary which is less effective in heat transfer.This paper investigated the thermal transport across polyethylene chains with molecular dynamics(MD)simulations.Thermal transport across two polymer chains overlapping with each other is studied with different chain length(75 nm,150 nm and 251 nm)and chain-chain overlapping length.The results show that with increasing overlapping length,the total thermal conductance across the two chains exhibits maximum value,which is due to the increasing thermal resistance along the chains and the decreasing inter-chain thermal boundary resistance.Mathematically,we show that the total thermal resistance can be decomposed into two terms.The coupling term related to the inter-chain thermal resistance tends to saturate even with long overlapping length.