arXiv subjects

John F. Dobson

Publications and source records attributed to John F. Dobson.

At least 19 recordsLinked to original sources

arXiv2026

Ballistic atomic transport in narrow carbon nanotubes

Friction forces are conventionally modeled via semiclassical theories that associate energy dissipation with newtonian motion on corrugated interface potentials. This consolidated approach is challenged at the nanoscale by observation of nearly unimpeded water flow in narrow carbon nanotubes (CNTs), in spite of nonvanishing energy corrugations. Here we go beyond the standard newtonian perspective, adopting a quantum mechanical description of 4 He flow through narrow CNTs. Building upon our Bloch-wave dynamics [Phys. Rev. Lett. 131, 206301 (2023)] we explore realistic flow conditions, including non-negligible interface interactions, finite temperatures, and imperfect CNTs. At T = 0 K we found that 4 He waves can propagate through ideally periodic, corrugated interface potentials with no friction: below a critical velocity regulated by interface corrugations, energy loss by emission of plasmon and phonon quanta is forbidden. Introducing realistic impurities/defects one still finds very large mean free paths that can exceed the micrometer scale, while thermal phonons and plasmons yield even lower scattering rates. This establishes the unexpected emergence of ballistic wavelike transport in narrow CNTs within realistic nanoscale devices, and demonstrates the intrinsic quantumness of nanoscale interfaces.

cond-mat.mes-hall↗

arXiv2026

Attractive and repulsive terms in multi-filament dispersion interactions

Filamentary objects such as nano-wires, nanotubes and DNA are of current interest in physics, nanoscience, chemistry, biology and medicine. They can interact via strong, exceptionally long-ranged many-object van der Waals (vdW, dispersion) forces, causing them to cluster into multi-object bundles. We analyse their vdW interactions perturbatively, predicting $N$-object vdW energy contributions that alternate in sign with increasing $N$. Our findings are confirmed here via the first detailed analysis of a 4-cylinder vdW model. We also provide novel insights permitting these tendencies to be understood simply in terms of electronic screening and anti-screening. Our results suggest that a non-perturbative calculation will be required for reliable prediction of dispersion interactions in these ubiquitous systems.

cond-mat.mtrl-sci↗

arXiv2025

Do 1-dimensional metals prefer to form even-numbered van der Waals clusters ?

Parallel quasi-one-dimensional metals are known to experience strong dispersion (van der Waals, vdW) interactions that fall off unusually slowly with separation between the metals. Examples include nanotube brushes, nano-wire arrays, and also common biological structures. In a many-stranded bundle, there are potentially strong multi-strand vdW interactions that go beyond a simple sum of negative (attractive) pairwise inter-strand energies. Perturbative analysis showed that these contributions alternate in sign, with the odd (triplet, quintuplet, ...) terms being positive (repulsive). The triplet case leds to the intriguing speculation that these strands may prefer to coalesce into even-numbered bundles, which could have implications for the formation kinetics of DNA, for example. Here we use a non-perturbative vdW energy analysis to show that this conjecture is not true in general. As our counter-example we consider 6 strands and show that 2 well-separated bundles of 3 strands have a more negative total vdW energy than 3 well-separated bundles of 2 strands ( i.e. an odd-number preference). We also discuss a bundle of 6 strands and explore the relative contributions beyond pairwise interactions.

cond-mat.mtrl-sci↗

arXiv2023

MBD+C: how to incorporate metallic character into atom-based dispersion energy schemes

The dispersion component of the van der Waals (vdW) interaction in low-dimensional metals is known to exhibit anomalous "Type-C non-additivity" [Int. J. Quantum Chem. 114, 1157 (2014)]. This causes dispersion energy behavior, at asymptotically large separations, that is missed by popular atom-based schemes for dispersion energy calculations. For example, the dispersion interaction energy between parallel metallic nanotubes at separation $D$ falls off aymptotically as approximately $D^{-2}$, whereas current atom-based schemes predict $D^{-5}$ asymptotically. To date it has not been clear whether current atom-based theories also give the dispersion interaction inaccurately at smaller separations for low-dimensional metals. Here we introduce a new theory that we term "MBD+C" . It permits inclusion of Type C effects efficiently within atom-based dispersion energy schemes such as Many Body Dispersion (MBD) and Universal MBD (uMBD). This allows us to investigate asymptotic, intermediate and near-contact regimes with equal accuracy. (The large contact energy of intimate metallic bonding is not primarily governed by dispersion energy and is described well by semi-local density functional theory.) Here we apply a simplified version,"nn-MBD+C", of our new theory to calculate the dispersion interaction for three low-dimensional metallic systems: parallel metallic chains of gold atoms, parallel Li-doped graphene sheets; and parallel (4,4) armchair carbon nanotubes. In addition to giving the correct asymptotic behavior, the new theory seamlessly gives the dispersion energy down to near-contact geometry, where it is similar to MBD but can give up to 15% more dispersion energy than current MBD schemes, in the systems studied so far. This percentage increases with separation until nn-MBD+C dominates MBD at asymptotic separations.

cond-mat.mes-hall↗

arXiv2018

Faraday-cage screening reveals intrinsic aspects of the van der Waals attraction

General properties of the recently observed screening of the van der Waals (vdW) attraction between a silica substrate and silica tip by insertion of graphene are predicted using basic theory and first-principles calculations. Results are then focused on possible practical applications, as well as an understanding of the nature of vdW attraction, considering recent discoveries showing it competing against covalent and ionic bonding. The traditional view of the vdW attraction as arising from pairwise-additive London dispersion forces is considered using Grimme's "D3" method, comparing results to those from Tkatchenko's more general many-body dispersion (MBD) approach, all interpreted in terms of Dobson's general dispersion framework. Encompassing the experimental results, MBD screening of the vdW force between two silica bilayers is shown to scale up to medium separations as 1.25 de/d, where d is the bilayer separation and de its equilibrium value, depicting antiscreening approaching and inside de. Means of unifying this correlation effect with those included in modern density functionals are urgently required.

cond-mat.mtrl-sci↗

arXiv2017

Casimir-Polder size consistency -- a constraint violated by some dispersion theories

A key goal in quantum chemistry methods, whether ab initio or otherwise, is to achieve size consistency. In this manuscript we formulate the related idea of "Casimir-Polder size consistency" that manifests in long-range dispersion energetics. We show that local approximations in time-dependent density functional theory dispersion energy calculations violate the consistency condition because of incorrect treatment of highly non-local "xc kernel" physics, by up to 10% in our tests on closed-shell atoms.

physics.chem-ph↗

arXiv2016

Spooky correlations and unusual van der Waals forces between gapless and near-gapless molecules

We consider the zero-temperature van der Waals interaction between two molecules, each of which has a zero or near-zero electronic gap between a groundstate and the first excited state, using a toy model molecule ( equilateral H3) as an example. We show that the van der Waals energy between two groundstate molecules falls off as D^(-3) instead of the usual D^(-6) dependence, when the molecules are separated by distance D: We show that this is caused by perfect "spooky" correlation between the two fluctuating electric dipoles. The phenomenon is related to, but not the same as, the "resonant" interaction between an electronically excited and a groundstate molecule introduced by Eisenschitz and London in 1930. It is also an example of "type C van der Waals non- additivity" recently introduced by one of us ( Int. J. Quantum Chem. 114, 1157 (2014)). Our toy molecule H3 is not stable, but symmetry considerations suggest that a similar vdW phenomenon may be observable, despite Jahn-Teller effects, in molecules with discrete rotational symmetry and broken inversion symmetry, such as certain metal atom clusters. The motion of the nuclei will need to be included for a definitive analysis of such cases, however.

cond-mat.other↗

arXiv2016

Layer Response Theory: Energetics of layered materials from semi-analytic high-level theory

We present a readily computable semi-analytic Layer Response Theory (LRT) for analysis of cohesive energetics involving two-dimensional layers such as BN or graphene. The theory approximates the Random Phase Approximation (RPA) correlation energy. Its RPA character ensures that the energy has the correct van der Waals asymptotics for well-separated layers, in contrast to simple pairwise atom-atom theories which fail qualitatively for layers with zero electronic energy gap. At the same time our theory is much less computationally intensive than the full RPA energy. It also gives accurate correlation energies near to the binding minimum, in contrast to Lifshitz-type theory. We apply our LRT theory successfully to graphite and to BN, and to a graphene-BN heterostructure.

cond-mat.mtrl-sci↗

arXiv2014

The flexible nature of exchange, correlation and Hartree physics: resolving "delocalization" errors in a 'correlation free' density functional

By exploiting freedoms in the definitions of 'correlation', 'exchange' and 'Hartree' physics in ensemble systems we better generalise the notion of 'exact exchange' (EXX) to systems with fractional occupations functions of the frontier orbitals, arising in the dissociation limit of some molecules. We introduce the Linear EXX ("LEXX") theory whose pair distribution and energy are explicitly \emph{piecewise linear} in the occupations $f^σ_{i}$. {\hi}We provide explicit expressions for these functions for frontier $s$ and $p$ shells. Used in an optimised effective potential (OEP) approach it yields energies bounded by the piecewise linear 'ensemble EXX' (EEXX) energy and standard fractional optimised EXX energy: $E^{EEXX}\leq E^{LEXX} \leq E^{EXX}$. Analysis of the LEXX explains the success of standard OEP methods for diatoms at large spacing, and why they can fail when both spins are allowed to be non-integer so that "ghost" Hartree interactions appear between \emph{opposite} spin electrons in the usual formula. The energy $E^{LEXX}$ contains a cancellation term for the spin ghost case. It is evaluated for H, Li and Na fractional ions with clear derivative discontinuities for all cases. The $p$-shell form reproduces accurate correlation-free energies of B-F and Al-Cl. We further test LEXX plus correlation energy calculations on fractional ions of C and F and again shows both derivative discontinuities and good agreement with exact results.

physics.atom-ph↗

arXiv2014

How many-body effects modify the van der Waals interaction between graphene sheets

Undoped graphene (Gr) sheets at low temperatures are known, via Random Phase Approximation (RPA) calculations, to exhibit unusual van der Waals (vdW) forces. Here we show that graphene is the first known system where effects beyond the RPA make qualitative changes to the vdW force. For large separations, $D \gtrsim 10$nm where only the $π_z$ vdW forces remain, we find the Gr-Gr vdW interaction is substantially reduced from the RPA prediction. Its $D$ dependence is very sensitive to the form of the long-wavelength many-body enhancement of the velocity of the massless Dirac fermions, and may provide independent confirmation of the latter via direct force measurements.

cond-mat.str-el↗

arXiv2013

Binding and interlayer force in the near-contact region of two graphite slabs: experiment and theory

Via a novel experiment, Liu \emph{et al.} [Phys. Rev. B, {\bf 85}, 205418 (2012)] estimated the graphite binding energy, specifically the cleavage energy, an important physical property of bulk graphite. We re-examine the data analysis and note that within the standard Lennard-Jones model employed, there are difficulties in achieving internal consistency in the reproduction of the graphite elastic properties. By employing similar models which guarantee consistency with the elastic constant, we find a wide range of model dependent binding energy values from the same experimental data. We attribute some of the difficulty in the determination of the binding energy to: i) limited theoretical understanding of the van der Waals dispersion of graphite cleavage, ii) the mis-match between the strong bending stiffness of the graphite-SiO$_2$ cantilever and the weak asymptotic inter-layer forces that are integrated over to produce the binding energy. We find, however, that the data does support determination of a maximum inter-layer force that is relatively model independent. We conclude that the peak force per unit area is $1.1 \pm 0.15$GPa for cleavage, and occurs at an inter-layer spacing of $0.377\pm 0.013$nm.

cond-mat.mtrl-sci↗

arXiv2013

Dispersion corrections in graphenic systems: a simple and effective model of binding

We combine high-level theoretical and \emph{ab initio} understanding of graphite to develop a simple, parametrised force-field model of interlayer binding in graphite, including the difficult non-pairwise-additive coupled-fluctuation dispersion interactions. The model is given as a simple additive correction to standard density functional theory (DFT) calculations, of form $ΔU(D)=f(D)[U^{vdW}(D)-U^{DFT}(D)]$ where $D$ is the interlayer distance. The functions are parametrised by matching contact properties, and long-range dispersion to known values, and the model is found to accurately match high-level \emph{ab initio} results for graphite across a wide range of $D$ values. We employ the correction on the difficult bigraphene binding and graphite exfoliation problems, as well as lithium intercalated graphite LiC$_6$. We predict the binding energy of bigraphene to be 0.27 J/m^2, and the exfoliation energy of graphite to be 0.31 J/m^2, respectively slightly less and slightly more than the bulk layer binding energy 0.295 J/m^2/layer. Material properties of LiC$_6$ are found to be essentially unchanged compared to the local density approximation. This is appropriate in view of the relative unimportance of dispersion interactions for LiC$_6$ layer binding.

cond-mat.mtrl-sci↗

arXiv2013

Assessment of range-separated time-dependent density-functional theory for calculating C6 dispersion coefficients

We assess a variant of linear-response range-separated time-dependent density-functional theory (TDDFT), combining a long-range Hartree-Fock (HF) exchange kernel with a short-range adiabatic exchange-correlation kernel in the local-density approximation (LDA) for calculating isotropic C6 dispersion coefficients of homodimers of a number of closed-shell atoms and small molecules. This range-separated TDDFT tends to give underestimated C6 coefficients of small molecules with a mean absolute percentage error of about 5%, a slight improvement over standard TDDFT in the adiabatic LDA which tends to overestimate them with a mean absolute percentage error of 8%, but close to time-dependent Hartree-Fock which has a mean absolute percentage error of about 6%. These results thus show that introduction of long-range HF exchange in TDDFT has a small but beneficial impact on the values of C6 coefficients. It also confirms that the present variant of range-separated TDDFT is a reasonably accurate method even using only a LDA-type density functional and without adding an explicit treatment of long-range correlation.

physics.chem-ph↗

arXiv2012

Quantum Continuum Mechanics Made Simple

In this paper we further explore and develop the quantum continuum mechanics (CM) of [Tao \emph{et al}, PRL{\bf 103},086401] with the aim of making it simpler to use in practice. Our simplifications relate to the non-interacting part of the CM equations, and primarily refer to practical implementations in which the groundstate stress tensor is approximated by its Kohn-Sham version. We use the simplified approach to directly prove the exactness of CM for one-electron systems via an orthonormal formulation. This proof sheds light on certain physical considerations contained in the CM theory and their implication on CM-based approximations. The one-electron proof then motivates an approximation to the CM (exact under certain conditions) expanded on the wavefunctions of the Kohn-Sham (KS) equations. Particular attention is paid to the relationships between transitions from occupied to unoccupied KS orbitals and their approximations under the CM. We also demonstrate the simplified CM semi-analytically on an example system.

physics.chem-ph↗

arXiv2012

Correlation energies beyond the random-phase approximation: ISTLS applied to spherical atoms and ions

The inhomogeneous Singwi, Tosi, Land and Sjolander (ISTLS) correlation energy functional of Dobson, Wang and Gould [PRB {\bf 66} 081108(R) (2008)] has proved to be excellent at predicting correlation energies in semi-homogeneous systems, showing promise as a robust `next step' fifth-rung functional by using dynamic correlation to go beyond the limitations of the direct random-phase approximation (dRPA), but with similar numerical scaling with system size. In this work we test the functional on fourteen spherically symmetric, neutral and charged atomic systems and find it gives excellent results (within 2mHa/$e^-$ except Be) for the absolute correlation energies of the neutral atoms tested, and good results for the ions (within 4mHa/$e^-$). In all cases it performs better than the dRPA. When combined with the previous successes, these new results point to the ISTLS functional being a prime contender for high-accuracy, benchmark DFT correlation energy calculations.

physics.atom-ph↗

arXiv2011

Efficient, long-range correlation from occupied wavefunctions only

We use continuum mechanics [Tao \emph{et al}, PRL{\bf 103},086401] to approximate the dynamic density response of interacting many-electron systems. Thence we develop a numerically efficient exchange-correlation energy functional based on the Random Phase Approximation (dRPA). The resulting binding energy curve $E(D)$ for thin parallel metal slabs at separation $D$ better agrees with full dRPA calculations than does the Local Density Approximation. We also reproduce the correct non-retarded van der Waals (vdW) power law $E(D)\aeq -C_{5/2}D^{-5/2}$ as $D\to\infty$, unlike most vdW functionals.

cond-mat.mes-hall↗

arXiv2009

Dispersion interaction between crossed conducting wires

We compute the $T=0K$ Van der Waals (nonretarded Casimir) interaction energy $E$ between two infinitely long, crossed conducting wires separated by a minimum distance $D$ much greater than their radius. We find that, up to a logarithmic correction factor, $E\propto -D^{-1}| \sin θ| ^{-1}f(θ)$ where $f(θ)$ is a smooth bounded function of the angle $θ$ between the wires. We recover a conventional result of the form $E\propto -D^{-4}|\sinθ| ^{-1}g(θ)$ when we include an electronic energy gap in our calculation. Our prediction of gap-dependent energetics may be observable experimentally for carbon nanotubes, either via AFM detection of the vdW force or torque, or indirectly via observation of mechanical oscillations. This shows that strictly parallel wires, as assumed in previous predictions, are not needed to see a novel effect of this type.

cond-mat.other↗

arXiv2009

Residual attractive force between superparamagnetic nanoparticles

A superparamagnetic nanoparticle (SPN) is a nanometre-sized piece of a material that would, in bulk, be a permanent magnet. In the SPN the individual atomic spins are aligned via Pauli effects into a single giant moment that has easy orientations set by shape or magnetocrystalline anisotropy. Above a size-dependent blocking temperature $T_{b}(V,τ_{obs})$, thermal fluctuations destroy the average moment by flipping the giant spin between easy orientations at a rate that is rapid on the scale of the observation time $τ_{obs}$. We show that, depite the vanising of the average moment, two SPNs experience a net attractive force of magnetic origin, analogous to the van der Waals force between molecules that lack a permanent electric dipole. This could be relevant for ferrofluids, for the clumping of SPNs used for drug delivery, and for ultra-dense magnetic recording media.

cond-mat.other↗