arXiv subjects

D. R. Bowler

Publications and source records attributed to D. R. Bowler.

At least 19 recordsLinked to original sources

arXiv2024

Polarity vs Chirality: Functionality from competing magneto-structural instabilities

We report a phenomenological magneto-structural model based on competing free-energy terms that couple either polar or chiral distortions in cubic quadruple perovskites, depending on the global direction of magnetic moments. The model naturally explains why some compounds in this material system host magnetically-induced ferroelectricity at low temperature, while others such as CaMn$_3$(Cr$_3$Mn)O$_{12}$, which we characterise experimentally, do not. Importantly, our results suggest a new approach towards developing an applied multiferroic functionality, and can be generalised to other multi-sublattice systems where the magnetic interaction between sublattices is prohibited by spatial inversion.

cond-mat.mtrl-sci↗

arXiv2024

Ab initio study of subsurface diffusion of Cu on the H-passivated Si(001) surface

In this paper we use density-functional theory calculations to analyze both the stability and diffusion of Cu adatoms near and on the H-passivated Si(001) surface. Two different Cu sources are considered: depositing Cu from vacuum, and contaminating Cu outdiffusing from bulk Si. Deposited Cu from vacuum quickly moves subsurface to an interstitial site in the third Si layer (T2). Once there, Cu adatoms enter a subsurface zigzag migration route between T2 and another subsurface site, T2->HSL->T2, along the dimer row direction. Contaminating Cu outdiffusing from bulk is found to be a fast diffuser along both parallel and perpendicular directions to the dimer row when far from the surface. It is attracted to the layers close to the surface and becomes trapped at an interstitial site located at the sixth Si layer (T3). As the outdiffusing Cu atoms get closer to the surface, a channeling zigzag diffusion along the dimer row direction, similar to that one followed by deposited Cu from vacuum, is favoured over diffusion along the perpendicular direction. These results are consistent with previous experimental work done on similar systems and will motivate further experiments on the interesting interaction between Cu and Si surfaces.

cond-mat.mtrl-sci↗

arXiv2022

The CONQUEST code: large scale and linear scaling DFT

CONQUEST is a DFT code which was designed from the beginning to enable extremely large-scale calculations on massively parallel platforms, implementing both exact and linear scaling solvers for the ground state. It uses local basis sets (both pseudo-atomic orbitals, PAOs, and systematically convergent B-splines) and sparse matrix storage and operations to ensure locality in all aspects of the calculation. Using exact diagonalisation approaches and a full PAO basis set, systems of up to 1,000 atoms can be modelled with relatively modest resources (200-500 cores), while use of multi-site support functions (MSSF) enable calculations of up to 10,000 atoms with similar resources. With linear scaling, the code demonstrates essentially perfect weak scaling (fixed atoms per process), and has been applied to over 1,000,000 atoms, scaling to nearly 200,000 cores; it has been run on both the K computer and Fugaku, among other computers. CONQUEST calculates the total energy, forces and stresses exactly, and allows structural optimisation of both ions and simulation cell. Molecular dynamics calculations within the NVE, NVT and NPT ensembles are possible with both exact diagonalisation and linear scaling[6]. The code interfaces with LibXC to implement LDA and GGA functionals, with metaGGA and hybrid functionals under development. Dispersion interactions can be included using semi-empirical methods (DFT-D2/3, TS) and vdW-DF. The polarisation can be calculated using Resta's approach.

cond-mat.mtrl-sci↗

arXiv2021

A re-examination of antiferroelectric PbZrO$_3$ and PbHfO$_3$: an 80-atom $Pnam$ structure

First principles density functional theory (DFT) simulations of antiferroelectric (AFE) PbZrO$_3$ and PbHfO$_3$ reveal a dynamical instability in the phonon spectra of their purported low temperature $Pbam$ ground states. This instability doubles the $c$-axis of $Pbam$ and condenses five new small amplitude phonon modes giving rise to an 80-atom $Pnam$ structure. Compared with $Pbam$, the stability of this structure is slightly enhanced and highly reproducible as demonstrated through using different DFT codes and different treatments of electronic exchange & correlation interactions. This suggests that $Pnam$ is a new candidate for the low temperature ground state of both materials. With this finding, we bring parity between the AFE archetypes and recent observations of a very similar AFE phase in doped or electrostatically engineered BiFeO$_3$.

cond-mat.mtrl-sci↗

arXiv2019

Building bridges: matching density functional theory with experiment

We will discuss the key concepts in density functional theory (DFT), how it can be used to model experimental data, and consider how the synergy between DFT and experiment can give significant insights. The discussion will centre on the scanning tunnelling microscope (STM) and surface problems, tracking the author's personal interest, though the general principles are widely applicable.

cond-mat.mtrl-sci↗

arXiv2018

Semimetal-to-semiconductor transition and charge-density-wave melting in $1T$-TiSe$_{2-x}$S$_x$ single crystals

The transition metal dichalcogenide $1T$-TiSe$_2$ is a quasi-two-dimensional layered material with a phase transition towards a commensurate charge density wave (CDW) at a critical temperature T$_{c}\approx 200$K. The relationship between the origin of the CDW instability and the semimetallic or semiconducting character of the normal state, i.e., with the non-reconstructed Fermi surface topology, remains elusive. By combining angle-resolved photoemission spectroscopy (ARPES), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations, we investigate $1T$-TiSe$_{2-x}$S$_x$ single crystals. Using STM, we first show that the long-range phase coherent CDW state is stable against S substitutions with concentrations at least up to $x=0.34$. The ARPES measurements then reveal a slow but continuous decrease of the overlap between the electron and hole ($e$-$h$) bands of the semimetallic normal-state well reproduced by DFT and related to slight reductions of both the CDW order parameter and $T_c$. Our DFT calculations further predict a semimetal-to-semiconductor transition of the normal state at a higher critical S concentration of $x_c$=0.9 $\pm$0.1, that coincides with a melted CDW state in TiSeS as measured with STM. Finally, we rationalize the $x$-dependence of the $e$-$h$ band overlap in terms of isovalent substitution-induced competing chemical pressure and charge localization effects. Our study highlights the key role of the $e$-$h$ band overlap for the CDW instability.

cond-mat.mtrl-sci↗

arXiv2018

Local Real-Space View of the Achiral 1$T$-TiSe$_2$ 2 $\times$ 2 $\times$ 2 Charge Density Wave

The transition metal dichalcogenide 1$T$-TiSe$_2$ is a quasi-two-dimensional layered material undergoing a commensurate 2 $\times$ 2 $\times$ 2 charge density wave (CDW) transition with a weak periodic lattice distortion (PLD) below $\approx$ 200 K. Scanning tunneling microscopy (STM) combined with intentionally introduced interstitial Ti atoms allows to go beyond the usual spatial resolution of STM and to intimately probe the three-dimensional character of the PLD. Furthermore, the inversion-symmetric, achiral nature of the CDW in the $z$-direction is revealed, contradicting the claimed existence of helical CDW stacking and associated chiral order. This study paves the way to a simultaneous real-space probing of both charge and structural reconstructions in CDW compounds.

cond-mat.mtrl-sci↗

arXiv2017

Electronic coupling between Bi nanolines and the Si(001) substrate: An experimental and theoretical study

Atomic nanolines are one dimensional systems realized by assembling many atoms on a substrate into long arrays. The electronic properties of the nanolines depend on those of the substrate. Here, we demonstrate that to fully understand the electronic properties of Bi nanolines on clean Si(001) several different contributions must be accounted for. Scanning tunneling microscopy reveals a variety of different patterns along the nanolines as the imaging bias is varied. We observe an electronic phase shift of the Bi dimers, associated with imaging atomic p-orbitals, and an electronic coupling between the Bi nanoline and neighbouring Si dimers, which influences the appearance of both. Understanding the interplay between the Bi nanolines and Si substrate could open a novel route to modifying the electronic properties of the nanolines.

cond-mat.mtrl-sci↗

arXiv2017

Sub-atomic electronic feature from dynamic motion of Si dimer defects in bismuth nanolines on Si(001)

Scanning tunneling microscopy (STM) reveals unusual sharp features in otherwise defect free bismuth nanolines self-assembled on Si(001). They appear as subatomic thin lines perpendicular to the bismuth nanoline at positive biases and as atomic size beads at negative biases. Density functional theory (DFT) simulations show that these features can be attributed to buckled Si dimers substituting for Bi dimers in the nanoline, where the sharp feature is the counterintuitive signature of these dimers flipping during scanning. The perfect correspondence between the STM data and the DFT simulation demonstrated in this study highlights the detailed understanding we have of the complex Bi-Si(001) Haiku system.

cond-mat.mes-hall↗

arXiv2016

Stripe and short range order in the charge density wave of 1T-Cu$_x$TiSe$_2$

We study the impact of Cu intercalation on the charge density wave (CDW) in 1T-Cu$_{\text{x}}$TiSe$_{\text{2}}$ by scanning tunneling microscopy and spectroscopy. Cu atoms, identified through density functional theory modeling, are found to intercalate randomly on the octahedral site in the van der Waals gap and to dope delocalized electrons near the Fermi level. While the CDW modulation period does not depend on Cu content, we observe the formation of charge stripe domains at low Cu content (x$<$0.02) and a breaking up of the commensurate order into 2$\times$2 domains at higher Cu content. The latter shrink with increasing Cu concentration and tend to be phase-shifted. These findings invalidate a proposed excitonic pairing as the primary CDW formation mechanism in this material.

cond-mat.mtrl-sci↗

arXiv2016

Local resilience of the $1T$-TiSe$_2$ charge density wave to Ti self-doping

In Ti-intercalated self-doped $1T$-TiSe$_2$ crystals, the charge density wave (CDW) superstructure induces two nonequivalent sites for Ti dopants. Recently, it has been shown that increasing Ti doping dramatically influences the CDW by breaking it into phase-shifted domains. Here, we report scanning tunneling microscopy and spectroscopy experiments that reveal a dopant-site dependence of the CDW gap. Supported by density functional theory, we demonstrate that the loss of the longrange phase coherence introduces an imbalance in the intercalated-Ti site distribution and restrains the CDW gap closure. This local resilient behavior of the $1T$-TiSe$_2$ CDW reveals a novel mechanism between CDW and defects in mutual influence.

cond-mat.mtrl-sci↗

arXiv2016

Short-range phase coherence and origin of the 1T-TiSe2 charge density wave

The impact of variable Ti self-doping on the 1T-TiSe2 charge density wave (CDW) is studied by scanning tunneling microscopy. Supported by density functional theory we show that agglomeration of intercalated-Ti atoms acts as preferential nucleation centers for the CDW that breaks up in phaseshifted CDW domains whose size directly depends on the intercalated-Ti concentration and which are separated by atomically-sharp phase boundaries. The close relationship between the diminution of the CDW domain size and the disappearance of the anomalous peak in the temperature dependent resistivity allows to draw a coherent picture of the 1T-TiSe2 CDW phase transition and its relation to excitons.

cond-mat.mtrl-sci↗

arXiv2015

STM microscopy of the CDW in 1T-TiSe2 in the presence of single atom defects

We present a detailed low temperature scanning tunneling microscopy study of the commensurate charge density wave (CDW) in 1$T$-TiSe$_2$ in the presence of single atom defects. We find no significant modification of the CDW lattice in single crystals with native defects concentrations where some bulk probes already measure substantial reductions in the CDW phase transition signature. Systematic analysis of STM micrographs combined with density functional theory modelling of atomic defect patterns indicate that the observed CDW modulation lies in the Se surface layer. The defect patterns clearly show there are no 2$H$-polytype inclusions in the CDW phase, as previously found at room temperature [Titov A.N. et al, Phys. Sol. State 53, 1073 (2011). They further provide an alternative explanation for the chiral Friedel oscillations recently reported in this compound [J. Ishioka et al., Phys. Rev. B 84, 245125, (2011)].

cond-mat.mtrl-sci↗

arXiv2014

Doping nature of native defects in 1T-TiSe2

The transition metal dichalcogenide 1T-TiSe2 is a quasi two-dimensional layered material with a charge density wave (CDW) transition temperature of TCDW 200 K. Self-doping effects for crystals grown at different temperatures introduce structural defects, modify the temperature dependent resistivity and strongly perturbate the CDW phase. Here we study the structural and doping nature of such native defects combining scanning tunneling microscopy/spectroscopy and ab initio calculations. The dominant native single atom dopants we identify in our single crystals are intercalated Ti atoms, Se vacancies and Se substitutions by residual iodine and oxygen.

cond-mat.mtrl-sci↗

arXiv2013

Density-functional theory study of gramicidin A ion channel geometry and electronic properties

Understanding the mechanisms underlying ion channel function from the atomic-scale requires accurate ab initio modelling as well as careful experiments. Here, we present a density functional theory (DFT) study of the ion channel gramicidin A, whose inner pore conducts only monovalent cations and whose conductance has been shown to depend on the side chains of the amino acids in the channel. We investigate the ground-state geometry and electronic properties of the channel in vacuum, focusing on their dependence on the side chains of the amino acids. We find that the side chains affect the ground state geometry, while the electrostatic potential of the pore is independent of the side chains. This study is also in preparation for a full, linear scaling DFT study of gramicidin A in a lipid bilayer with surrounding water. We demonstrate that linear scaling DFT methods can accurately model the system with reasonable computational cost. Linear scaling DFT allows ab initio calculations with 10,000 to 100,000 atoms and beyond, and will be an important new tool for biomolecular simulations.

q-bio.BM↗

arXiv2013

Half-filled orbital and unconventional geometry of a common dopant in Si(001)

The determining factor of the bulk properties of doped Si is the column rather than the row in the periodic table from which the dopants are drawn. It is unknown whether the basic properties of dopants at surfaces and interfaces, steadily growing in importance as microelectronic devices shrink, are also solely governed by their column of origin. The common light impurity P replaces individual Si atoms and maintains the integrity of the dimer superstructure of the Si(001) surface, but loses its valence electrons to surface states. Here we report that isolated heavy dopants are entirely different: Bi atoms form pairs with Si vacancies, retain their electrons and have highly localized, half-filled orbitals.

cond-mat.mtrl-sci↗

arXiv2011

O(N) methods in electronic structure calculations

Linear scaling methods, or O(N) methods, have computational and memory requirements which scale linearly with the number of atoms in the system, N, in contrast to standard approaches which scale with the cube of the number of atoms. These methods, which rely on the short-ranged nature of electronic structure, will allow accurate, ab initio simulations of systems of unprecedented size. The theory behind the locality of electronic structure is described and related to physical properties of systems to be modelled, along with a survey of recent developments in real-space methods which are important for efficient use of high performance computers. The linear scaling methods proposed to date can be divided into seven different areas, and the applicability, efficiency and advantages of the methods proposed in these areas is then discussed. The applications of linear scaling methods, as well as the implementations available as computer programs, are considered. Finally, the prospects for and the challenges facing linear scaling methods are discussed.

cond-mat.mtrl-sci↗

arXiv2011

Endotaxial Si nanolines in Si(001):H

We present a detailed study of the structural and electronic properties of a self-assembled silicon nanoline embedded in the H-terminated silicon (001) surface, known as the Haiku stripe. The nanoline is a perfectly straight and defect free endotaxial structure of huge aspect ratio; it can grow micrometre long at a constant width of exactly four Si dimers (1.54nm). Another remarkable property is its capacity to be exposed to air without suffering any degradation. The nanoline grows independently of any step edges at tunable densities, from isolated nanolines to a dense array of nanolines. In addition to these unique structural characteristics, scanning tunnelling microscopy and density functional theory reveal a one-dimensional state confined along the Haiku core. This nanoline is a promising candidate for the long sought after electronic solid-state one-dimensional model system to explore the fascinating quantum properties emerging in such reduced dimensionality.

cond-mat.mes-hall↗