A hybrid Gaussian and plane wave density functional scheme

LIPPERT, GERALD; Hutter, Jürg; Parrinello, Michele

doi:10.1080/00268979709482119

Cited by 1,167 publications

(987 citation statements)

References 0 publications

Supporting

Mentioning

984

Contrasting

Unclassified

Order By: Relevance

“…The software WSXM was used to analyse the STM images. 39 The DFT calculations were performed using the CP2K package (CP2K version 2.3.43; CP2K is freely available in http://www.cp2k.org/) with the mixed Gaussian and plane wave formalism 40 and periodic boundary conditions. The exchange and correlation functional used was the revised 41 version of the Perdew-Burke-Ernzerhof (PBE) 42 function.…”

Section: Methodsmentioning

confidence: 99%

Dehalogenation and Coupling of a Polycyclic Hydrocarbon on an Atomically Thin Insulator

et al. 2014

View full text Add to dashboard Cite

Catalytic activity is of pivotal relevance in enabling efficient and selective synthesis processes.Recently, covalent coupling reactions catalyzed by solid metal surfaces opened the rapidly evolving field of on-surface chemical synthesis. Tailored molecular precursors in conjunction with the catalytic activity of the metal substrate allow the synthesis of novel, technologically highly relevant materials such as atomically precise graphene nanoribbons. However, the reaction path on the metal substrate remains unclear in most cases and the intriguing question is how a specific atomic configuration between reactant and catalyst controls the reaction processes. In this study, we cover the metal substrate with a monolayer of hexagonal boron nitride (h-BN), reducing the reactivity of the metal, and gain unique access to atomistic details during the activation of a polyphenylene precursor by sequential dehalogenation and the subsequent coupling to extended oligomers. We use scanning tunneling microscopy (STM) and density functional theory (DFT) to reveal a reaction site anisotropy, induced by the registry mismatch between the precursor and the nano-structured h-BN monolayer. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 3 An atomically thin layer of insulating h-BN is a structurally analogous counterpart for graphene -a single layer of sp 2 -hybridised carbon atoms 1 -matching the graphene lattice almost perfectly with a small mismatch of approx. 2%. Currently, the fabrication of two-dimensional materials follows two main approaches: i) the bottom-up synthesis by substrate supported chemical vapor deposition (CVD) with suitable precursors and ii) the top-down approach by exfoliation. The assembly of graphene/h-BN heterostructures, leading to novel devices or devices with enhanced performance, usually relies on elaborate, sequential transfer processes of the produced layers. 2 The main obstacles are possible misalignment, introduction of defects and contaminations resulting from transferring layers that are just one atom thick. Only recently, the direct CVD growth of graphene on h-BN was demonstrated, offering superior properties. [3][4][5] However, the growth conditions are harsh (long exposure time, high temperatures, several cycles, etc.). Metal substrates are favored, because of their high catalytic activity, 6 but they have the disadvantage that they strongly alter the properties of the grown layers, which therefore cannot be directly used for electronic device fabrication.A common motif in on-surface chemical reactions is the activation of a precursor, the intermittent complex formed between precursor and substrate, and finally the coupling reaction. 7A long-standing question is the impact of the specific atomic configuration between substrate and reactant on the catalytic efficiency and how does the specific atomic arrangement chan...

show abstract

Section: Methodsmentioning

confidence: 99%

Dehalogenation and Coupling of a Polycyclic Hydrocarbon on an Atomically Thin Insulator

et al. 2014

View full text Add to dashboard Cite

show abstract

“…DFT calculations are performed with the hybrid Gaussian and plane wave (GPW) [7] scheme implemented in CP2K package. [8] We used the revised PBE for the exchange and correlation functional [9] plus van der Waals dispersion corrections computed through the Grimme pair-potential.…”

Section: Methodsmentioning

confidence: 99%

Investigation of h -BN/Rh(111) Nanomesh Interacting with Water and Atomic Hydrogen

Ding

Iannuzzi

Hutter

2011

Chimia

View full text Add to dashboard Cite

Recent STM experiments show that by exposing h-BN/Rh(111) nanomesh to water or atomic hydrogen interesting phenomena can be observed. We investigated by Density Functional Theory (DFT) the structure of bare nanomesh as well as in the presence of water clusters and atomic hydrogen. Our simulations allow the correct interpretation of the observed modifications of the STM topography under different tested conditions. For example, we could determine that the frequently observed three protrusions within the pore appearing in STM images obtained after dosing small amounts of water, are most likely determined by water hexamers. We also could confirm that the flattening of the h-BN overlayer after dosing atomic hydrogen is determined by the intercalation of the latter between BN and metal, which prevents the effective binding between N and Rh.256 CHIMIA 2011, 65, No. 4 Laureates: awards and Honors, sCs FaLL Meeting 2010 (111) nanomesh to water or atomic hydrogen interesting phenomena can be observed. We investigated by Density Functional Theory (DFT) the structure of bare nanomesh as well as in the presence of water clusters and atomic hydrogen. Our simulations allow the correct interpretation of the observed modifications of the STM topography under different tested conditions. For example, we could determine that the frequently observed three protrusions within the pore appearing in STM images obtained after dosing small amounts of water, are most likely determined by water hexamers. We also could confirm that the flattening of the h-BN overlayer after dosing atomic hydrogen is determined by the intercalation of the latter between BN and metal, which prevents the effective binding between N and Rh.

show abstract

“…38,39 Structure optimization and calculation of V QM for nm and nm-H are performed at the Kohn-Sham DFT level within the GPW approach. 40,41 Single-ζ valence plus polarization (SZVP) basis sets are used to describe the valence electrons of Rh, whereas basis sets of at least double-ζ quality (DZVP) are used for the other elements. 42 Norm-conserving pseudo-potentials [43][44][45] are employed to approximate the interactions between valence electrons and atomic cores.…”

Section: Charge Fittingmentioning

confidence: 99%

Wetting of water on hexagonal boron nitride@Rh(111): a QM/MM model based on atomic charges derived for nano-structured substrates

Golze

Hutter

Iannuzzi

2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The wetting of water on corrugated and flat hexagonal boron nitride (h-BN) monolayers on Rh(111) is studied within a hybrid quantum mechanics/molecular mechanics (QM/MM) approach. Water is treated by QM methods, whereas the interactions between liquid and substrate are described at the MM level. The electrostatic properties of the substrate are reproduced by assigning specifically generated partial charges to each MM atom. We propose a method to determine restrained electrostatic potential (RESP) charges that can be applied to periodic systems. Our approach is based on the Gaussian and plane waves algorithm and allows an easy tuning of charges for nano-structured substrates. We have successfully applied it to reproduce the electrostatic potential of the corrugated and flat h-BN/Rh(111) known as nanomesh. Molecular dynamics simulations of water films in contact with these substrates are performed and structural and dynamic properties of the interfaces are analyzed. Based on this analysis and on the interaction energies between water film and substrate, we found that the corrugated nanomesh is slightly more hydrophilic. On a macroscopic scale, we expect a smaller contact angle for a droplet on the corrugated surface. The wetting of water on corrugated and flat hexagonal boron nitride (h-BN) monolayers on Rh (111) is studied within a hybrid quantum mechanics/molecular mechanics (QM/MM) approach. Water is treated by QM methods, whereas the interactions between liquid and substrate are described at the MM level. The electrostatic properties of the substrate are reproduced by assigning specifically generated partial charges to each MM atom. We propose a method to determine restrained electrostatic potential (RESP) charges that can be applied to periodic systems. Our approach is based on the Gaussian and plane waves algorithm and allows an easy tuning of charges for nano-structured substrates. We have successfully applied it to reproduce the ESP of the corrugated and flat (h-BN)/Rh(111) known as nanomesh. Molecular dynamics simulations of water films in contact with these substrates are performed and structural and dynamic properties of the interfaces are analyzed. Based on these analyses and on the interaction energies between water film and substrate, we found that the corrugated nanomesh is slightly more hydrophilic. On a macroscopic scale, we predict a smaller contact angle for a droplet on the corrugated surface.

show abstract

A hybrid Gaussian and plane wave density functional scheme

Cited by 1,167 publications

References 0 publications

Dehalogenation and Coupling of a Polycyclic Hydrocarbon on an Atomically Thin Insulator

Dehalogenation and Coupling of a Polycyclic Hydrocarbon on an Atomically Thin Insulator

Investigation of h -BN/Rh(111) Nanomesh Interacting with Water and Atomic Hydrogen

Wetting of water on hexagonal boron nitride@Rh(111): a QM/MM model based on atomic charges derived for nano-structured substrates

Contact Info

Product

Resources

About