Bulletin of the American Physical Society
APS March Meeting 2021
Volume 66, Number 1
Monday–Friday, March 15–19, 2021; Virtual; Time Zone: Central Daylight Time, USA
Session A19: Van Der Waals Interactions in Molecules, Materials, and Complex Environments IFocus Live
|
Hide Abstracts |
Sponsoring Units: DCOMP Chair: Robert Distasio, Cornell University |
Monday, March 15, 2021 8:00AM - 8:36AM Live |
A19.00001: A low-cost composite variant of the r2SCAN density functional approximation Invited Speaker: Stefan Grimme The recently proposed second revision of the SCAN meta density functional approximation (DFA) [Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208−8215, termed r2SCAN] is used to construct an efficient composite electronic-structure method termed r2SCAN-3c, in analogy to the well established PBEh-3c and B97-3c approaches. It combines the unmodified r2SCAN functional with a specifically adapted def2-TZVP Gaussian AO-basis, the D4 dispersion model and a re-adjusted gCP correction for inter- and intramolecular BSSE. Due to the inherently higher accuracy of r2SCAN over many other (m)GGAs, further empirical adjustments for covalent bond lengths as in B97-3c are not required. The performance of r2SCAN-3c is evaluated comprehensively on several thousand energy evaluations, i.e., the GMTKN55 thermochemical database, extended benchmarks for non-covalent interactions (e.g., S30L, HB300SPXx10), organometallic reaction energies (MOR41), lattice energies of organic molecules (DMC8, X23) and ices (ICE10), as well as for the adsorption of small molecules on apolar coinage metals and polar surfaces. These tests reveal spectacularly accurate and consistent reaction energies and non-covalent interactions in molecular and periodic systems, as well as particularly outstanding conformational energies. For a suprisingly wide range of chemistry, r2SCAN-3c competes with hybrid/QZ-based methods at a small fraction (factor of about 100) of computational cost, surpassing the accuracy of its already efficient predecessor B97-3c at only twice the cost. As other (m)GGAs, r2SCAN-3c suffers from effects of the SIE but this is notably reduced as indicated by smaller artificial charge-transfer in various complexes. We thus chose this numerically robust method as our new group default in standard DFT applications for medium to large systems or large scale screening projects. |
Monday, March 15, 2021 8:36AM - 8:48AM Live |
A19.00002: Ab-initio approaches in surface chemistry: a new vdW meta-exchange-correlation functional Kai Trepte, Johannes Voss The development of exchange-correlation (XC) functionals has a long-standing history. |
Monday, March 15, 2021 8:48AM - 9:00AM Live |
A19.00003: Van der Waals Attraction and Pauli Repulsion: Learning New Tricks from an Old Dog Ornella Vaccarelli, Dmitry Fedorov, Martin Stoehr, Alexandre Tkatchenko The complex interplay of long-range van der Waals (vdW) attraction and shortrange (Pauli) repulsion plays a major role for the structure and dynamics of molecular systems. Arising from different physical origins, these forces do not seem to have a simple connection. Here, we build a consistent approach to study these interactions within the coarse-grained quantum Drude oscillator (QDO) model. This is an efficient tool to describe long-range correlation forces, where response properties of all valence electrons are represented just by a Drude particle. Treating these Drude oscillator particles as indistinguishable, we introduce the Pauli repulsion into this model and evaluate the exchange energy based on the multipole expansion of the Coulomb interaction. This allows us to reveal a remarkable compensation between dispersion and exchange forces for closed-shell dimers. The hidden symmetry between these two energies explains the recently discovered relationship between the vdW radius and atomic polarizabilities with a surprising connection between electronic and geometric properties of quantum-mechanical systems. Altogether, our results pave the way to explore the potential usefulness of the QDO model as a complete building block to develop next-generation quantum force fields. |
Monday, March 15, 2021 9:00AM - 9:12AM Live |
A19.00004: Attracting Opposites: Promiscuous Ion-π Binding in the Nucleobases Brian Ernst, Robert Distasio, Andrew Sullivan, Ka Un Lao
|
Monday, March 15, 2021 9:12AM - 9:24AM Live |
A19.00005: NENCI-2020: A Large Benchmark Database of Non-Equilibrium Non-Covalent Interactions with an Emphasis on Close Contacts Zachary Sparrow, Brian Ernst, Paul Joo, Ka Un Lao, Robert Distasio In this work, we present NENCI-2020: a benchmark database of non-equilibrium non-covalent interaction energies for a large and diverse set of intermolecular complexes. Designed with an emphasis on close contacts, NENCI-2020 simultaneously samples both intermolecular distances (spanning 0.7-1.1x the equilibrium separation) and intermolecular angles for ~150 molecular dimers, yielding ~8,000 benchmark intermolecular interaction energies computed at the CCSD(T)/CBS level. Using SAPT, we demonstrate that NENCI-2020 contains a diverse array of binding motifs, making this database well-suited for testing and developing next-generation force fields, density functional theory (DFT) approximations, quantum chemical (QC) methods, and machine-learning based approaches. This is followed by a critical assessment of ~75 DFT and QC methods, in which we find that most of these approaches can describe equilibrium and near-equilibrium intermolecular interaction energies to within chemical accuracy (1 kcal/mol). However, we find that nearly all methods suffer from a rapid and systematic increase in error as the intermolecular distance becomes small, thereby suggesting that more work will be needed to describe intermolecular potential energy surfaces with uniform accuracy. |
Monday, March 15, 2021 9:24AM - 9:36AM Live |
A19.00006: Reaching high precision of binding energies in molecular solids using quantum chemistry methods Khanh Ngoc Pham, Jiri Klimes Accurate calculation of binding energies of molecular solids is challenging due to the need to reliably model electron correlations in extended systems. Moreover, the energy differences between different phases or polymorphs are often small, leading to high requirements not only on the accuracy but also on the precision of the numerical set-up. To date, two main approaches are in use to obtain binding energies: direct evaluation using periodic boundary conditions (PBC) and many-body expansion (MBE). Here we compare their efficiency on calculations of four molecular solids: ethane, ethylene, and two forms of acetylene using the random phase approximation (RPA) and second-order Møller-Plesset perturbation theory (MP2). We assess how difficult it is to reach highly precise values (converged with numerical parameters) in the MBE and PBC approaches. The RPA and MP2 binding energies are also compared with reference values obtained using the coupled cluster scheme (CCSD(T)). We find that RPA with singles corrections is more accurate than MP2 for all considered systems. |
Monday, March 15, 2021 9:36AM - 9:48AM Live |
A19.00007: Reproducibility of potential energy surfaces of organic/metal interfaces on the example of PTCDA on Ag(111) Lukas Hörmann, Andreas Jeindl, Oliver T. Hofmann The correct geometry is arguably key to studying the properties of molecules adsorbed on metallic substrates. The energetics of molecular adsorption depend on the interplay of various mechanisms: Covalent bonds, charge transfer, Pauli repulsion and van-der-Waals (vdW) interactions shape the potential energy surface (PES). Describing PESs with density functional theory (DFT) requires carefully selecting the exchange correlation functional and vdW correction. To explore the robustness of the PES with respect to the choice of the method, we benchmark common local, semi-local and non-local functionals in combination with various vdW corrections. We investigate these methods using perylenetetracarboxylic dianhydride (PTCDA) on Ag(111). [1] |
Monday, March 15, 2021 9:48AM - 10:00AM Live |
A19.00008: Alkane Adsorption on Pt(111): the Dispersion Interaction on Metal Surfaces Christopher Sheldon, Joachim Paier, Joachim Sauer Alkane adsorption on metal surfaces occurs primarily through the vdW-type dispersion interaction. This is unaccounted for by most DFT methods, with the exception of the vdW-functionals.1-2 Instead, corrective terms must be added or higher-level methods used. However, this is a challenge for periodic systems, such as metal surfaces, where few high-level methods can be applied without prohibitive cost. |
Monday, March 15, 2021 10:00AM - 10:12AM Live |
A19.00009: Long-range Correlation Energy in the Interaction of Molecules with Surfaces Alina Umerbekova, Michele Pavanello By exploiting the fluctuation-dissipation theorem of DFT and a formally exact decomposition of the density-density linear response function evaluated at imaginary frequency, subsystem Density Functional Theory makes an excellent platform for developing non-local long-range correlation energy functionals [1,2]. We present a computational protocol to extract embedded C6 coefficients for molecules surrounded by complex environments from a real-time subsystem TDDFT simulation [3]. The C6 coefficients fully account for environmental screening effects through the many-body response [4]. We showcase a pilot calculation of the C6 coefficient of Benzene adsorbed on monolayer MoS2 and we show a surface enhancement of the van der Waals interaction between two benzene molecules nearby a MoS2 surface of 11 meV compared to the interaction estimated from C6 coefficients derived from isolated benzene molecules. |
Monday, March 15, 2021 10:12AM - 10:24AM Live |
A19.00010: Toward Systematic Quantum Embedding of Electrons and Charged Harmonic Oscillators Matej Ditte, Matteo Barborini, Alexandre Tkatchenko Many phenomena in physics, chemistry, and biology (solvents, membranes, nano-inclusions) can be described by embedding explicit molecules into an implicit environment. The coupling between both subsystems is typically treated via an approximate electrostatic or polarizable model [1]. Here, we aim at a systematic quantum treatment of molecular and environmental degrees of freedom modelled by a system of merged nuclei/electrons and charged quantum harmonic oscillators (QHOs). For this purpose, we construct a general Hamiltonian describing an embedded electronic domain in an environment of QHOs and present a variational ansatz, describing the full correlated ground state, integrated and optimized through quantum Monte Carlo methods [2]. Since charged QHOs, obtained by mapping many-body interactions onto a single quantum particle, are able to successfully reproduce the long-range response of real matter [3] with a reduced number of degrees of freedom, our new approach opens to the possibility of describing large systems at the full quantum level, yet at a low computational cost, uncovering important quantum effects between the electronic domain and the environment. |
Monday, March 15, 2021 10:24AM - 10:36AM Live |
A19.00011: Effective screening of van der Waals interactions in continuous environments Michael Walter, Johannes Fiedler, Stefan Buhmann, Shubham Sharma Computational investigations of supramolecular ordering under electrochemical conditions required density functional theory (DFT) studies of inter-molecular potentials in aqueous environment [1]. These interactions are partly of van der Waals (vdW) type where corrections to the usual DFT functionals have to be applied. While the aqueous environment can be conveniently included through a continuum solvent model, the vdW corrections lack this information. Starting from the Casimir-Polder Integral [2], we derive simple expressions for the correction of the vdW contribution relative to vacuum. Single point Gauss quadrature leads to the intuitive result, where the vacuum van der Waals C6 coefficient is screened by the squared environment's permittivity evaluated near to the resonance frequencies of the interacting particles. |
Monday, March 15, 2021 10:36AM - 10:48AM Live |
A19.00012: Second Quantization of Many-Body Dispersion Formalism: Towards Efficient Quantum Modeling of Million-Atom Systems in Complex Environments Matteo Gori, Alexandre Tkatchenko, Philip Kurian Dispersive van der Waals and Casimir interactions play a key role in an accurate description of the structure, stability, and dynamical properties in physical, chemical, and biological systems. In particular, the many-body dispersion (MBD) formalism, relying on a system of electrostatically coupled quantum harmonic oscillators, provides a tool to understand and numerically investigate many-body van der Waals interactions in systems up to tens of thousands of atoms [Chemical Society Reviews 48, 4118 (2019)]. However, the analysis of MBD collective normal modes in such large systems is not trivial. Moreover, it is not easy to define the coupling among such plasmon-like modes with the degrees of freedom of the surrounding environment (phonons, photons, polaritons). We present a quantum field theoretical approach based on second quantization formalism to describe MBD modes. Such a theoretical description i) enables improved computational efficiency, ii) allows a straightforward application of quantum information tools to MBD modes analysis, and iii) provides a suitable framework to describe the interaction of MBD modes with the surrounding environment. This paves the way to describe MBD effects in large systems such as realistic biomolecular complexes in an arbitrary environment. |
Monday, March 15, 2021 10:48AM - 11:00AM Live |
A19.00013: Next-generation nonlocal van der Waals density functional Timo Thonhauser, Kristian Berland, Debajit Chakraborty In 2004, a seminal paper introduced the first practical non-local van der Waals density functional called vdW-DF. However, since then, the functional form of vdW-DF has remained unchanged. Bringing together different insights from almost two decades of development and testing, we present the next-generation non-local correlation functional called vdW-DF3 [J. Chem. Theory Comput. 16, 5893 (2020)], in which we change the functional form while staying true to the original design philosophy. Although many popular functionals show good performance around the binding separation of van der Waals complexes, they often result in significant errors at larger separations. With vdW-DF3, we address this problem by taking advantage of a recently uncovered and largely unconstrained degree of freedom within the vdW-DF framework that can be constrained through empirical input, making our functional semi-empirical. We benchmark vdW-DF3 against a large set of well-studied test cases, finding good performance in general and a significant improvement in accuracy at larger separations. |
Follow Us |
Engage
Become an APS Member |
My APS
Renew Membership |
Information for |
About APSThe American Physical Society (APS) is a non-profit membership organization working to advance the knowledge of physics. |
© 2024 American Physical Society
| All rights reserved | Terms of Use
| Contact Us
Headquarters
1 Physics Ellipse, College Park, MD 20740-3844
(301) 209-3200
Editorial Office
100 Motor Pkwy, Suite 110, Hauppauge, NY 11788
(631) 591-4000
Office of Public Affairs
529 14th St NW, Suite 1050, Washington, D.C. 20045-2001
(202) 662-8700