Modeling coarse-grained van der Waals interactions using dipole-coupled anisotropic quantum Drude oscillators.

The Quantum Drude Oscillator (QDO) model is a promising candidate for accurately calculating the van der Waals (vdW) interaction. Anisotropic QDO models have recently been used to represent quantum fluctuations of molecular fragments rather than that of single atoms. While this model promises accurate calculation of vdW energy, there is significant room for improvements, such as incorporating a proper fragmentation method, higher-order dispersion corrections, and so forth. The present work attempts to gauge dipole-dipole interactions' ability without fragmentation. A suitable anisotropic damping function is also introduced to work with anisotropic QDO. This revised model accurately predicts the binding energies of vdW complexes for most of the systems considered. This work indicates the limit of dipole approximation for an anisotropic QDO-based model.

A simple fragment-based method for van der Waals corrections over density functional theory.

Modeling intermolecular noncovalent interactions between large molecules remains a challenge for the electron structure theory community due to the high cost. Fragment-based methods usually fare well in reducing the cost of computations in such systems. On the other hand, the interactions between quantum mechanical fluctuations of electron density can be modeled well by the interaction between atom-centered quantum Drude oscillators. In this paper, we have developed a simple yet effective method to describe intermolecular van der Waals interactions based on an amalgamation of Drude oscillator with the fragmentation of molecular systems. The resulting interaction energies have been used as corrections over low-cost DFT functional PBE. We have tested our method on the S66X8 database with significant success. While this work is a proof-of-concept study to employ anisotropic oscillators for modeling electron fluctuation, we have also reduced the number of empirical parameters compared to DFT-D methods without any loss of accuracy in the process. The resulting method shows accuracy at par with Grimme's DFT-D3 method while only using dipole-dipole interactions.

Coulomb interactions between dipolar quantum fluctuations in van der Waals bound molecules and materials.

Mutual Coulomb interactions between electrons lead to a plethora of interesting physical and chemical effects, especially if those interactions involve many fluctuating electrons over large spatial scales. Here, we identify and study in detail the Coulomb interaction between dipolar quantum fluctuations in the context of van der Waals complexes and materials. Up to now, the interaction arising from the modification of the electron density due to quantum van der Waals interactions was considered to be vanishingly small. We demonstrate that in supramolecular systems and for molecules embedded in nanostructures, such contributions can amount to up to 6 kJ/mol and can even lead to qualitative changes in the long-range van der Waals interaction. Taking into account these broad implications, we advocate for the systematic assessment of so-called Dipole-Correlated Coulomb Singles in large molecular systems and discuss their relevance for explaining several recent puzzling experimental observations of collective behavior in nanostructured materials.

Quantum-Mechanical Relation between Atomic Dipole Polarizability and the van der Waals Radius.

The atomic dipole polarizability α and the van der Waals (vdW) radius R_{vdW} are two key quantities to describe vdW interactions between atoms in molecules and materials. Until now, they have been determined independently and separately from each other. Here, we derive the quantum-mechanical relation R_{vdW}=const×α^{1/7}, which is markedly different from the common assumption R_{vdW}∝α^{1/3} based on a classical picture of hard-sphere atoms. As shown for 72 chemical elements between hydrogen and uranium, the obtained formula can be used as a unified definition of the vdW radius solely in terms of the atomic polarizability. For vdW-bonded heteronuclear dimers consisting of atoms A and B, the combination rule α=(α_{A}+α_{B})/2 provides a remarkably accurate way to calculate their equilibrium interatomic distance. The revealed scaling law allows us to reduce the empiricism and improve the accuracy of interatomic vdW potentials, at the same time suggesting the existence of a nontrivial relation between length and volume in quantum systems.

An investigation into possible quantum chaos in the H2 molecule under intense laser fields via Ehrenfest phase space (EPS) trajectories.

By employing the Ehrenfest "phase space" trajectory method for studying quantum chaos, developed in our laboratory, the present study reveals that the H2 molecule under intense laser fields of three different intensities, I = 1 × 1014 W/cm2, 5 × 1014 W/cm2, and 1 × 1015 W/cm2, does not show quantum chaos. A similar conclusion is also reached through the Loschmidt echo (also called quantum fidelity) calculations reported here for the first time for a real molecule under intense laser fields. Thus, a long-standing conjecture about the possible existence of quantum chaos in atoms and molecules under intense laser fields has finally been tested and not found to be valid in the present case.

Long-Range Repulsion Between Spatially Confined van der Waals Dimers.

It is an undisputed textbook fact that nonretarded van der Waals (vdW) interactions between isotropic dimers are attractive, regardless of the polarizability of the interacting systems or spatial dimensionality. The universality of vdW attraction is attributed to the dipolar coupling between fluctuating electron charge densities. Here, we demonstrate that the long-range interaction between spatially confined vdW dimers becomes repulsive when accounting for the full Coulomb interaction between charge fluctuations. Our analytic results are obtained by using the Coulomb potential as a perturbation over dipole-correlated states for two quantum harmonic oscillators embedded in spaces with reduced dimensionality; however, the long-range repulsion is expected to be a general phenomenon for spatially confined quantum systems. We suggest optical experiments to test our predictions, analyze their relevance in the context of intermolecular interactions in nanoscale environments, and rationalize the recent observation of anomalously strong screening of the lateral vdW interactions between aromatic hydrocarbons adsorbed on metal surfaces.