Coarse-grained interaction potentials for polyaromatic hydrocarbons

Using Kohn-Sham density functional theory (KS-DFT), we have studied the interaction between various polyaromatic hydrocarbon molecules. The systems range from mono-cyclic benzene up to hexabenzocoronene (hbc). For several conventional exchange-correlation functionals potential energy curves of interaction of the $\pi$-$\pi$ stacking hbc dimer are reported. It is found that all pure local density or generalized gradient approximated functionals yield qualitatively incorrect predictions regarding structure and interaction. Inclusion of a non-local, atom-centered correction to the KS-Hamiltonian enables quantitative predictions. The computed potential energy surfaces of interaction yield parameters for a coarse-grained potential, which can be employed to study discotic liquid-crystalline mesophases of derived polyaromatic macromolecules

Understanding molecular representations in machine learning: The role of uniqueness and target similarity

The predictive accuracy of Machine Learning (ML) models of molecular properties depends on the choice of the molecular representation. Based on the postulates of quantum mechanics, we introduce a hierarchy of representations which meet uniqueness and target similarity criteria. To systematically control target similarity, we rely on interatomic many body expansions, as implemented in universal force-fields, including Bonding, Angular, and higher order terms (BA). Addition of higher order contributions systematically increases similarity to the true potential energy and predictive accuracy of the resulting ML models. We report numerical evidence for the performance of BAML models trained on molecular properties pre-calculated at electron-correlated and density functional theory level of theory for thousands of small organic molecules. Properties studied include enthalpies and free energies of atomization, heatcapacity, zero-point vibrational energies, dipole-moment, polarizability, HOMO/LUMO energies and gap, ionization potential, electron affinity, and electronic excitations. After training, BAML predicts energies or electronic properties of out-of-sample molecules with unprecedented accuracy and speed

Toward transferable interatomic van der Waals interactions without electrons: The role of multipole electrostatics and many-body dispersion

We estimate polarizabilities of atoms in molecules without electron density, using a Voronoi tesselation approach instead of conventional density partitioning schemes. The resulting atomic dispersion coefficients are calculated, as well as many-body dispersion effects on intermolecular potential energies. We also estimate contributions from multipole electrostatics and compare them to dispersion. We assess the performance of the resulting intermolecular interaction model from dispersion and electrostatics for more than 1,300 neutral and charged, small organic molecular dimers. Applications to water clusters, the benzene crystal, the anti-cancer drug ellipticine---intercalated between two Watson-Crick DNA base pairs, as well as six macro-molecular host-guest complexes highlight the potential of this method and help to identify points of future improvement. The mean absolute error made by the combination of static electrostatics with many-body dispersion reduces at larger distances, while it plateaus for two-body dispersion, in conflict with the common assumption that the simple $1/R^6$ correction will yield proper dissociative tails. Overall, the method achieves an accuracy well within conventional molecular force fields while exhibiting a simple parametrization protocol.Comment: 13 pages, 8 figure

Real-time observation of interfering crystal electrons in high-harmonic generation

Accelerating and colliding particles has been a key strategy to explore the texture of matter. Strong lightwaves can control and recollide electronic wavepackets, generating high-harmonic (HH) radiation which encodes the structure and dynamics of atoms and molecules and lays the foundations of attosecond science. The recent discovery of HH generation in bulk solids combines the idea of ultrafast acceleration with complex condensed matter systems and sparks hope for compact solid-state attosecond sources and electronics at optical frequencies. Yet the underlying quantum motion has not been observable in real time. Here, we study HH generation in a bulk solid directly in the time-domain, revealing a new quality of strong-field excitations in the crystal. Unlike established atomic sources, our solid emits HH radiation as a sequence of subcycle bursts which coincide temporally with the field crests of one polarity of the driving terahertz waveform. We show that these features hallmark a novel non-perturbative quantum interference involving electrons from multiple valence bands. The results identify key mechanisms for future solid-state attosecond sources and next-generation lightwave electronics. The new quantum interference justifies the hope for all-optical bandstructure reconstruction and lays the foundation for possible quantum logic operations at optical clock rates

Ferromagnetic coupling and magnetic anisotropy in molecular Ni(II) squares

We investigated the magnetic properties of two isostructural Ni(II) metal complexes [Ni4Lb8] and [Ni4Lc8]. In each molecule the four Ni(II) centers form almost perfect regular squares. Magnetic coupling and anisotropy of single crystals were examined by magnetization measurements and in particular by high-field torque magnetometry at low temperatures. The data were analyzed in terms of an effective spin Hamiltonian appropriate for Ni(II) centers. For both compounds, we found a weak intramolecular ferromagnetic coupling of the four Ni(II) spins and sizable single-ion anisotropies of the easy-axis type. The coupling strengths are roughly identical for both compounds, whereas the zero-field-splitting parameters are significantly different. Possible reasons for this observation are discussed.Comment: 7 pages, 7 figure

Pion-nucleon scattering in a meson-exchange model

The pi-N interaction is studied within a meson-exchange model and in a coupled-channels approach which includes the channels pi-N, eta-N, as well as three effective pi-pi-N channels namely rho-N, pi-Delta, and sigma-N. Starting out from an earlier model of the Julich group systematic improvements in the dynamics and in some technical aspects are introduced. With the new model an excellent quantitative reproduction of the pi-N phase shifts and inelasticity parameters in the energy region up to 1.9 GeV and for total angular momenta J leq 3/2 is achieved. Simultaneously, good agreement with data for the total and differential pi-N -> eta-N transition cross sections is obtained. The connection of the pi_N dynamics in the S_{11} partial wave with the reaction pi-N -> eta-N is discussed.Comment: 32 pages, 9 figure

Metal-insulator transitions: Influence of lattice structure, Jahn-Teller effect, and Hund's rule coupling

We study the influence of the lattice structure, the Jahn-Teller effect and the Hund's rule coupling on a metal-insulator transition in AnC60 (A= K, Rb). The difference in lattice structure favors A3C60 (fcc) being a metal and A4C60 (bct) being an insulator, and the coupling to Hg Jahn-Teller phonons favors A4C60 being nonmagnetic. The coupling to Hg (Ag) phonons decreases (increases) the value Uc of the Coulomb integral at which the metal-insulator transition occurs. There is an important partial cancellation between the Jahn-Teller effect and the Hund's rule coupling.Comment: 4 pages, RevTeX, 3 eps figure, additional material available at http://www.mpi-stuttgart.mpg.de/docs/ANDERSEN/fullerene

Prevalence of Mentoring on Clinical Versus Experimental Doctoral Programs: Survey Findings, Implications, and Recommendations

Previous research suggests that mentorships are quite important in the development of junior professionals in a range of fields, including psychology. Yet some evidence suggests that clinical doctoral students may be less frequently mentored by graduate faculty than other psychology doctoral students. Results of a survey of clinical and experimental psychology doctorates who earned the degree in four distinct time frames from 1945 to the present indicated that clinical PhDs (53%) were indeed less likely than experimental PhDs (69%) to be mentored. Potential explanations for this discrepancy include the nature of clinical training, diffusion in clinical training, and the advent of professional training models. The implications of less frequent mentoring for clinical doctorates are discussed, and several recommendations for addressing this phenomenon are offered