Scalar Relativistic Effects with Multiwavelets: Implementation and Benchmark.

The importance of relativistic effects in quantum chemistry is widely recognized, not only for heavier elements but throughout the periodic table. At the same time, relativistic effects are strongest in the nuclear region, where the description of electrons through a linear combination of atomic orbitals becomes more challenging. Furthermore, the choice of basis sets for heavier elements is limited compared with lighter elements where precise basis sets are available. Thanks to the framework of multiresolution analysis, multiwavelets provide an appealing alternative to overcoming this challenge: they lead to robust error control and adaptive algorithms that automatically refine the basis set description until the desired precision is reached. This allows one to achieve a proper description of the nuclear region. In this work, we extended the multiwavelet-based code MRChem to the scalar zero-order regular approximation framework. We validated our implementation by comparing the total energies for a small set of elements and molecules. To confirm the validity of our implementation, we compared both against a radial numerical code for atoms and the plane-wave-based code EXCITING.

MRChem Multiresolution Analysis Code for Molecular Electronic Structure Calculations: Performance and Scaling Properties.

MRChem is a code for molecular electronic structure calculations, based on a multiwavelet adaptive basis representation. We provide a description of our implementation strategy and several benchmark calculations. Systems comprising more than a thousand orbitals are investigated at the Hartree-Fock level of theory, with an emphasis on scaling properties. With our design, terms that formally scale quadratically with the system size in effect have a better scaling because of the implicit screening introduced by the inherent adaptivity of the method: all operations are performed to the requested precision, which serves the dual purpose of minimizing the computational cost and controlling the final error precisely. Comparisons with traditional Gaussian-type orbitals-based software show that MRChem can be competitive with respect to performance.

Role of conical intersection seam topography in the chemiexcitation of 1,2-dioxetanes.

Chemiexcitation, the generation of electronic excited states by a thermal reaction initiated on the ground state, is an essential step in chemiluminescence, and it is mediated by the presence of a conical intersection that allows a nonadiabatic transition from ground state to excited state. Conical intersections classified as sloped favor chemiexcitation over ground state relaxation. The chemiexcitation yield of 1,2-dioxetanes is known to increase upon methylation. In this work we explore to which extent this trend can be attributed to changes in the conical intersection topography or accessibility. Since conical intersections are not isolated points, but continuous seams, we locate regions of the conical intersection seams that are close to the configuration space traversed by the molecules as they react on the ground state. We find that conical intersections are energetically and geometrically accessible from the reaction trajectory, and that topographies favorable to chemiexcitation are found in all three molecules studied. Nevertheless, the results suggest that dynamic effects are more important for explaining the different yields than the static features of the potential energy surfaces.

Multiwavelets applied to metal-ligand interactions: Energies free from basis set errors.

Transition metal-catalyzed reactions invariably include steps where ligands associate or dissociate. In order to obtain reliable energies for such reactions, sufficiently large basis sets need to be employed. In this paper, we have used high-precision multiwavelet calculations to compute the metal-ligand association energies for 27 transition metal complexes with common ligands, such as H2, CO, olefins, and solvent molecules. By comparing our multiwavelet results to a variety of frequently used Gaussian-type basis sets, we show that counterpoise corrections, which are widely employed to correct for basis set superposition errors, often lead to underbinding. Additionally, counterpoise corrections are difficult to employ when the association step also involves a chemical transformation. Multiwavelets, which can be conveniently applied to all types of reactions, provide a promising alternative for computing electronic interaction energies free from any basis set errors.

Static Polarizabilities at the Basis Set Limit: A Benchmark of 124 Species.

Benchmarking molecular properties with Gaussian-type orbital (GTO) basis sets can be challenging, because one has to assume that the computed property is at the complete basis set (CBS) limit, without a robust measure of the error. Multiwavelet (MW) bases can be systematically improved with a controllable error, which eliminates the need for such assumptions. In this work, we have used MWs within Kohn-Sham density functional theory to compute static polarizabilities for a set of 92 closed-shell and 32 open-shell species. The results are compared to recent benchmark calculations employing the GTO-type aug-pc4 basis set. We observe discrepancies between GTO and MW results for several species, with open-shell systems showing the largest deviations. Based on linear response calculations, we show that these discrepancies originate from artifacts caused by the field strength and that several polarizabilies from a previous study were contaminated by higher order responses (hyperpolarizabilities). Based on our MW benchmark results, we can affirm that aug-pc4 is able to provide results close to the CBS limit, as long as finite difference effects can be controlled. However, we suggest that a better approach is to use MWs, which are able to yield precise finite difference polarizabilities even with small field strengths.

Dynamical Insights into the Decomposition of 1,2-Dioxetane.

Chemiluminescence in 1,2-dioxetane occurs through a thermally activated decomposition reaction into two formaldehyde molecules. Both ground-state and nonadiabatic dynamics (including singlet excited states) of the decomposition reaction have been simulated, starting from the first O-O bond-breaking transition structure. The ground-state dissociation occurs between t = 30 fs and t = 140 fs. The so-called entropic trap leads to frustrated dissociations, postponing the decomposition reaction. Specific geometrical conditions are necessary for the trajectories to escape from the entropic trap and for dissociation to be possible. The singlet excited states participate as well in the trapping of the molecule: dissociation including the nonadiabatic transitions to singlet excited states now occurs from t = 30 fs to t = 250 fs and later. Specific regions of the seam of the S0/S1 conical intersections that would "retain" the molecule for longer on the excited state have been identified.