Minimum-Energy Conical Intersections by Compressed Multistate Pair-Density Functional Theory.

Compressed multistate pair-density functional theory (CMS-PDFT) is a multistate version of multiconfiguration pair-density functional theory that can capture the correct topology of coupled potential energy surfaces (PESs) around conical intersections. In this work, we develop interstate coupling vectors (ISCs) for CMS-PDFT in the OpenMolcas and PySCF/mrh electronic structure packages. Yet, the main focus of this work is using ISCs to calculate minimum-energy conical intersections (MECIs) by CMS-PDFT. This is performed using the projected constrained optimization method in OpenMolcas, which uses ISCs to restrain the iterations to the conical intersection seam. We optimize the S1/S0 MECIs for ethylene, butadiene, and benzene and show that CMS-PDFT gives smooth PESs in the vicinities of the MECIs. Furthermore, the CMS-PDFT MECIs are in good agreement with the MECI calculated by the more expensive XMS-CASPT2 method.

Resolving the Structural Debate for the Hydrated Excess Proton in Water.

It has long been proposed that the hydrated excess proton in water (aka the solvated "hydronium" cation) likely has two limiting forms, that of the Eigen cation (H9O4+) and that of the Zundel cation (H5O2+). There has been debate over which of these two is the more dominant species and/or whether intermediate (or "distorted") structures between these two limits are the more realistic representation. Spectroscopy experiments have recently provided further results regarding the excess proton. These experiments show that the hydrated proton has an anisotropy reorientation time scale on the order of 1-2 ps. This time scale has been suggested to possibly contradict the picture of the more rapid "special pair dance" phenomenon for the hydrated excess proton, which is a signature of a distorted Eigen cation. The special pair dance was predicted from prior computational studies in which the hydrated central core hydronium structure continually switches (O-H···O)* special pair hydrogen-bond partners with the closest three water molecules, yielding on average a distorted Eigen cation with three equivalent and dynamically exchanging distortions. Through state-of-art simulations it is shown here that anisotropy reorientation time scales of the same magnitude are obtained that also include structural reorientations associated with the special pair dance, leading to a reinterpretation of the experimental results. These results and additional analyses point to a distorted and dynamic Eigen cation as the most prevalent hydrated proton species in aqueous acid solutions of dilute to moderate concentration, as opposed to a stabilized or a distorted (but not "dancing") Zundel cation.

The hopping mechanism of the hydrated excess proton and its contribution to proton diffusion in water.

In this work, a series of analyses are performed on ab initio molecular dynamics simulations of a hydrated excess proton in water to quantify the relative occurrence of concerted hopping events and "rattling" events and thus to further elucidate the hopping mechanism of proton transport in water. Contrary to results reported in certain earlier papers, the new analysis finds that concerted hopping events do occur in all simulations but that the majority of events are the product of proton rattling, where the excess proton will rattle between two or more waters. The results are consistent with the proposed "special-pair dance" model of the hydrated excess proton wherein the acceptor water molecule for the proton transfer will quickly change (resonate between three equivalent special pairs) until a decisive proton hop occurs. To remove the misleading effect of simple rattling, a filter was applied to the trajectory such that hopping events that were followed by back hops to the original water are not counted. A steep reduction in the number of multiple hopping events is found when the filter is applied, suggesting that many multiple hopping events that occur in the unfiltered trajectory are largely the product of rattling, contrary to prior suggestions. Comparing the continuous correlation function of the filtered and unfiltered trajectories, we find agreement with experimental values for the proton hopping time and Eigen-Zundel interconversion time, respectively.

Water plays a dynamical role in a hydrogen-bonded, hexameric supramolecular assembly.

The hexameric resorcin[4]arene supramolecular assembly has attracted significant interest as a self-assembled capsule that exhibits dynamic host-guest chemistry. Many studies have been carried out to investigate the structure and thermodynamics of the assembly, but considerably less is known about its dynamical properties. Here, molecular dynamics simulations are used to investigate the timescales of water encapsulation in this assembly in wet chloroform. We have previously shown [A. Katiyar et al., Chem. Commun. 2019, 55, 6591-6594] that at low water content there are three distinct populations of water molecules present, while at higher water content an additional population, long water chains interacting with the assembly, appears. The relative free energies of these different water positions are calculated and time correlation functions are used to determine the timescales for interconversion between the populations. This analysis demonstrates that the water molecules are in rapid exchange with each other on timescales of tens of ps to a few ns, and suggests that water molecules might be acting as a critical component in the guest exchange mechanism.

The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry.

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.

Nonadiabatic Molecular Dynamics by Multiconfiguration Pair-Density Functional Theory.

We present the first implementation of multiconfiguration pair-density functional theory (MC-PDFT) ab initio molecular dynamics. MC-PDFT is a multireference electronic structure method that in many cases has a similar accuracy (or even better accuracy) the complete active space second-order perturbation theory (CASPT2) at a significantly lower computational cost. In this study, we introduced MC-PDFT analytical gradients into the SHARC molecular dynamics program for ab initio, nonadiabatic molecular dynamics simulations. We verify our implementation by examining the intersystem crossing dynamics of thioformaldehyde, and we observe excellent agreement with recent CASPT2 and experimental findings. Moreover, with MC-PDFT, we could perform dynamics simulations with the 12 electron in 10 orbitals active space that was computationally too expensive for direct dynamics with CASPT2.

Electron transitions in a Ce(III)-catecholate metal-organic framework.

A rare three-dimensional catecholate-based Ce(III) metal-organic framework (MOF), denoted as NU-1701, has been synthesized and crystallographically characterized. Density functional theory calculations highlight various possible electronic transitions that may present in NU-1701. These transitions are competitive and indicate increased lanthanide character of Ce(III).

Molecular Origins of the Barriers to Proton Transport in Acidic Aqueous Solutions.

The self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) method is used to analyze the structure, thermodynamics, and dynamics of hydrochloric acid solutions. The reorientation time scales of irreversible proton transport are elucidated by simulating 0.43, 0.85, 1.68, and 3.26 M HCl solutions at 270, 285, 300, 315, and 330 K. The results indicate increased counterion pairing with increasing concentration, which manifests itself via a reduced hydronium oxygen-chloride (O*-Cl) structuring in the radial distribution functions. Increasing ionic concentration also reduces the diffusion of the hydrated excess protons, principally by reducing the contribution of the Grotthuss proton hopping (shuttling) mechanism to the overall diffusion process. In agreement with prior experimental findings, a decrease in the activation energy of reorientation time scales was also observed, which is explicitly explained by using activated rate theory and an energy-entropy decomposition of the state-averaged radial distribution functions. These results provide atomistic verification of suggestions from recent two-dimensional infrared spectroscopy experiments that chloride anions (as opposed to hydrated excess protons) create entropic barriers to proton transport.

Minimal Experimental Bias on the Hydrogen Bond Greatly Improves Ab Initio Molecular Dynamics Simulations of Water.

Experiment directed simulation (EDS) is a method within a class of techniques seeking to improve molecular simulations by minimally biasing the system Hamiltonian to reproduce certain experimental observables. In a previous application of EDS to ab initio molecular dynamics (AIMD) simulation based on electronic density functional theory (DFT), the AIMD simulations of water were biased to reproduce its experimentally derived solvation structure. In particular, by solely biasing the O-O pair correlation function, other structural and dynamical properties that were not biased were improved. In this work, the hypothesis is tested that directly biasing the O-H pair correlation (and hence the H-O···H hydrogen bonding) will provide an even better improvement of DFT-based water properties in AIMD simulations. The logic behind this hypothesis is that for most electronic DFT descriptions of water the hydrogen bonding is known to be deficient due to anomalous charge transfer and over polarization in the DFT. Using recent advances to the EDS learning algorithm, we thus train a minimal bias on AIMD water that reproduces the O-H radial distribution function derived from the highly accurate MB-pol model of water. It is then confirmed that biasing the O-H pair correlation alone can lead to improved AIMD water properties, with structural and dynamical properties even closer to experiment than the previous EDS-AIMD model.

Water plays a diverse role in a hydrogen-bonded, hexameric supramolecular assembly.

The interactions between water and a hexameric resorcin[4]arene assembly formed in wet chloroform are examined by molecular dynamics simulations of the diffusion coefficients. It is found that the water diffusion coefficients provide a route to understanding the degree of water association with the assembly. The simulated diffusion coefficients are in excellent agreement with prior measurements and the diffusion data are well described by a simple adsorption model. This analysis demonstrates that a significant number of waters are encapsulated within the assembly or hydrogen-bonded to its exterior, consistent with and elucidated by a direct examination of the water molecules in the simulations.