化学物理
One-body reduced density matrix functional theory (RDMFT) provides an alternative to Density Functional Theory (DFT), able to treat static correlation while keeping a relatively low computation scaling. Its disadvantageous cost comes mainly…
Identifying transition states -- saddle points on the potential energy surface connecting reactant and product minima -- is central to predicting kinetic barriers and understanding chemical reaction mechanisms. In this work, we train an…
An azeotrope is a constant boiling point mixture, and its behavior is important for fluid separation processes. Predicting azeotropes from atomistic simulations is difficult, due to the complexities and convergence problems in Monte Carlo…
Mesoscale water-hydrophobic interfaces are of fundamental importance in multiple disciplines, but their molecular properties have remained elusive for decades due to experimental complications and alternate theoretical explanations.…
To gain insight into the dynamics of the CN + C2H6 gas-phase reaction, quasi-classical trajectory (QCT) calculations were performed on a full-dimensional analytical potential energy surface. This reaction presents very high exothermicity,…
In charged water microdroplets, which occur in nature or in the lab upon ultrasonication or in electrospray processes, the thermodynamics for reactive chemistry can be dramatically altered relative to the bulk phase. Here, we provide a…
Predicting how a material's microscopic structure and dynamics determine its transport properties remains a fundamental challenge. To alleviate this task's often prohibitive computational expense, we propose a Mori-based generalized quantum…
Recently, a new distributed implementation of the full configuration interaction (FCI) method has been reported [Gao et al. J. Chem Theory Comput. 2024, 20, 1185]. Thanks to a hybrid parallelization scheme, the authors were able to compute…
Quantum computing has emerged as a promising platform for simulating strongly correlated systems in chemistry, for which the standard quantum chemistry methods are either qualitatively inaccurate or too expensive. However, due to the…
Intermolecular charge-transfer is a highly important process in biology and energy-conversion applications where generated charges need to be transported over several moieties. However, its theoretical description is challenging since the…
Understanding the dynamic nature of the semiconductor-water interface is crucial for developing efficient photoelectrochemical water splitting catalysts, as it governs reactivity through charge and mass transport. In this study, we employ…
The present work shows that the free energy landscape associated with alanine dipeptide isomerization can be effectively represented by specific interatomic distances without explicit reference to dihedral angles. Conventionally, two stable…
Wavelets and Multiwavelets have lately been adopted in Quantum Chemistry to overcome challenges presented by the two main families of basis sets: Gaussian atomic orbitals and plane waves. In addition to their numerical advantages (high…
We have studied the stability of C$_{59}$ anions as a function of time, from their formation on femtosecond timescales to their stabilization on second timescales and beyond, using a combination of theory and experiments. The C$_{59}^-$…
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 effect are strongest in the nuclear region, where the…
New techniques in core-electron spectroscopy are necessary to resolve the structures of oxides of $f$-elements and other strongly correlated materials that are present only as powders and not as single crystals. Thus, accurate quantum…
In this manuscript, we provide a general theory for how surface phonons couple to molecular adsorbates. Our theory maps the extended dynamics of a surface's atomic vibrational motions to a generalized Langevin equation, and by doing so…
The implementation of an efficient self-consistent field (SCF) method including both scalar relativistic effects and spin-orbit interaction in density functional theory (DFT) is presented. We make use of Gaussian-type orbitals (GTOs) and…
The atomic vibrations of a solid surface can play a significant role in the reactions of surface-bound molecules, as well as their adsorption and desorption. Relevant phonon modes can involve the collective motion of atoms over a wide array…
A new reference state for density functional theory, termed the independent atom ansatz, is introduced in this work. This ansatz allows for the exact representation of electron density in terms of non-interacting, atom-localized orbitals.…