The Journal of Chemical Physics
Articles in this Issue
Revealing the photochemical pathways of nitrate in water through first-principles simulations
The nitrate anion (NO3−) is abundant in environmental aqueous phases, including aerosols, surface waters, and snow, where its photolysis releases nitrogen oxides back into the atmosphere. Nitrate phot...
A basis-free phase space electronic Hamiltonian that recovers beyond Born–Oppenheimer electronic momentum and current density
We present a phase-space electronic Hamiltonian ĤPS (parameterized by both nuclear position X and momentum P) that boosts each electron into the moving frame of the nuclei that are closest in real sp...
Approximations of density matrices in N-electron valence state second-order perturbation theory (NEVPT2). III. Large active space calculations with selected configuration interaction reference
In multi-reference (MR) methods, addressing systems with large active spaces remains a challenge in the field. In Papers I and II of this series, we demonstrated that full rank N-electron valence stat...
Accurate and efficient parameterization of an atomic cluster expansion (ACE) potential for ammonia under extreme conditions
We present a machine learning interatomic potential for ammonia designed to capture its complex multiphase behavior, including both molecular and superionic phases. The potential is based on the atomi...
Photophysics of <i>meta</i>- and <i>para</i>-nitrophenolate. I. The role of configuration, microsolvation, and solvation on the charge transfer transition
The structure of the first five singlet excited electronic states of meta-nitrophenolate (m-NP) and para-nitrophenolate (p-NP) is investigated here in the gas phase, micro-solvent, and bulk solvent en...
Diagrammatic multiplet-sum method (MSM) density-functional theory (DFT): Completion of the two-orbital two-electron model (TOTEM) with an application to the avoided crossing in lithium hydride (LiH)
The Ziegler–Rauk–Baerends multiplet sum method (MSM) assumes that density functional theory (DFT) provides a good description of states dominated by a single determinant. It then uses symmetry to add...
Photophysics of <i>meta</i>- and <i>para</i>-nitrophenolate. II. Electronic spectra and quantum dynamics
The vibronic structure and nuclear dynamics underlying the first absorption bands of meta-nitrophenolate (m-NP) and para-nitrophenolate (p-NP) in the coupled manifold of S1–S2–S3–S4–S5 electronic stat...
Copula methods for modeling pair densities in density functional theory
We propose a new approach toward approximating the density-to-pair-density map based on copula theory from statistics. We extend the copula theory to multi-dimensional marginals and deduce that one ca...
Signatures of rotation–translation couplings, symmetry-breaking, and intermolecular interactions in the rovibrational spectra of solid H2O@C60
Some spectral features observed in the rovibrational spectra of solid H2O@C60 are shown to provide spectroscopic signatures of confinement-induced perturbations related to the coupling between the ori...
A simple confined rotor model to describe the ro-translational dynamics of water endofullerenes and to assign the ro-vibrational spectra of solid H2O@C60
A simple Confined Rotor Model (CRM) is used to assign the thirty-nine ro-vibrational transitions observed through the HOH bending and OH stretching ranges of the solid H2O@C60 mid-infrared (MIR) spect...
Influence of quantum corrections on the predicted isobaric heat capacity of polarizable water models
The isobaric heat capacity (Cp) is frequently used as a benchmark property whenever a new model is proposed or when comparing different force fields with classical molecular dynamics (MD) simulations....
Using a basis of products of contracted intra-molecular and contracted inter-molecular functions to compute the rovibrational spectrum of H2O–HF
In this paper, we report the J = 0–2 energy levels of H2O–HF calculated using our previous 9-D PES and compare the results with those of the experiment. The Schrodinger equation is solved variationall...
Amino acid coating of Fe3O4 surfaces under dry and hydrated conditions
This study explores the adsorption behavior of two amino acids (glycine - gly and glutamic acid - glu) as coating molecules for Fe3O4 nanoparticles to improve their biocompatibility for medical applic...
Smart navigation through a rotating barrier: Deep reinforcement learning with application to size-based separation of active microagents
We employ deep reinforcement learning methods to investigate shortest-time navigation strategies for smart active Brownian particles (microagents), which self-propel through a rotating potential barri...
Computing photodissociation cross sections and quasi-continuum properties of the NH radical
Photodissociation cross sections of NH for 250 &gt; λ &gt; 100 nm are studied using (i) the recently reported spectroscopic model of the five lowest electronic states of NH, (ii) a new set of...
Simulating inverse patchy colloid models
Nano- to micro-sized particles with differently charged surface areas exhibit complex interaction patterns, characterized by both opposite-charge attraction and like-charge repulsion. While several su...
Trust the force, but pull wisely: Structural insights into non-equilibrium response forces from pulling MD simulations
We analyze the coarse-grained equations of motion of molecular systems subject to external driving. As exemplary processes, we study by means of targeted and steered molecular dynamics simulations the...
Understanding nonlinear molecular responses in highly inhomogeneous electric fields: Insights from imidazole and pyrrole
The study of molecules subjected to highly inhomogeneous electric fields, whether static or time-dependent, is relatively unexplored. Advances in this area, as shown in condensed matter physics, could...
Systematic discrepancies between reference methods for noncovalent interactions within the S66 dataset
The accurate treatment of noncovalent interactions is necessary to model a wide range of applications, from molecular crystals to surface catalysts to aqueous solutions and many more. Quantum diffusio...
Systematic characterization of the homogeneous and heterogeneous hydrogen halide dimers
This study systematically characterizes the four homogeneous and six heterogeneous hydrogen-bonded dimers formed by hydrogen halide pairs (HX/HY where X, Y = F, Cl, Br, and I). The notation HX⋯HY indi...
Linear-scaling quadruple excitations in local pair natural orbital coupled-cluster theory
We present a fast, asymptotically linear-scaling implementation of the perturbative quadruples energy correction in coupled-cluster theory using local natural orbitals. Our work follows the domain-bas...
<i>In situ</i> and <i>operando</i> characterization: Advancing our understanding of functional materials
Energy conservation in real-time nuclear–electronic orbital Ehrenfest dynamics
Real-time nuclear–electronic orbital Ehrenfest (RT-NEO-Ehrenfest) dynamics methods provide a first-principles approach for describing nonadiabatic molecular processes with nuclear quantum effects. For...
Solvation enhances folding cooperativity and the topology dependence of folding rates in a lattice protein model
The aqueous solvent profoundly influences protein folding, yet its effects are relatively poorly understood. In this study, we investigate the impact of solvation on the folding of lattice proteins by...
Fast and flexible long-range models for atomistic machine learning
Most atomistic machine learning (ML) models rely on a locality ansatz and decompose the energy into a sum of short-ranged, atom-centered contributions. This leads to clear limitations when trying to d...