The Journal of Chemical Physics
Articles in this Issue
The nuts and bolts of gauge invariance of heat transport
In this study, I revisit the notion of gauge invariance in thermal transport and show, in the simplest and most general possible terms, why heat conductivity is unaffected by the specific choice of en...
Multiscale simulation of Raman images of water hexamers in a plasmonic nanocavity
Tip-enhanced Raman imaging can provide insights into the structural and chemical properties of adsorbed systems at the single-molecule scale. In this work, we demonstrate a multiscale method that comb...
Toward the “platinum standard” of quantum chemistry on quantum computers: Perturbative quadruple corrections in unitary coupled cluster theory
We propose a non-iterative, post-hoc correction to the unitary coupled cluster theory with the single, double, and triple excitations (UCCSDT) Ansatz, which considers the leading-order effects of negl...
A quantum field theory of polarization propagators
We present a field-theoretical quantum formalism to describe the space–time response of molecular electronic systems to external, particle-number-conserving perturbations. This work continues previous...
Natural excitation framework for defining the external space: Uncontracted and internally contracted multireference nonorthogonal wavefunction theories
In this article, we examine new formalisms for the construction of the external space when correlating reference wavefunctions built from nonorthogonal determinant expansions. Defining the external sp...
Predicting Newtonian viscosity using machine learning trained on equilibrium molecular dynamics
Newtonian viscosity (η0) defines the reference state for liquid rheology and serves as a cornerstone for constitutive modeling. Equilibrium molecular dynamics (EMD) provides a rigorous route to η0 thr...
A force-constant approach to O–H interactions in the light of the chained interactions conjecture
The chain interaction conjecture (ChIC) establishes that as any chemical bond is stretched, it must undergo a concatenated sequence of pair interactions of decreasing strength at specific distances de...
Pore-collapse in amorphous solid water: A dynamics study
Vapor-deposited amorphous ice, so-called amorphous solid water, exhibits complex structural and morphological transformations upon heating. A network of micropores, present at the deposition temperatu...
Using stereodynamical portraits to visualize polarized rotational angular momentum distributions in H2–surface collisions
The magnetic molecular interferometer (MMI) is a molecular beam scattering apparatus, which allows the polarization of the rotational angular momentum (J) of ortho-H2 molecules to be controlled using...
Analytic gradients for EOM-DEA-CCSD and EOM-DIP-CCSD: Theory, implementation, and application to diradicals
Equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD) provides a robust framework for describing a wide range of electronically excited and open-shell states. Among i...
Phase-regulated energy funneling and carrier relaxation dynamics in quasi-2D perovskites revealed by micro-area transient absorption spectroscopy
Two-dimensional (2D) perovskites have attracted considerable attention as promising candidates for optoelectronic devices due to their excellent optical properties, structural tunability, and intrinsi...
Beyond one-fluid approximations for the thermodynamics of fluid mixtures
Developing analytic equations of state for fluid mixtures based on perturbation theories requires simplifying approximations, in which mixture properties are determined from effective pure component p...
Whither BCH2? An <i>ab initio</i> inquiry
The boron methylene (BCH2) free radical has never been identified spectroscopically. We have undertaken a series of ab initio calculations to predict the molecular structures, vibrational frequencies,...
Autoionizing excited states of N2 using complex-basis function spin-flip coupled cluster theory
Collision-induced autoionizing excited states play an important role in plasma formation through associative ionization, where excited states lie in resonance with the continuum. In this work, we comp...
Log-time algorithms for exact stochastic simulation of fully connected reaction networks using low-rank decomposition and rejection sampling
We show how to adapt and improve the stochastic simulation algorithm (SSA), also known as the Lanore–Gillespie algorithm, to exactly and efficiently simulate a large, fully connected network of chemic...
Selectivity in gas–liquid interactions: Molecular beam scattering of CD4 and ND3 from an aqueous flat liquid jet
The dynamics of polar and nonpolar molecules colliding with an aqueous surface are characterized by scattering molecular beams of deuterated methane and ammonia, CD4 and ND3 (Ei = 28.9 and 30.3 kJ mol...
Partial widths of shape resonances in pyridine and uracil using the stabilization method
Low-energy electron attachment to molecules often leads to the formation of shape resonances, which play a pivotal role in electron-driven chemical processes. While the total decay width of a resonanc...
Modeling incoherent exciton transport between chlorosome tubes
Chlorosomes are the antennae of the efficient light harvesting complex in green (non-sulfur) bacteria. The ultrafast energy transfer process in natural light harvesting systems can be understood in te...
Calculating Coulomb interactions in molecular dynamics simulations: The Evjen method revisited
A new way is invented for computing Coulomb interactions in molecular dynamics simulations, which works well for bulk phase and lamina systems. This direct summation (DS) or cell dipole approach is an...
Density dependence of measured line intensities for O2 transitions
We report predictions and measurements of O2 absorption spectra that exhibit line intensity depletion with increasing gas density. This effect, which is attributed to the finite duration of collisions...
Two-state reaction path search using a quantum Monte Carlo-inspired approach
We present an algorithm for finding chemical reaction pathways using a Monte Carlo transition state search (MCTSS) scheme. Our strategy is a bidirectional two-state approach that simultaneously drives...
X-ray emission spectroscopy in liquid jets: A effective tool to probe valence and <i>p</i> -shells in organometallics and the influence of the solvation
In this combined experimental and theoretical work, we present state-of-the-art liquid jet experiments based on x-ray emission spectroscopy of the [Fe(CN)6]4− and [Fe(CN)6]3− molecular ions in the har...
Modeling the behavior of concentrated aqueous HNO3 using machine learning interatomic potentials
We develop two multi-defect machine learning interatomic potentials (MLIPs) trained at the BLYP-D2 and PBE-D3 density functional theories using the DeepMD-kit, allowing for the investigation of struct...
An 8-dimensional symmetry-adapted neural network potential energy surface for H2 dissociative chemisorption on hexagonal boron nitride <i>ortho</i> site with explicit surface atom motion
We developed an 8D, site-specific, reduced-dimensionality potential energy surface (PES) for H2 dissociation at the ortho site of hexagonal BN, treating two surface atom degrees of freedom explicitly....
Vibrational spectra of the radiation-induced cationic species resulting from phosphine monomers and dimers: A matrix isolation and CCSD(T) study
Phosphine (PH3) is the simplest phosphorus compound detected in the extrasolar and planetary environments, where it can be subjected to ionizing radiation. In this study, we first report the vibration...