The Journal of Chemical Physics
Articles in this Issue
The influence of chirality on the macroscopic behavior of multiferroic smectic phases
We study the influence of chirality on various types of multiferroic phases, which show simultaneously liquid crystalline order, as well as long range electric or magnetic order, including the possibi...
Polaron transformed canonically consistent quantum master equation
A central challenge in the theory of open quantum systems is the development of theoretical frameworks capable of accurately describing large, strongly interacting quantum many-body systems in the reg...
The x-ray absorption spectrum of the propargyl radical C3H3●
We report a combined experimental and computational study of the near-edge X-ray absorption fine structure (NEXAFS) spectrum of the propargyl radical, C3H3●. As a central intermediate in the formation...
Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. II. Isomer-resolved unimolecular dynamics
Transient carbon-centered hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation are characterized by their time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) and cy...
Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. I. Conformer- and isomer-resolved infrared spectra
Transient carbon-centered hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation are characterized by infrared (IR) action spectroscopy under jet-cooled conditions with selective detection of...
Quantum state-to-state dynamics studies of the C(3P) + OH(X2Π) → CO(a3Π) + H(2S) reaction based on a new HCO(12A″) potential energy surface
Using the multi-reference configuration interaction method with the aug-cc-pV(Q/5)Z basis set, 7762 ab initio energy points were computed and used to construct an analytical potential energy surface (...
Scaling transferable coarse-graining with mean force matching
Coarse-grained molecular dynamics often sacrifices accuracy and transferability for computational efficiency, but the use of machine-learned potentials helps coarse-grained models attain performance o...
Coherent biexciton transport in the presence of exciton–exciton annihilation in molecular aggregates
Biexciton dynamics in molecular aggregates provides a sensitive probe of the interplay between quantum coherence, band structure, and dissipation under strong excitation conditions. We present a theor...
Time-resolved ultrabroadband far-to-mid-infrared spectroscopy directly reveals doorway-mediated vibrational energy flow in an energetic crystal (β-HMX)
Understanding how vibrational energy flows from molecular vibrations to lattice phonons is critical for controlling the sensitivity of energetic molecular crystals. The intervening low-frequency doorw...
Structural definition of water activity reveals near-ideal thermodynamic behavior in electrolyte solutions
Chemical activity is central to thermodynamics and, through the chemical potential, governs phase equilibria and transport. While activity appears formally in thermodynamics, it is typically accessed...
Modeling crossflow filtration: Effect of shear on particle-enriched polarization and cake layers
Crossflow filtration is a pressure-driven separation and enrichment process of colloidal particles, where a feed dispersion is continuously pumped through a hollow cylindrical membrane channel permeab...
Anomalous phase behaviors near the multiphase coexistence point in 1-alkyl-3-methylimidazolium ionic liquids
The complex phase behaviors of ionic liquids near the multiphase coexistence point (MCP) were examined using synchrotron small- and wide-angle x-ray scattering. The cations utilized in this study were...
Microscopic origin of droplet line tension
The size dependence of the equilibrium contact angle of sessile droplets, commonly termed line tension, lies beyond classic Young’s law. Here, we identify a fundamental contribution to line tension ar...
Infrared spectrum of HCl–O2 dimer and tentative assignment of HCl–(O2)3 tetramer
Spectra of the weakly bound dimer HCl–O2 were studied in the mid-infrared region of the HCl fundamental band (≈2890 cm−1) using a tunable optical parametric oscillator source to probe a pulsed superso...
Cooperative elastic mechanism of activated structural relaxation in glassy liquids
The dramatic slowdown of dynamics in deeply supercooled liquids remains a central problem in condensed matter physics, chemistry, and materials science. Within the inherent-structure framework, struct...
Uniform distributions in nonuniform systems: Wall potentials generating constant density profiles in classical density functional theory
We study the inverse problem of classical density functional theory for inhomogeneous fluids: finding the wall potential that produces a constant equilibrium density profile, i.e., a perfectly flat de...
Exploring nanographene for single molecule imaging at cryogenic temperatures
Imaging single fluorescent molecules at cryogenic temperatures can increase photon budgets by suppressing photobleaching and non-radiative loss. Combined with rapid-freezing vitrification, it enables...
Intrinsic Raman scattering activity of OH and OD oscillators in liquid H2O, D2O, and HOD: Roles of zero-point energy and vibrational coupling
Liquid water is a strongly associated and vibrationally delocalized system in which nuclear quantum effects (NQEs), particularly zero-point energy and vibrational anharmonicity, influence the structur...
The entropic barrier around the conical intersection seam
Conical intersections (CIs) are seen as the main mediators of nonadiabatic transitions; yet, mixed quantum–classical (MQC) simulations that treat nuclei as classical point particles rarely, if ever, s...
Metallic hydrogen confined by graphene
The metallization of hydrogen is a prerequisite for the emergence of superconducting properties, along with those of hydrides. Chemical precompression has enabled a class of high-transition-temperatur...
Spectroscopic identification and structural characterization of Ag2H2− by mass-selected photoelectron velocity-map imaging
Ag2H2− is identified and characterized by photoelectron velocity-map imaging and quantum chemical calculations. High-resolution mass selection unambiguously confirms the formation of Ag2H2−, yielding...
Multiconfigurational Gaussian wavepacket simulations of exciton diffusion in semiconducting polymer chains: Efficient finite-temperature simulations with Langevin driving
First-principles quantum-dynamical simulations of photoinduced exciton dynamics are carried out using the variational two-layer Gaussian-based multiconfiguration time-dependent Hartree (2L-GMCTDH) met...
Coherent nonlinear optical probes for cavity-dressed vibrational mode mixing: Multidimensional double-quantum coherence and photon-echo spectroscopy
Cavity dressing of molecular vibrational dynamics expands the role of characteristic vibrations as spectroscopic markers of underlying ultrafast dynamics. Interacting vibrational modes exhibit pronoun...
Scalar machine learning of tensorial quantities—Born effective charges from monopole models
Predicting tensorial properties with machine learning models typically requires carefully designed tensorial descriptors. In this work, we introduce an alternative strategy for learning tensorial quan...
Exact tunneling splittings from path-integral hybrid Monte Carlo with enveloping bridging potentials
A path-integral hybrid Monte Carlo approach with enveloping bridging potentials (PIHMC-EBP) is proposed for calculating numerically exact tunneling splittings in molecular systems. The central idea is...