The Journal of Chemical Physics
Articles in this Issue
Activity-driven swelling and dynamics in segmentally active Rouse chains
We study a segmentally active Rouse chain in which activity is confined to a single contiguous segment of tunable length and position along the contour. Employing analytical normal-mode theory togethe...
Full-dimensional quantum scattering calculations of rovibrationally excited HD+HD collisions
Full-dimensional quantum scattering calculations are reported for rovibrational transitions in HD+HD collisions using a highly accurate interaction potential for the H2–H2 system. Several near-resonan...
Vibrational energy relaxation of excited free OH stretching mode at the surface of ice: An <i>ab initio</i> molecular dynamics simulation study
The vibrational energy relaxation dynamics of the excited free OH bond on the ice surface are investigated using ab initio molecular dynamics (AIMD) simulations. The present AIMD study reproduces expe...
Characterization of diarylethene-based photoswitches with core and valence photoabsorption and photoemission spectroscopies
We investigate the electronic structure of two dithienylethene (DTE) molecular photoswitches, BTF6 and PTF6, in the gas phase by combining valence photoelectron spectroscopy (PES), x-ray photoelectron...
Equation-of-motion coupled-cluster methods for doubly ionized and doubly electron-attached states with single, double, and triple substitutions: Theory, implementation, and benchmarks
We present new and computationally efficient implementation of the equation-of-motion (EOM) coupled-cluster methods for doubly ionized (DIP) and doubly electron-attached (DEA) states including single,...
Efficient implementation of analytical Raman intensities
In this study, we report an analytical derivative implementation of static polarizability gradients, needed for the prediction of Raman spectra, in the ORCA program. Our implementation is capable of h...
Ring-polymer instanton theory for tunneling between asymmetric wells
Instanton theory has arisen as a practical tool for calculating tunneling splittings in molecular systems. Unfortunately, the original formulation of instanton theory fundamentally breaks down when tr...
Fast evaluation of unbiased atomic forces in <i>ab initio</i> variational Monte Carlo via the Lagrangian technique
Ab initio quantum Monte Carlo (QMC) methods are state-of-the-art electronic structure calculations based on highly parallelizable stochastic frameworks for accurate solutions of the many-body Schrödin...
IEPDYN: Integral-equation formalism of population dynamics
We propose the integral-equation formalism of population dynamics (IEPDYN) to describe the population dynamics of distinct configurational states. According to classical reaction dynamics theory, the...
Theory of ion chemical potentials in heterogeneous electrolyte environments
Electrochemical applications, ranging from energy storage to electrocatalysis and separations, involve ions in heterogeneous environments such as electrode/electrolyte interfaces, material interphases...
Scaling laws and paradoxical metastable states in nanofilament entropic separation
Entropic forces play a fundamental role in nanoscale phenomena, from colloidal self-assembly to biomolecular disaggregation. Here, we develop an exact analytical theory and find general scaling laws f...
Quadrupole susceptibility automatic calculator in sum frequency generation spectroscopy incorporating magnetic contributions and refined local fields
While sum frequency generation (SFG) spectroscopy is known to have acute interface selectivity owing to the dipole approximation, it has been a long-standing concern to understand the contribution of...
Bootstrap embedding for interacting electrons in phonon coherent-state mean field
We develop a Fermi–Bose bootstrap embedding framework for the ground state of interacting electrons coupled to a phonon mean field. The method combines bootstrap embedding for correlated electrons wit...
Isolating solvent–solute hydrogen bonding interactions via 2D IR solvation shell spectroscopy
The solvation shell around a solute is a fundamental feature of liquid-phase solutions, determining the behavior and properties of both the solute and the overall solution. Direct experimental measure...
Pump–probe fluorescence lifetime imaging microscopy
Pump–probe spectroscopy is the most popular technique to resolve ultrafast photo-induced dynamics. Its fluorescence-detected variant connects it to fluorescence microscopy, for a combined spatial and...
Accordion-like tuning of composite pulse dipolar recoupling in solid-state NMR
Solid-state nuclear magnetic resonance (NMR) spectroscopy, being an important analytical tool in materials science and structural biology, typically relies on magic-angle-spinning (MAS). Often, it is...
Machine learning for biomolecular modeling
On the boroxol ring fraction in melt-quenched B2O3 glass: Insights from machine learning potentials
An atomistic structural model for melt-quenched B2O3 glass has eluded the simulation community so far. The difficulty lies in the abundance of six-membered boroxol rings—an intermediate-range order mo...
Effect of dynamics on anomalous thermal relaxations and information exchange
The Mpemba effect, an example of anomalous thermal relaxation, occurs when a system prepared at a higher temperature overtakes an identical system prepared at a lower temperature and cools down faster...
Harnessing the charge-transfer-to-solvent state of aqueous triiodide: A strategy to mitigate I2 trapping and enhance hydrated electron yield
The charge-transfer-to-solvent (CTTS) states of aqueous halides serve as prototypical systems for probing electron-transfer dynamics. In the photogeneration of hydrated electrons [e−(aq)] from iodide...
Tuning fragility in sodium lead borate glasses: Unveiling the interplay between compositions, Stokes–Einstein breakdown, and dynamical heterogeneity
Viscosity is a critical determinant of a liquid’s ability to form a glass upon cooling from a high-temperature state. As glass-forming liquids are cooled, their viscosity, or equivalently the structur...
Systematically improved potential energy surfaces via sinNN models and sparse grid sampling
Accurate, global Potential Energy Surfaces (PESs) expressed in sum-of-products (SOP) form are a prerequisite for efficient high-dimensional quantum dynamics simulations using the multi-configuration t...
Herzberg–Teller coupling in coherent multidimensional spectroscopy: Analytical response functions for multilevel systems
Coherent multidimensional spectroscopy enables detailed investigations of vibronic effects in molecular and solid-state systems. We present explicit analytical expressions for multidimensional nonline...
GenSym: A tool for random symmetric structure generation and its application in crystal structure prediction software
Crystal structure prediction (CSP) methods have become essential tools in materials discovery. As the initial step in CSP, the quality of the generated structures critically determines efficiency. It...
Theoretical relationship between the macro-texture and micro-structure in dairy processing revealed by the multi-scale simulation of coupled map lattice
The theoretical relationship between the macroscopic textural quality and microscopic structural quality appearing in the phase inversion processes from fresh cream via whipped cream to butter is reve...