-
Nature and energetics of low-lying excited singlets/triplets and intersystem crossing rates in selone analogs of perylenediimide: A theoretical perspective J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-18 Annette Mariya Tedy, Arun K. Manna
The structural rigidity and chemical diversity of the highly fluorescent perylenediimide (PDI) provide wide opportunities for developing triplet photosensitizers with sufficiently increased energy efficiency. Remarkably high intersystem crossing (ISC) rates with a complete fluorescence turn-off reported recently for several thione analogs of PDI due to substantially large spin–orbit coupling garners
-
QuTree: A tree tensor network package J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-18 Roman Ellerbrock, K. Grace Johnson, Stefan Seritan, Hannes Hoppe, J. H. Zhang, Tim Lenzen, Thomas Weike, Uwe Manthe, Todd J. Martínez
We present QuTree, a C++ library for tree tensor network approaches. QuTree provides class structures for tensors, tensor trees, and related linear algebra functions that facilitate the fast development of tree tensor network approaches such as the multilayer multiconfigurational time-dependent Hartree approach or the density matrix renormalization group approach and its various extensions. We investigate
-
Deciphering the conformational preference and ionization dynamics of tetrahydrofuran: Insights from advanced spectroscopic techniques J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-18 Sung Man Park, Chan Ho Kwon
Tetrahydrofuran (THF) has garnered significant attention due to its pivotal role in biological and chemical processes. The diverse array of conformations exhibited by THF profoundly impacts its reactivity and interactions with other molecules. Understanding these conformational preferences is crucial for comprehending its molecular behavior. In this study, we utilize infrared (IR) resonant vacuum ultraviolet
-
Energy-dependent photoion angular distributions in two-body Coulomb explosions of molecules J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Keyu Guo, Yingbin Li, Min Li, Chuanpeng Cao, Xueqing Duan, Yang Liu, Yupeng Liu, Zichen Li, Jingkun Xu, Yueming Zhou, Benhai Yu, Peixiang Lu
We experimentally study two-body Coulomb explosions of CO2, O2, and CH3Cl molecules in intense femtosecond laser pulses. We observe an obvious variation in the ionic angular distribution of the fragments with respect to the kinetic energy releases (KERs). Using a classical model based on ab initio potential energy curves, we find that the dependence of the ionic angular distribution on the KER is relevant
-
Relativistic effect influencing the diverse bonding character of the interfacial Ag staple motifs in thiolate-protected nanoclusters J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Endong Wang, Yi Gao
Thiolate-protected noble-metal nanoclusters have recently attracted extensive attention due to their appealing properties in optics, catalysis, etc. Within the same group element, experiments indicate that Ag staples exhibit di-, tri-, or even tetra-coordination, in contrast to the di-coordination observed in Au staples, rendering the structures of Ag nanoclusters more intricate. However, the underlying
-
Experimental two-dimensional infrared spectra of methyl thiocyanate in water and organic solvents J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Joseph C. Shirley, Carlos R. Baiz
Thiocyanates, nitriles, and azides represent a versatile set of vibrational probes to measure the structure and dynamics in biological systems. The probes are minimally perturbative, the nitrile stretching mode appears in an otherwise uncongested spectral region, and the spectra report on the local environment around the probe. Nitrile frequencies and lineshapes, however, are difficult to interpret
-
Unveiling the structural and bonding properties of AuSi2− and AuSi3− clusters: A comprehensive analysis of anion photoelectron spectroscopy and ab initio calculations J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Sheng-Jie Lu
Silicon clusters infused with transition metals, notably gold, exhibit distinct characteristics crucial for advancing microelectronics, catalysts, and energy storage technologies. This investigation delves into the structural and bonding attributes of gold-infused silicon clusters, specifically AuSi2− and AuSi3−. Utilizing anion photoelectron spectroscopy and ab initio computations, we explored the
-
Influence of Zr aggregation on Li-ion conductivity of amorphous solid-state electrolyte Li–La–Zr–O J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Dexin Zhang, Yiwei You, Chundong Zhao, Xinrui Cao, Tie-Yu Lü, Zi-Zhong Zhu, Shunqing Wu
In our study, we investigated the influence of the local structure of amorphous Li–La–Zr–O (a-LLZO) on Li-ion conductivity using ab initio molecular dynamics (AIMD). A-LLZO has shown promising properties in inhibiting the growth of lithium dendrites, making it a potential candidate for solid electrolytes in all-solid-state lithium batteries. The low Li-ion conductivity of a-LLZO is currently limiting
-
Diffuse basis functions for explicitly correlated calculations on the heavy p-block: aug-cc-pVnZ-PP-F12 sets for Ga–Kr, In–Xe, and Tl–Rn J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 J. Grant Hill
New aug-cc-pVnZ-PP-F12 basis sets (n = D, T, Q) for the heavy p-block elements, Ga–Kr, In–Xe, and Tl–Rn, have been developed by augmenting the cc-pVnZ-PP-F12 sets with additional higher angular momentum diffuse functions. These basis sets have been optimized for use in explicitly correlated F12 calculations, and matching auxiliary basis sets for density fitting of conventional and F12 integrals have
-
Thermodynamics and collective modes in hydrogen-bonded fluids J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Cillian Cockrell, Aleksandra Dragović
The thermodynamics of liquids and supercritical fluids is notorious for eluding a general theory, as can be done for crystalline solids on the basis of phonons and crystal symmetry. The extension of solid state notions, such as configurational entropy and phonons, to the liquid state remains an intriguing but challenging topic. This is particularly true for liquids, such as water, whose many structural
-
Predicting pressure-dependent rate constants for the furan + OH reactions and their impact under tropospheric conditions J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Joel Leitão Nascimento, Murillo H. Queiroz, Roberto Rivelino, Tiago Vinicius Alves
In this work, we have evaluated the influence of temperature and pressure on the mechanism of furan oxidation by the OH radical. The stationary points on the potential energy surface were described at the M06-2X/aug-cc-pVTZ level of theory. In the kinetic treatment at the high-pressure limit (HPL), we have combined the multistructural canonical variational theory with multidimensional small-curvature
-
Potential energy landscape of a coarse grained model for water: ML-BOP J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Andreas Neophytou, Francesco Sciortino
We quantify the statistical properties of the potential energy landscape for a recently proposed machine learning coarse grained model for water, machine learning-bond-order potential [Chan et al., Nat. Commun. 10, 379 (2019)]. We find that the landscape can be accurately modeled as a Gaussian landscape at all densities. The resulting landscape-based free-energy expression accurately describes the
-
Photofragmentation of cyclobutanone at 200 nm: TDDFT vs CASSCF electron diffraction J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Alberto Martín Santa Daría, Javier Hernández-Rodríguez, Lea M. Ibele, Sandra Gómez
To simulate a 200 nm photoexcitation in cyclobutanone to the n-3s Rydberg state, classical trajectories were excited from a Wigner distribution to the singlet state manifold based on excitation energies and oscillator strengths. Twelve singlet and 12 triplet states are treated using TD-B3LYP-D3/6-31+G** for the electronic structure, and the nuclei are propagated with the Tully surface hopping method
-
Unraveling the rapid ion migration in perovskite solar cells by circuit-switched transient photoelectric technique J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Ziyou Wu, Shuai Yuan, Shaoshuai Miao, Yiyi Li, Wenqi Zhang, Dandan Cao, Junyu Nie, Yi Wang, Xi-Cheng Ai, Jian-Ping Zhang
Ion migration activated by illumination is a critical factor responsible for the performance decline and stability degradation of perovskite solar cells (PSCs). While ion migration has been widely believed to be much slower than charge transport, recent research suggests that, despite the lack of understanding of the mechanism, it may also be involved in a series of rapid photoelectric responses of
-
Can GW handle multireference systems? J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-15 Abdallah Ammar, Antoine Marie, Mauricio Rodríguez-Mayorga, Hugh G. A. Burton, Pierre-François Loos
Due to the infinite summation of bubble diagrams, the GW approximation of Green’s function perturbation theory has proven particularly effective in the weak correlation regime, where this family of Feynman diagrams is important. However, the performance of GW in multireference molecular systems, characterized by strong electron correlation, remains relatively unexplored. In the present study, we investigate
-
Reducing the time-step errors in diffusion Monte Carlo J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-14 Tyler A. Anderson, Manolo C. Per, C. J. Umrigar
We modify the reweighting factor of the projector used in diffusion Monte Carlo to reduce the time-step error of the total energy. Furthermore, we present a reweighting scheme that has the desirable feature that it is exactly size-consistent, i.e., the energy of a system containing widely separated fragments is the same as the sum of the energies of the individual fragments. The practical utility of
-
Assumption-free analysis for amplification-based quantitative nucleic acid detection J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-14 Yu Fu, Lu Lin, Chuanbo Liu, Jin Wang
The accurate detection and quantification of biological species that are rarely present but potentially devastating is of paramount importance for the life sciences, biosecurity, food safety, and environmental monitoring. Consequently, there has been significant interest in the sensitive and accurate detection of nucleic acids, leveraging both chemical and biological methods. Among these, quantitative
-
The 2D-IR spectrum of hydrogen-bonded silanol groups in pyrogenic silica J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-14 Paul M. Donaldson
Pyrogenic silica is a form of amorphous silica with a high surface area and a heterogeneous distribution of silanol hydroxyl terminations and defects. In this work, the interesting and unusual form of the hydroxyl-stretch 2D-IR spectrum of pyrogenic silica is presented and explored in the deuterated (deuteroxyl) form. Transition dipole couplings between hydrogen-bonded and non-hydrogen-bonded silanol
-
Tensor-SqRA: Modeling the transition rates of interacting molecular systems in terms of potential energies J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-14 Alexander Sikorski, Amir Niknejad, Marcus Weber, Luca Donati
Estimating the rate of rare conformational changes in molecular systems is one of the goals of molecular dynamics simulations. In the past few decades, a lot of progress has been done in data-based approaches toward this problem. In contrast, model-based methods, such as the Square Root Approximation (SqRA), directly derive these quantities from the potential energy functions. In this article, we demonstrate
-
Temperature dependence of the dynamics and interfacial width in nanoconfined polymers via atomistic simulations J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-14 Nikolaos Patsalidis, George Papamokos, George Floudas, Vagelis Harmandaris
We present a detailed computational study on the temperature effect of the dynamics and the interfacial width of unentangled cis-1,4 polybutadiene linear chains confined between strongly attractive alumina layers via long, several μs, atomistic molecular dynamics simulations for a wide range of temperatures (143–473 K). We examine the spatial gradient of the translational segmental dynamics and of
-
Cluster perturbation theory IX: Perturbation series for the coupled cluster singles and doubles ground state energy J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-13 Andreas Erbs Hillers-Bendtsen, Frank Jensen, Kurt V. Mikkelsen, Jeppe Olsen, Poul Jørgensen
In this paper, we develop and analyze a number of perturbation series that target the coupled cluster singles and doubles (CCSD) ground state energy. We show how classical Møller–Plesset perturbation theory series can be restructured to target the CCSD energy based on a reference CCS calculation and how the corresponding cluster perturbation series differs from the classical Møller–Plesset perturbation
-
Rapid generation of massive thermodynamic datasets using frequency comb spectroscopy J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-13 Faisal Karim, Sarah K. Scholten, Christopher Perrella, Andre N. Luiten
We demonstrate massively parallel spectroscopic measurements of 12C2H2 using an optical frequency comb. This allows for the rapid and simultaneous estimation of self-broadening and self-shifting of more than 50 optical transitions between 1512 and 1538 nm. The use of a temperature-controlled sealed gas cell allows us to measure both pressure- and temperature-mediated broadening and shifting. We present
-
On-the-fly simulation of time-resolved fluorescence spectra and anisotropy J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-13 Chao Xu, Congru Lin, Jiawei Peng, Juanjuan Zhang, Shichen Lin, Feng Long Gu, Maxim F. Gelin, Zhenggang Lan
We combine on-the-fly trajectory surface hopping simulations and the doorway–window representation of nonlinear optical response functions to create an efficient protocol for the evaluation of time- and frequency-resolved fluorescence (TFRF) spectra and anisotropies of the realistic polyatomic systems. This approach gives the effective description of the proper (e.g., experimental) pulse envelopes
-
Wave packet dynamics and control in excited states of molecular nitrogen J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-12 Mizuho Fushitani, Hikaru Fujise, Akiyoshi Hishikawa, Daehyun You, Shu Saito, Yu Luo, Kiyoshi Ueda, Heide Ibrahim, Francois Légaré, Stephen T. Pratt, Per Eng-Johnsson, Johan Mauritsson, Anna Olofsson, Jasper Peschel, Emma R. Simpson, Paolo Antonio Carpeggiani, Dominik Ertel, Praveen Kumar Maroju, Matteo Moioli, Giuseppe Sansone, Ronak Shah, Tamás Csizmadia, Mathieu Dumergue, Harshitha Nandiga Gopalakrishna
Wave packet interferometry with vacuum ultraviolet light has been used to probe a complex region of the electronic spectrum of molecular nitrogen, N2. Wave packets of Rydberg and valence states were excited by using double pulses of vacuum ultraviolet (VUV), free-electron-laser (FEL) light. These wave packets were composed of contributions from multiple electronic states with a moderate principal quantum
-
Phase separation in the presence of fractal aggregates J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-12 Supriyo Ghosh, Jack F. Douglas
Liquid–liquid phase separation in diverse manufacturing and biological contexts often occurs in the presence of aggregated particles or complex-shaped structures that do not actively participate in the phase separation process, but these “background” structures can serve to direct the macroscale phase separation morphology by their local symmetry-breaking presence. We perform Cahn–Hilliard phase-field
-
Structure of liquid–vapor interfaces: Perspectives from liquid state theory, large-scale simulations, and potential grazing-incidence x-ray diffraction J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-12 F. Höfling, S. Dietrich
Grazing-incidence x-ray diffraction (GIXRD) is a scattering technique that allows one to characterize the structure of fluid interfaces down to the molecular scale, including the measurement of surface tension and interface roughness. However, the corresponding standard data analysis at nonzero wave numbers has been criticized as to be inconclusive because the scattering intensity is polluted by the
-
Pseudo-marginal approximation to the free energy in a micro–macro Markov chain Monte Carlo method J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Hannes Vandecasteele, Giovanni Samaey
We introduce a generalized micro–macro Markov chain Monte Carlo (mM-MCMC) method with pseudo-marginal approximation to the free energy that is able to accelerate sampling of the microscopic Gibbs distributions when there is a time-scale separation between the macroscopic dynamics of a reaction coordinate and the remaining microscopic degrees of freedom. The mM-MCMC method attains this efficiency by
-
Situating the phosphonated calixarene–cytochrome C association by molecular dynamics simulations J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Alessio Bartocci, Elise Dumont
Protein–calixarenes binding plays an increasingly central role in many applications, spanning from molecular recognition to drug delivery strategies and protein inhibition. These ligands obey a specific bio-supramolecular chemistry, which can be revealed by computational approaches, such as molecular dynamics simulations. In this paper, we rely on all-atom, explicit-solvent molecular dynamics simulations
-
Excitation energy transfer and vibronic relaxation through light-harvesting dendrimer building blocks: A nonadiabatic perspective J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Joachim Galiana, Benjamin Lasorne
The light-harvesting excitonic properties of poly(phenylene ethynylene) (PPE) extended dendrimers (tree-like π-conjugated macromolecules) involve a directional cascade of local excitation energy transfer (EET) processes occurring from the “leaves” (shortest branches) to the “trunk” (longest branch), which can be viewed from a vibronic perspective as a sequence of internal conversions occurring among
-
Prediction of water anomalous properties by introducing the two-state theory in SAFT J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Nefeli Novak, Xiaodong Liang, Georgios M. Kontogeorgis
Water is one of the most abundant substances on earth, but it is still not entirely understood. It shows unusual behavior, and its properties present characteristic extrema unlike any other fluid. This unusual behavior has been linked to the two-state theory of water, which proposes that water forms different clusters, one with a high density and one with a low density, which may even form two distinct
-
Quantum criticality in chains of planar rotors with dipolar interactions J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Tobias Serwatka, Pierre-Nicholas Roy
In this work, we perform a density matrix renormalization group study of chains of planar rotors interacting via dipolar interactions. By exploring the ground state from weakly to strongly interacting rotors, we find the occurrence of a quantum phase transition between a disordered and a dipole-ordered quantum state. We show that the nature of the ordered state changes from ferroelectric to antiferroelectric
-
Assessing molecular doping efficiency in organic semiconductors with reactive Monte Carlo J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Archana Verma, Nicholas E. Jackson
The addition of molecular dopants into organic semiconductors (OSCs) is a ubiquitous augmentation strategy to enhance the electrical conductivity of OSCs. Although the importance of optimizing OSC–dopant interactions is well-recognized, chemically generalizable structure–function relationships are difficult to extract due to the sensitivity and dependence of doping efficiency on chemistry, processing
-
An entropic theory of homogeneous ice nucleation in non-ionic aqueous solutions J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Matthew J. Powell-Palm, Hunter Smith, Mir Muhammad Fahad
The nucleation of ice from aqueous solutions is a process essential to myriad environmental and industrial processes, but the physical factors affecting the capacity of different solutes to depress the homogeneous nucleation temperature of ice are yet poorly understood. In this work, we demonstrate that for many binary aqueous solutions of non-ionic solutes, this depression is dominated by the entropy
-
Activation volume and quantum tunneling in the hydrogen transfer reaction between methyl radical and methane: A first computational study J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Roberto Cammi, Bo Chen
We present a theory of the effect of quantum tunneling on the basic parameter that characterizes the effect of pressure on the rate constant of chemical reactions in a dense phase, the activation volume. This theory results in combining, on the one hand, the extreme pressure polarizable continuum model, a quantum chemical method to describe the effect of pressure on the reaction energy profile in a
-
Translational eigenstates of He@C60 from four-dimensional ab initio potential energy surfaces interpolated using Gaussian process regression J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 K. Panchagnula, D. Graf, F. E. A. Albertani, A. J. W. Thom
We investigate the endofullerene system 3He@C60 with a four-dimensional potential energy surface (PES) to include the three He translational degrees of freedom and C60 cage radius. We compare second order Møller–Plesset perturbation theory (MP2), spin component scaled-MP2, scaled opposite spin-MP2, random phase approximation (RPA)@Perdew, Burke, and Ernzerhof (PBE), and corrected Hartree–Fock-RPA to
-
The temperature of maximum density for aqueous solutions J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Jacobo Troncoso, Diego González-Salgado
Experimental and theoretical advances for understanding the temperature of maximum density (TMD) of aqueous solutions are outlined. The main equations that relate the TMD behavior to key thermodynamic properties are stated. The experimental TMD data are classified as a function of the nature of the solute (inorganic electrolytes, non-electrolytes, organic salts and ionic liquids, and amino acids and
-
Photo-activated dynamic isomerization induced large density changes in liquid crystal polymers: A molecular dynamics study J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Akhil Reddy Peeketi, Edwin Joseph, Narasimhan Swaminathan, Ratna Kumar Annabattula
We use molecular dynamics simulations to unravel the physics underpinning the light-induced density changes caused by the dynamic trans–cis–trans isomerization cycles of azo-mesogens embedded in a liquid crystal polymer network, an intriguing experimental observation reported in the literature. We employ two approaches, cyclic and probabilistic switching of isomers, to simulate dynamic isomerization
-
Simple model for synchronization of two Belousov–Zhabotinsky gels interacting mechanically J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Taro Sukegawa, Yuhei Yamada, Shingo Maeda
A Belousov–Zhabotinsky (BZ) gel is a unique biomimetic system that undergoes autonomous volume oscillations induced by the redox oscillation of the BZ reaction. In a previous study, researchers reported that the oscillations of two BZ gels coupled by compression were synchronized by a mechanical interaction. They mathematically explained the synchronization behavior using a phase oscillator model.
-
Unraveling motion in proteins by combining NMR relaxometry and molecular dynamics simulations: A case study on ubiquitin J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Candide Champion, Marc Lehner, Albert A. Smith, Fabien Ferrage, Nicolas Bolik-Coulon, Sereina Riniker
Nuclear magnetic resonance (NMR) relaxation experiments shine light onto the dynamics of molecular systems in the picosecond to millisecond timescales. As these methods cannot provide an atomically resolved view of the motion of atoms, functional groups, or domains giving rise to such signals, relaxation techniques have been combined with molecular dynamics (MD) simulations to obtain mechanistic descriptions
-
Theoretical and experimental OD-stretch vibrational spectroscopy of heavy water J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-11 Tetsuyuki Takayama, Takuhiro Otosu, Shoichi Yamaguchi
In view of the current situation in which the OD-stretch vibrational spectra have been scarcely computed with non-polarizable rigid D2O models, we investigate the IR and Raman spectra of D2O by using a newly-reported model TIP4P/2005-HW. From the comparison between the calculations and experimental data, we find the excellent performance of TIP4P/2005-HW for vibrational spectroscopy of D2O in the same
-
Reducing contact resistance of MoS2-based field effect transistors through uniform interlayer insertion via atomic layer deposition J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Whang Je Woo, Seunggi Seo, Hwi Yoon, Sanghun Lee, Donghyun Kim, Seonyeong Park, Youngjun Kim, Inkyu Sohn, JuSang Park, Seung-min Chung, Hyungjun Kim
Molybdenum disulfide (MoS2), a semiconducting two-dimensional layered transition metal dichalcogenide (2D TMDC), with attractive properties enables the opening of a new electronics era beyond Si. However, the notoriously high contact resistance (RC) regardless of the electrode metal has been a major challenge in the practical applications of MoS2-based electronics. Moreover, it is difficult to lower
-
Application of density matrix Wigner transforms for ultrafast macromolecular and chemical x-ray crystallography J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Samuel Perrett, Viktoria Chatrchyan, Tiago Buckup, Jasper J. van Thor
Time-Resolved Serial Femtosecond Crystallography (TR-SFX) conducted at X-ray Free Electron Lasers (XFELs) has become a powerful tool for capturing macromolecular structural movies of light-initiated processes. As the capabilities of XFELs advance, we anticipate that a new range of coherent control and structural Raman measurements will become achievable. Shorter optical and x-ray pulse durations and
-
Structural effects of water clusters on viscosity at high shear rates J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Yitian Gao, Jian Wu, Yixuan Feng, Jiale Han, Hongwei Fang
In this study, we use molecular dynamics simulations of liquid water to investigate how shear thinning affects the viscosity of liquid water by structural changes of the hydrogen bond network. The effect of shear on viscosity can be divided into two parts: shear-induced destruction of the hydrogen bond network and the influence of the water structure on shear viscosity. First, strong shear destroys
-
Pathway selectivity in time-resolved spectroscopy using two-photon coincidence counting with quantum entangled photons J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Yuta Fujihashi, Akihito Ishizaki, Ryosuke Shimizu
Ultrafast optical spectroscopy is a powerful technique for studying the dynamic processes of molecular systems in condensed phases. However, in molecular systems containing many dye molecules, the spectra can become crowded and difficult to interpret owing to the presence of multiple nonlinear optical contributions. In this work, we theoretically propose time-resolved spectroscopy based on the coincidence
-
Influence of repulsion on entropy scaling and density scaling of monatomic fluids J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Denis Saric, Ian H. Bell, Gabriela Guevara-Carrion, Jadran Vrabec
Entropy scaling is applied to the shear viscosity, self-diffusion coefficient, and thermal conductivity of simple monatomic fluids. An extensive molecular dynamics simulation series is performed to obtain these transport properties and the residual entropy of three potential model classes with variable repulsive exponents: n, 6 Mie (n = 9, 12, 15, and 18), Buckingham’s exponential-six (α = 12, 14,
-
Quantum tomography of molecules using ultrafast electron diffraction J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Jiayang Jiang, Ming Zhang, Aosheng Gu, R. J. Dwayne Miller, Zheng Li
We propose a quantum tomography (QT) approach to retrieve the temporally evolving reduced density matrix in electronic state basis, where the populations and coherence between the ground state and excited state are reconstructed from the ultrafast electron diffraction signal. In order to showcase the capability of the proposed QT approach, we simulate the nuclear wavepacket dynamics and ultrafast electron
-
Free-energy landscape and spinodals for the liquid–liquid transition of the TIP4P/2005 and TIP4P/Ice models of water J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Francesco Sciortino, Thomas E. Gartner, Pablo G. Debenedetti
Continued increases in computational power now make it possible to evaluate the free-energy landscape associated with the first-order liquid–liquid transition in realistic models of water for which an accurate estimate of the liquid–liquid critical point exists, and to explore its change with pressure near the coexistence line. We report the results of 50 μs-long NPT umbrella sampling simulations for
-
Rationale for the extrapolation procedure in selected configuration interaction J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Hugh G. A. Burton, Pierre-François Loos
Selected configuration interaction (SCI) methods have emerged as state-of-the-art methodologies for achieving high accuracy and generating benchmark reference data for ground and excited states in small molecular systems. However, their precision relies heavily on extrapolation procedures to produce a final estimate of the exact result. Using the structure of the exact electronic energy landscape,
-
Production of positronium chloride: A study of the charge exchange reaction between Ps and Cl− J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 K. Lévêque-Simon, A. Camper, R. Taïeb, J. Caillat, C. Lévêque, E. Giner
We present cross sections for the formation of positronium chloride (PsCl) in its ground state from the charge exchange between positronium (Ps) and chloride (Cl−) in the range of 10 meV–100 eV Ps energy. We have used theoretical models based on the first Born approximation in its three-body formulation. We simulated the collisions between Ps and Cl− using ab initio binding energies and positronic
-
Molecular factors determining brightness in fluorescence-encoded infrared vibrational spectroscopy J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-08 Abhirup Guha, Lukas Whaley-Mayda, Seung Yeon Lee, Andrei Tokmakoff
Fluorescence-encoded infrared (FEIR) spectroscopy is a recently developed technique for solution-phase vibrational spectroscopy with detection sensitivity at the single-molecule level. While its spectroscopic information content and important criteria for its practical experimental optimization have been identified, a general understanding of the electronic and nuclear properties required for highly
-
GPAW: An open Python package for electronic structure calculations J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-07 Jens Jørgen Mortensen, Ask Hjorth Larsen, Mikael Kuisma, Aleksei V. Ivanov, Alireza Taghizadeh, Andrew Peterson, Anubhab Haldar, Asmus Ougaard Dohn, Christian Schäfer, Elvar Örn Jónsson, Eric D. Hermes, Fredrik Andreas Nilsson, Georg Kastlunger, Gianluca Levi, Hannes Jónsson, Hannu Häkkinen, Jakub Fojt, Jiban Kangsabanik, Joachim Sødequist, Jouko Lehtomäki, Julian Heske, Jussi Enkovaara, Kirsten Trøstrup
We review the GPAW open-source Python package for electronic structure calculations. GPAW is based on the projector-augmented wave method and can solve the self-consistent density functional theory (DFT) equations using three different wave-function representations, namely real-space grids, plane waves, and numerical atomic orbitals. The three representations are complementary and mutually independent
-
Vibrational signatures of dynamic excess proton storage between primary amine and carboxylic acid groups J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-07 F. Gámez, J. R. Avilés-Moreno, J. Martens, G. Berden, J. Oomens, B. Martínez-Haya
Ammonium and carboxylic moieties play a central role in proton-mediated processes of molecular recognition, charge transfer or chemical change in (bio)materials. Whereas both chemical groups constitute acid–base pairs in organic salt-bridge structures, they may as well host excess protons in acidic environments. The binding of excess protons often precedes proton transfer reactions and it is therefore
-
A reactive molecular dynamics model for uranium/hydrogen containing systems J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-07 Artem Soshnikov, Rebecca Lindsey, Ambarish Kulkarni, Nir Goldman
Uranium-based materials are valuable assets in the energy, medical, and military industries. However, understanding their sensitivity to hydrogen embrittlement is particularly challenging due to the toxicity of uranium and the computationally expensive nature of quantum-based methods generally required to study such processes. In this regard, we have developed a Chebyshev Interaction Model for Efficient
-
Assessing the reinforced molecular/mechanical behaviors of GOs@Mo-MOFs films deposited via electrophoresis onto microdevices: Experimental and theoretical perspectives J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-07 Zhiyong Cao, Chuang Gong, Qiannan Xue, Hairen Wang, June Qu, Junsong Jin, Lushi Sun, Xinyun Wang
One of the primary hurdles in microdevice fabrication lies in ascertaining the most impactful tactics for adapting metal surfaces. Through a one-pot tackle and distinct mechanochemical reactions evoked by 15 min aqueous wet sand-milling (SM-15), we successfully grafted Mo-based metal–organic frameworks (Mo-MOFs) onto graphene oxides (GOs). Following this, a convenient and readily scalable methodology
-
Effectiveness of inhibitors to prevent asphaltene aggregation: Insights from atomistic and molecular simulations J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-07 Anoop Kishore Vatti, Srikanth Divi, Poulumi Dey
The technological landscape for industrial processes handling asphaltene is evolving at a rapid pace due to the increase in the extraction of heavy crude oil. The main underlying challenges in this regard are the flow assurance, the recovery of the spent solvent, and the sophisticated extractor setup required to develop the process to an industrial scale. The number of studies focused on the handling
-
Revealing the reason for enhanced CZTSSe device performance after Ag heavily doped into absorber surface J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-06 Siyu Wang, Zhan Shen, Yue Liu, Yi Zhang
Ag-doping treatment is a popular method for enhancing the performance of kesterite-structured Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Among the various methods, incorporating a high concentration of Ag+ into an absorber surface has proven to be particularly effective. However, the exact mechanisms behind this improvement are still unclear. This study aims to investigate the key factors that improve device
-
Viscoelastic relaxation and topological fluctuations in glass-forming liquids J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-06 Chi-Huan Tung, Shou-Yi Chang, Sidney Yip, Yangyang Wang, Jan-Michael Y. Carrillo, Bobby G. Sumpter, Yuya Shinohara, Changwoo Do, Wei-Ren Chen
A method for characterizing the topological fluctuations in liquids is proposed. This approach exploits the concept of the weighted gyration tensor of a collection of particles and permits the definition of a local configurational unit (LCU). The first principal axis of the gyration tensor serves as the director of the LCU, which can be tracked and analyzed by molecular dynamics simulations. Analysis
-
Fragmentation of water clusters formed in helium nanodroplets by charge transfer and Penning ionization J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-06 S. De, A. R. Abid, J. D. Asmussen, L. Ben Ltaief, K. Sishodia, A. Ulmer, H. B. Pedersen, S. R. Krishnan, M. Mudrich
Helium nanodroplets (“HNDs”) are widely used for forming tailor-made clusters and molecular complexes in a cold, transparent, and weakly interacting matrix. The characterization of embedded species by mass spectrometry is often complicated by the fragmentation and trapping of ions in the HNDs. Here, we systematically study fragment ion mass spectra of HND-aggregated water and oxygen clusters following
-
Tailoring photocatalytic water splitting activity of boron–thiophene polymer through pore size engineering J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-06 Preeti Bhauriyal, Thomas Heine
Taking into account the electron-rich and visible light response of thiophene, first-principles calculations have been carried out to explore the photocatalytic activity of donor–acceptor polymers incorporating thiophene and boron. Honeycomb-kagome boron–thiophene (BTP) polymers with varying numbers of thiophene units and fixed B center atoms are direct bandgap semiconductors with tunable bandgaps
-
Predissociation dynamics of D2 revealed by variation in fragment anisotropy parameters along the Fano profile J. Chem. Phys. (IF 4.4) Pub Date : 2024-03-06 Peng Wang, Shiyan Gong, Yixuan Li, Yuxiang Mo
We conducted a study on the variations of the fragment anisotropy parameters (β) along the Fano profiles for the predissociation of the D2 molecule. These variations, known as β profiles, were measured for the D(2l) fragments from the predissociation of the 4pπD′Πu1υ′=1 and 4pσB″Σu+1υ′=2 states. The measured β profiles show significant asymmetry and broader linewidths compared to the corresponding