Article
Spectroscopy
Andrey Morozov, Tatiana Nazdracheva, Andrei Kochur, Victor Yavna
Summary: This study aims to investigate the influence of solvate shells interaction on the profiles of infrared spectra of sodium chloride solutions. Experimental measurements of infrared spectra were conducted on distilled water and sodium chloride solutions at limit and half-limit concentrations. Theoretical calculations using the DFT approach with the XLYP exchange-correlation potential were employed to compute the infrared spectra profiles for clusters containing 9 water molecules and one NaCl molecule. The results showed that the infrared spectrum is mainly influenced by the interaction of Na+ and Cl- solvation shells, each consisting of 4 water molecules, with the 9th water molecule providing bonding between the solvated ions.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Materials Science, Multidisciplinary
Sul Ki Park, Kang Ho Shin, Puritut Nakhanivej, Harpalsinh H. Rana, Ho Seok Park
Summary: The reversible redox charge transfer kinetics and reversibility of VO2(B) nanorod electrodes in both aqueous and organic electrolytes for Na-ion storage system were investigated. It was found that the VO2(B) nanorods demonstrated higher specific and rate capacitances in aqueous electrolytes than in organic electrolytes. Moreover, the temperature-dependent impedance measurements indicated a more facile interfacial charge transfer of Na ions into VO2(B) nanorods in aqueous electrolytes.
ENERGY & ENVIRONMENTAL MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Guofa Zheng, Xiaolei Lu, Qiang Li, Peng Du, Lina Zhang, Xin Cheng
Summary: The effect of Na2O doping on the formation and hydration properties of ye'elimite containing Fe (C(4)A(2.8)F(0.2)$) was investigated in this study. The results showed that Na2O-doped promoted the phase transition of ye'elimite from orthogonal to cubic phase, and the crystal structure of C(4)A(2.8)F(0.2)$ tended to be stable. However, when the amount of Na2O exceeded a certain threshold, the formation of C(4)A(2.8)F(0.2)$ was hindered. In addition, adding Na2O accelerated the grain growth of C(4)A(2.8)F(0.2)$ and changed its morphology. Moreover, Na2O doping accelerated the hydration process and shortened the induction period of C(4)A(2.8)F(0.2)$.
Article
Chemistry, Physical
Hassan Monhemi, Hai Nam Hoang, Daron M. Standley, Tomoko Matsuda, Mohammad Reza Housaindokht
Summary: We present a new water-dependent mechanism for the protein stabilizing osmolyte TMAO. Traditional theories fail to explain TMAO's behavior, but recent data suggests direct interactions between TMAO and proteins. Our study shows that altering the water environment and protein surface characteristics can address the weaknesses of existing theories about the mechanism of TMAO.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Denys Biriukov, Hsiu-Wen Wang, Nikhil Rampal, Carmelo Tempra, Patrik Kula, Joerg C. Neuefeind, Andrew G. Stack, Milan Predota
Summary: This study characterizes a concentrated CaCl2 solution and investigates ion pairing using neutron diffraction, chloride isotopic substitution, and molecular dynamics simulations. The dominant type of ion pairing is found to be solvent-shared, while contact ion pairing is insignificant even at high concentrations. Results also show that existing molecular dynamics models accurately reproduce most of the experimental data, but they tend to overestimate the extent of ion pairing.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Inorganic & Nuclear
Nina Huittinen, Isabelle Jessat, Florent Real, Valerie Vallet, Sebastian Starke, Manuel Eibl, Norbert Jordan
Summary: In this study, the coordination chemistry of Cm(III) with aqueous phosphates was investigated using laser-induced luminescence spectroscopy and ab initio simulations. The formation of Cm(H2PO4)(2)(+) was confirmed for the first time, along with deriving complexation constants and thermodynamic parameters. The results showed a temperature-dependent coordination change for the Cm(III)-phosphate complexes, with different coordination numbers observed at different temperatures.
INORGANIC CHEMISTRY
(2021)
Article
Construction & Building Technology
Xinming Wang, Jing Zhong
Summary: When graphene oxide (GO) is mixed with cement, it can exist in different dispersion states, including well-dispersed, grain-adsorbed, and self-agglomerated. The effects of GO in grain-adsorbed and self-agglomerated states on tricalcium silicate (C3S) hydration were investigated in this study. The results showed that GO in grain-adsorbed state limits the accessibility of reactant for hydration at early age, while GO in self-agglomerated state absorbs calcium ions from the pore solution, leading to inhibition of hydration. These findings enhance the understanding of GO in cement hydration and its potential use in cementitious materials.
CEMENT AND CONCRETE RESEARCH
(2023)
Article
Chemistry, Physical
Wanlin Chen, Stephanie E. Sanders, Burak Ozdamar, Dorian Louaas, Flavio Siro Brigiano, Simone Pezzotti, Poul B. Petersen, Marie-Pierre Gaigeot
Summary: In this study, density functional theory-based MD simulations and SFG spectroscopy were used to investigate the response of water molecules on tunable hydrophilic interfaces. A microscopic metric was introduced to track the transition between hydrophobic and hydrophilic interfaces. This metric builds a bridge between molecular descriptors of hydrophilicity/hydrophobicity and spectroscopically measured quantities, providing a method to interpret experimental SFG signals quantitatively or qualitatively.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Wanlin Chen, Stephanie E. Sanders, Burak Oezdamar, Dorian Louaas, Flavio Siro Brigiano, Simone Pezzotti, Poul B. Petersen, Marie-Pierre Gaigeot
Summary: Studying the microscopic hydrophilicity and hydrophobicity at heterogeneous aqueous interfaces is crucial for understanding the physico/chemical properties. A combination of DFT-MD simulations and SFG spectroscopy is used to explore the response of interfacial water in contact with tunable hydrophilic self-assembled monolayers. A microscopic metric is introduced to track the transition from hydrophobic to hydrophilic interfaces, bridging molecular descriptors and spectroscopic measurements for interpretation of experimental SFG signals.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
W. Q. Zhang, T. Yamaguchi, C. H. Fang, K. Yoshida, Y. Q. Zhou, F. Y. Zhu, S. Machida, T. Hattori, W. Li
Summary: The liquid structure of an aqueous 3 m RbCl solution in D2O under different temperature and pressure conditions was studied using neutron diffraction. The results showed that the structure parameters were temperature and pressure-dependent, and the hydration layer of ions and the hydrogen-bonded water structure changed under high temperature and pressure conditions.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Multidisciplinary
Shane W. Devlin, Sasawat Jamnuch, Qiang Xu, Amanda A. Chen, Jin Qian, Tod A. Pascal, Richard J. Saykally
Summary: This study finds that doubly charged carbonate anions exhibit a stronger surface affinity than singly charged bicarbonate anions to the air-water interface. The findings are supported by computer simulations and experimental results, and have implications for ion adsorption chemistry as well as practical processes such as ocean acidification, sea-spray aerosol chemistry, and mammalian respiration physiology.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Huibo Yan, Songmei Li, Hongfei Xu, Hao Chen, Shubin Yang, Bin Li
Summary: This study proposes a hydrated salt electrolyte that suppresses the presence of free water and elevates the decomposition voltage in zinc metal batteries. The electrolyte effectively inhibits parasitic reactions on the zinc anode and cathode, resulting in stable discharge capacity and high energy density.
ADVANCED ENERGY MATERIALS
(2022)
Article
Chemistry, Physical
Sophie Baker, Joshua Pagotto, Timothy T. Duignan, Alister J. Page
Summary: Neural network potentials have proven to be an efficient tool for accelerating ab initio molecular dynamics simulations. This study explores the use of existing DFTB molecular dynamics data to train graph neural network potentials and accurately reproduce solvation structures in NaCl solutions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Iwona Plowas-Korus, Richard Buchner
Summary: An extensive dielectric relaxation study was conducted on aqueous xylitol solutions, revealing weak hydration of xylitol and formation of aggregates due to the lack of separating bulk water. The aggregation of xylitol molecules is driven by rising temperature and results in the formation of larger fluctuating entities.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Physical
Boyuan Wang, Weixu Zhang, Xiaochao Jin, Guanghui Su
Summary: The diffusion model accounting for hydration force accurately predicts the swelling of Na-montmorillonite in water. The layer-to-layer distance increases due to diffusion motion controlled by various forces, including hydration, van der Waals, repulsive electrostatic double-layer, and repulsive entropic forces. The model defines diffusivity for a wide concentration range of montmorillonite and explains the dominance of different forces in crystalline, osmotic, and Brownian swelling.
APPLIED CLAY SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Trent R. Graham, Jaehun Chun, Gregory K. Schenter, Xin Zhang, Sue B. Clark, Carolyn I. Pearce, Kevin M. Rosso
Summary: This study utilized Al-27 NMR spectroscopy to investigate the translational diffusion of epsilon-Al-13 clusters, demonstrating that symmetric Al environments can be probed using this method.
MAGNETIC RESONANCE IN CHEMISTRY
(2022)
Article
Chemistry, Physical
Kevin Carter-Fenk, Britta A. Johnson, John M. Herbert, Gregory K. Schenter, Christopher J. Mundy
Summary: A new simulation method is used to directly study the generation of hydrated electrons from the charge-transfer-to-solvent state. The simulations reveal a two-step process involving ionization and solute reorganization leading to the equilibrated ground state of the solvated electron. This methodology has implications for photochemical electron transfer processes in solution, with potential application in photocatalysis and energy transfer.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Adrian-Iulian Borhan, Daniel-Dumitru Herea, Marius-Adrian Husanu, Dana Georgeta Popescu, Camelia Nicoleta Borca, Thomas Huthwelker, Georgiana Bulai, Ioana Radu, Alin Constantin Dirtu, Daniela Dirtu, Carmen Mita, George Stoian, Gabriel Ababei, Nicoleta Lupu, Aurel Pui, Daniel Gherca
Summary: Efforts have been made to develop efficient heterogeneous nano-particle systems for solar light-driven photodegradation. In this study, a chemically-engineered multi-component system was formulated as a recyclable, nontoxic, active and inexpensive catalyst for the degradation of tetracycline antibiotic. The nanoflower-like heteronanostructure showed enhanced photodegradation capability by using FeOOH nanografting of Al-based SrTiO3 perovskite material.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Adrian Iulian Borhan, Adrian Iulian Ghemes, Marius-Adrian Husanu, Dana-Georgeta Popescu, Camelia Nicoleta Borca, Thomas Huthwelker, Ioana Radu, Alin Constantin Dirtu, Daniela Dirtu, Georgiana Bulai, Nicoleta Lupu, Mircea Nicolae Palamaru, Alexandra-Raluca Iordan, Daniel Gherca
Summary: We reported the development of a high-operative photocatalyst with improved charge trapping characteristics for enhanced solar light-driven photocatalytic degradation. The synthesized samples were investigated using various characterization techniques to understand their structural, morphological, optical, and electronic properties. The fibrous photocatalyst achieved a high-to-total degradation of tetracycline antibiotic under visible light irradiation, demonstrating its potential for efficient pollutant removal.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Inorganic & Nuclear
Fabiana Machado Ferreira de Araujo, Daniel Duarte-Ruiz, Holger-Dietrich Sassnick, Marie C. Gentzmann, Thomas Huthwelker, Caterina Cocchi
Summary: In this study, the stability and electronic structure of six ScF3 polymorphs were evaluated using first-principles calculations and X-ray spectroscopy. The results showed the transition between low- and high-temperature phases mainly consists of a rigid rotation of the lattice. Analysis of the computational results provided insights into the electronic origin of the absorption maxima and the excitonic effects in the spectra. Comparison with experimental measurements confirmed the presence of high- and low-temperature polymorphs, but also suggested the presence of defects or residual traces of metastable phases in the sample.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Benjamin I. Poulter, Elisa Biasin, Stanislaw H. Nowak, Thomas Kroll, Roberto Alonso-Mori, Robert W. Schoenlein, Niranjan Govind, Dimosthenis Sokaras, Munira Khalil
Summary: Using L-3-edge 2p3d resonant inelastic X-ray scattering (RIXS), we investigated the electronic structure and dynamics of different solution phase Ru complexes, providing insights into the 4d and 3d orbitals and their interactions. This technique allows for direct measurement of 3d spin orbit coupling and splitting of orbitals. The study examined three model Ru complexes and demonstrated the higher spectral information provided by 2p3d RIXS compared to L-3 X-ray absorption near edge structure (XANES). The direct measurement of spin-orbit splitting was carried out for the studied complexes.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Trent R. Graham, Maxime Pouvreau, Rafal Gorniak, Hsiu-Wen Wang, Emily T. Nienhuis, Quin R. S. Miller, Jian Liu, Micah P. Prange, Gregory K. Schenter, Carolyn I. Pearce, Kevin M. Rosso, Aurora E. Clark
Summary: The thermal transformation of crystalline sodium aluminum salt hydrate was studied in this research. It was found that the change in aluminum coordination during melting occurs within a highly disordered quasi-two-dimensional phase at the solid-solution interface. This study provides insights into the mechanisms controlling aluminum phase transformations in highly alkaline solutions.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Physical
Shashank G. G. Mehendale, Bo Peng, Niranjan Govind, Yuri Alexeev
Summary: The unitary coupled-cluster (UCC) ansatz is a commonly used chemically inspired approach in variational quantum computing. However, the standard UCC ansatz has an unfavorable scaling of the number of parameters with respect to the system size, which hinders its practical use on near-term quantum devices. This paper explores the parameter redundancy in the preparation of the unitary coupled-cluster singles and doubles (UCCSD) ansatz and proposes techniques to reduce the number of parameters and improve convergence time. Experimental results on small molecules demonstrate significant cost reduction and faster convergence compared to conventional UCCSD-VQE simulations. The potential application of machine learning techniques in further exploring parameter redundancy is also discussed as a future direction for research.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Soumen Ghosh, Shaul Mukamel, Niranjan Govind
Summary: This letter investigates the predictive ability of multiconfiguration pair-density functional theory (MC-PDFT) for X-ray absorption spectra (XAS) by calculating the metal K pre‑edge features of aquated 3d transition metal ions in common oxidation states. It is found that MC-PDFT provides quantitatively accurate results for all excited states with significantly lower computational cost compared to restricted active-space second-order perturbation theory (RASPT2) and time-dependent density functional theory (TDDFT).
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Fernanda Brandalise Nunes, Nicolo Comini, J. Trey Diulus, Thomas Huthwelker, Marcella Iannuzzi, Jurg Osterwalder, Zbynek Novotny
Summary: Carboxylic acids can bind to titanium dioxide (TiO2) and form surface superstructures, but exposure to water leads to loss of the ordered surface structure. Research shows that a dynamic equilibrium exists between adsorbed formic acid and water molecules on the formate-covered surface. Understanding and controlling this equilibrium process is crucial for enhancing the self-cleaning properties of TiO2.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Daniel Mejia-Rodriguez, Edoardo Apra, Jochen Autschbach, Nicholas P. Bauman, Eric J. Bylaska, Niranjan Govind, Jeff R. Hammond, Karol Kowalski, Alexander Kunitsa, Ajay Panyala, Bo Peng, John J. Rehr, Huajing Song, Sergei Tretiak, Marat Valiev, Fernando D. Vila
Summary: This paper provides an overview of the recent developments in the NWChem computational chemistry suite, including the functionality in the current stable release (NWChem 7.2.0) and the ongoing developments in the master development branch. It highlights the interfaces to quantum computing simulators, external libraries, the NWChem github repository, and containerization of NWChem executable images.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Rosa Di Felice, Maricris L. Mayes, Ryan M. Richard, David B. Williams-Young, Garnet Kin-Lic Chan, Wibe A. de Jong, Niranjan Govind, Martin Head-Gordon, Matthew R. Hermes, Karol Kowalski, Xiaosong Li, Hans Lischka, Karl T. Mueller, Erdal Mutlu, Anders M. N. Niklasson, Mark R. Pederson, Bo Peng, Ron Shepard, Edward F. Valeev, Mark van Schilfgaarde, Bess Vlaisavljevich, Theresa L. Windus, Sotiris S. Xantheas, Xing Zhang, Paul M. Zimmerman
Summary: The sustainability and interoperability of computational chemistry software development are pressing issues. A flexible forward strategy is needed to take full advantage of existing and forthcoming computational resources and provide unique computational tools for next-generation science problems and scientific discoveries.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Multidisciplinary
Victor M. Freixas, Jeïreïmy R. Rouxel, Yeonsig Nam, Sergei Tretiak, Niranjan Govind, Shaul Mukamel
Summary: Chirality is a fundamental property of molecules that has significant implications in biophysics and drug design. Optical circular dichroism (OCD) and X-ray circular dichroism (XCD) are two important spectroscopic probes that can detect global and local molecular chirality, respectively.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Diwash Dhakal, Darren M. M. Driscoll, Niranjan Govind, Andrew G. G. Stack, Nikhil Rampal, Gregory Schenter, Christopher J. J. Mundy, Timothy T. T. Fister, John L. L. Fulton, Mahalingam Balasubramanian, Gerald T. T. Seidler
Summary: The study focuses on the emergence of cation-anion species in aqueous solutions and their impact on the physical properties of high solute concentration systems. Zn halide solutions are used as a model system to investigate the halide coordination number and changing coordination geometry. The results provide new insights into the physical chemistry of concentrated electrolytes and open up new research directions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Fernanda Brandalise Nunes, Nicolo Comini, Trey Diulus, Thomas Huthwelker, Marcella Iannuzzi, Jurg Osterwalder, Zbynek Novotny
Summary: Carboxylic acids dissociatively bind to titanium dioxide (TiO2), forming surface superstructures detected by low-energy electron diffraction. However, exposure to water disrupts the ordered surface structure. Investigation of the formate-covered surface using diffraction, spectroscopy, and ab initio simulations reveals a dynamic equilibrium between adsorbed formic acid and water molecules. This equilibrium process is crucial for understanding the self-cleaning properties of TiO2, as the formic acid monolayer contributes to the surface's amphiphilic character.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)