Article
Chemistry, Physical
Jingyi L. Chen, J. Ilja Siepmann
Summary: This study investigates the vapor-liquid equilibrium of group V hydrides using Monte Carlo simulations, finding discrepancies in critical temperature predictions for PH3 with different exchange-correlation functionals. System size has minimal effects on the VLCC and liquid structure of PH3, while critical temperatures for AsH3 and SbH3 are slightly higher than literature values.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Physical
Wenrui Li, Jun Li, Hongbo Ning, Yanlei Shang, Sheng-Nian Luo
Summary: Theoretical investigation of the H-abstraction reaction kinetics of methyl acrylate (MA) with various radicals was conducted, with calculations of reaction energies, barrier heights, and rate constants using different density functionals and transition-state theory. Comparison of different kinetic models showed similar results within the combustion temperature range but discrepancies at lower temperatures. Branching ratios were found to vary with temperature, with different radicals playing dominant roles in the low and high-temperature ranges. The updated kinetic model accurately predicted ignition delay times of MA and showed good agreement with experimental results, providing valuable insights for understanding and predicting the combustion properties of unsaturated methyl esters.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Physics, Nuclear
Wei Zhang, Wan-Li Lv, Ting-Ting Sun
Summary: The study investigates the temperature dependence of shell corrections in closed-shell nuclei using covariant density functional theory. It is found that delta E-shell exhibits non-monotonous behavior and delta F-shell and T delta S-shell can be approximated well using specific formulas. Similar temperature dependencies are observed in other closed-shell nuclei such as Sn-100 and Pb-208.
Article
Chemistry, Physical
Gang Zhang, Honggang Liu, Zhiyu He, Baojun Chen
Summary: In this study, a nonspin-Hamiltonian method combining density functional theory (DFT)-based geometric optimization is used to accurately obtain the hyperfine structure and clock transitions of rare-earth ion-doped crystals. The results demonstrate that this approach can predict the hyperfine structure and clock transitions of these crystals accurately, which is important for designing and searching for quantum memory materials with longer coherence time.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Inorganic & Nuclear
Dipak Prasad, Nilanjan Mitra
Summary: This study demonstrates the catalytic activity of hydrogen bonds in the silicate oligomerization reaction pathway and shows that the presence of hydrogen bonding enhances the energetic favorability of the anionic-I mechanism. It also reveals that hydrogen bonds play a role in the Si-OH rupture process and that the strength of hydrogen bonds affects the activation barrier. Furthermore, the study suggests that similar effects can be observed in the oligomerization of silicates containing metallic ions in sol-gel chemistry and zeolite synthesis.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Janus J. Eriksen
Summary: This study presents a robust protocol for probing localized electronic structure in condensed-phase systems, with initial application in liquid water where solvent-induced shift in dipole moment is significantly reduced. The methodology allows for evaluation of convergence of bulk properties, paving the way for future research on local effects and defects in more complex phases.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Mohsen Doust Mohammadi, Nikolaos Patsalidis, Somnath Bhowmick, Vagelis A. Harmandaris, George Biskos
Summary: We investigated the intermolecular interactions between atmospheric gaseous pollutants and Ag-n and Au-n atomic clusters using density functional theory. Our results show that SO2 and NO2 exhibit a higher preference for adsorption on the clusters compared to other gas molecules. This information can be used for molecular dynamics simulations and material design.
Article
Chemistry, Physical
Arthur Hagopian, Marie-Liesse Doublet, Jean-Sebastien Filhol, Tobias Binninger
Summary: Computational studies of electrochemical interfaces based on density-functional theory are vital for energy conversion and storage research. The homogeneous background method simplifies charge calculations in DFT simulations, with an advanced version now eliminating the need for certain specifications, allowing for versatile applications. Results show excellent agreement between the advanced HBM and the Poisson-Boltzmann model for charged interfaces in high-dielectric-constant solvents.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Materials Science, Multidisciplinary
Luke J. Wirth, Christopher Woodward, Amir A. Farajian
Summary: Advances in first principles methods are used to study the atom-vacancy exchanges near a screw dislocation in fcc Ni, revealing direction-dependent free energy profiles and temperature-dependent correlation effects. The dynamic approach shows intra-cell energy profile asymmetry related to dynamic geometry rearrangements. Despite absolute values of rate constants being similar, the HTST method generally underestimates rates by a factor of 2-5, partially explaining discrepancies between theoretical works and experiments in pipe diffusion diffusivities.
Article
Chemistry, Physical
Timothy W. Marin, Ireneusz Janik, David M. Bartels, Daniel M. Chipman
Summary: The study investigates the lowest band in the charge-transfer-to-solvent ultraviolet absorption spectrum of aqueous chloride ion through experiment and computation. Interestingly, it is found that ionic strength does not have a notable effect on the spectrum up to a certain concentration, despite significant ion pairing as indicated by calculations. Experimental spectra are fitted for comparison with computations, and classical molecular dynamics simulations are utilized to produce radial distribution functions in agreement with experiment, with clear evidence of ion pairing for NaCl.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Organic
Ayan Datta, Chandralekha Hajra, Sucharita Mandal
Summary: This article explores the influence of an external electric field on the reactivity of 1,3-dienes with SO2. DFT calculations show that the chelotropic reaction becomes kinetically favorable under the influence of a moderate electric field.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Carmen Baiano, Jacopo Lupi, Vincenzo Barone, Nicola Tasinato
Summary: In this study, the isomerization of hydrogen cyanide on icy grain surfaces was investigated using a composite method (jun-Cheap) and density functional approaches. The results showed that four water molecules were involved in a proton relay mechanism, leading to a reduction in activation energy and facilitating the isomerization process.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Multidisciplinary
Yueshao Zheng, Xingxing Jiang, Xiong-Xiong Xue, Xiaolong Yao, Jiang Zeng, Ke-Qiu Chen, Enge Wang, Yexin Feng
Summary: Understanding the origin of charge-density wave (CDW) instability is crucial for manipulating novel collective electronic states. This study investigates the influence of electron correlation effects and nuclear quantum effects on the CDW ordering in layered transition metal dichalcogenides (TMDs). The results show that the quantum motion of sulfur anions significantly reduces the CDW transition temperature in NbS2, resulting in distinct CDW features compared to NbSe2.
Article
Chemistry, Inorganic & Nuclear
Xin Yang, Corey P. Burns, Michael Nippe, Michael B. Hall
Summary: Lanthanide-transition metal complexes exhibit strong Ln-TM dative bonds with a small increase in bond dissociation energy and decrease in Ln-Fe bond lengths from La to Lu. Energy decomposition analyses attribute this trend to an increase in electrostatic contribution and modest increase in orbital contribution. Natural bond orbital analysis indicates 3d(6) lone pairs in [FeCp(CO)(2)](-) fragment act as Lewis bases donating nearly 0.5 electron to mainly d character Ln virtual orbitals.
INORGANIC CHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
S. Bae, Y-G Kang, M. Khazaei, K. Ohno, Y-H Kim, M. J. Han, K. J. Chang, H. Raebiger
Summary: Transition metal compounds are challenging for ab initio calculations due to the localized nature of d electrons, leading to errors in electronic and magnetic properties. This study used density functional theory to calculate 22 carbide MXenes with different methods, revealing new ground-state structures and magnetic states. Various methods were compared to improve the reliability of theoretical studies on MXenes.
MATERIALS TODAY ADVANCES
(2021)
