Special Issue "Physical Chemistry Perspectives for the New Decade"

A special issue of Physchem (ISSN 2673-7167).

Deadline for manuscript submissions: closed (30 June 2021).

Special Issue Editors

Prof. Dr. Jacinto Sá
E-Mail Website
Guest Editor
Department of Chemistry-Ångström Laboratory, Uppsala University, 75120 Uppsala, Sweden
Interests: plasmonic hybrid systems; artificial photosynthesis; solar cells; ultrafast spectroscopy
Special Issues and Collections in MDPI journals
Dr. Sergei Manzhos
E-Mail Website
Guest Editor
School of Materials and Chemical Technology, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8552, Japan
Interests: metal ion batteries; solar cells; computational spectroscopy; machine learning
Special Issues and Collections in MDPI journals

Special Issue Information

Dear Colleague,

“Physical chemistry is everything that is interesting and exciting!” is a quote often attributed to G. N. Lewis. While there are many different definitions of the discipline, it is characterized by the use of physical theory, models and methods in the study of chemistry. The discipline is defined by its approach rather than by the nature of the systems studied—a stark contrast to the other chemistry disciplines.

Physchem is the first exclusive open-source journal dedicated to the disciplines of Physical Chemistry and Chemical Physics. In this inaugural Issue, we want to showcase the contributions of the discipline to solve the pressing problems facing mankind in the coming decade, such as climate change, renewable energy security, and sustainable development. We aim to publish manuscripts covering the multitude of themes at the intersection of physics and chemistry. In particular, we welcome manuscripts on research contributing to the achievement of the UN Sustainable Development Goals.

Prof. Dr. Jacinto Sá
Dr. Sergei Manzhos
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Physchem is an international peer-reviewed open access quarterly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Published Papers (13 papers)

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Research

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Article
Predicting 1,9-Decadiene−Water Partition Coefficients Using the 3D-RISM-KH Molecular Solvation Theory
Physchem 2021, 1(2), 215-224; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1020015 - 04 Sep 2021
Viewed by 239
Abstract
The Three-Dimensional Reference Interaction Site Model (3D-RISM) with Kovalenko−Hirata (KH) closure is applied to calculate the 1,9-Decadiene/Water partition coefficients for a diverse class of compounds. The liquid state of 1,9-Decadiene is represented with the united atom TraPPE force field parameters. The 3D-RISM-KH computed [...] Read more.
The Three-Dimensional Reference Interaction Site Model (3D-RISM) with Kovalenko−Hirata (KH) closure is applied to calculate the 1,9-Decadiene/Water partition coefficients for a diverse class of compounds. The liquid state of 1,9-Decadiene is represented with the united atom TraPPE force field parameters. The 3D-RISM-KH computed partition functions are in good agreement with the experimental results. Our computational scheme can be used for a quantitative structure partitioning prediction for decadiene-water system, which has been used in membrane-mimicking of the egg-lecithin/water permeability experiments. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Article
The Water Polymorphism and the Liquid–Liquid Transition from Transport Data
Physchem 2021, 1(2), 202-214; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1020014 - 25 Aug 2021
Viewed by 227
Abstract
NMR spectroscopic literature data are used, in a wide temperature-pressure range (180–350 K and 0.1–400 MPa), to study the water polymorphism and the validity of the liquid–liquid transition (LLT) hypothesis. We have considered the self-diffusion coefficient DS and the reorientational correlation time [...] Read more.
NMR spectroscopic literature data are used, in a wide temperature-pressure range (180–350 K and 0.1–400 MPa), to study the water polymorphism and the validity of the liquid–liquid transition (LLT) hypothesis. We have considered the self-diffusion coefficient DS and the reorientational correlation time τθ (obtained from spin-lattice T1 relaxation times), measured, respectively, in bulk and emulsion liquid water from the stable to well inside the metastable supercooled region. As an effect of the hydrogen bond (HB) networking, the isobars of both these transport functions evolve with T by changing by several orders of magnitude, whereas their pressure dependence become more and more pronounced at lower temperatures. Both these transport functions were then studied according to the Adam–Gibbs model, typical of glass forming liquids, obtaining the water configurational entropy and the corresponding specific heat contribution. The comparison of the evaluated CP,conf isobars with the experimentally measured water specific heat reveals the full consistency of this analysis. In particular, the observed CP,conf maxima and its diverging behaviors clearly reveals the presence of the LLT and with a reasonable approximation the liquid–liquid critical point (LLCP) locus in the phase diagram. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Article
Unusual Para-Substituent Effects on the Intramolecular Hydrogen Bond in Hydrazone-Based Switches: Insights from Chemical Landscape Analysis and DFT Calculations
Physchem 2021, 1(2), 189-201; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1020013 - 05 Aug 2021
Viewed by 215
Abstract
Тhe adequacy of chemical property predictions strongly depends on the structure representation, including the proper treatment of the tautomeric and isomeric forms. A combination of an in-house developed open-source tool for automatic generation of tautomers, Ambit-Tautomer, based on H-atom shift rules and standard [...] Read more.
Тhe adequacy of chemical property predictions strongly depends on the structure representation, including the proper treatment of the tautomeric and isomeric forms. A combination of an in-house developed open-source tool for automatic generation of tautomers, Ambit-Tautomer, based on H-atom shift rules and standard quantum chemical (DFT) calculations is used for a detailed investigation of the possible geometric isomers, conformers and tautomers of unsubstituted and para-substituted phenylhydrazones, systems with experimentally observed unusual para-substituent effects on the intramolecular hydrogen bond (IMHB) for E-isomers of the compounds. The computational results show that the energetically preferred E-isomers are characterized by stronger IMHBs than the corresponding Z-isomers. The HN–N=C–C=N molecular fragment in the E-configurations is less sensitive to the substitution effect than the HN–N=C–C=O fragment in the isomers with Z-configuration. A probable reason for this decreased sensitivity of E-isomers to phenyl ring substitution is the more efficient conjugation and charge distribution in the HN–N=C–C=N fragment. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Article
Raman Sensor for the Determination of Gas Solubility
Physchem 2021, 1(2), 176-188; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1020012 - 04 Aug 2021
Viewed by 370
Abstract
Efficient and environmentally responsible use of resources requires the development and optimization of gas separation processes. A promising approach is the use of liquids that are designed for specific tasks, e.g., the capture of carbon dioxide or other greenhouse gases. This requires an [...] Read more.
Efficient and environmentally responsible use of resources requires the development and optimization of gas separation processes. A promising approach is the use of liquids that are designed for specific tasks, e.g., the capture of carbon dioxide or other greenhouse gases. This requires an accurate determination of gas solubilities for a broad range of temperatures and pressures. However, state of the art measurement techniques are often very time consuming or exhibit other pitfalls that prevent their use as efficient screening tools. Here, we show that the application of Raman spectroscopy through a compact measuring system can simplify data acquisition for the determination of gas solubilities in liquids. To demonstrate that this approach is expedient, we determined gas solubilities of carbon dioxide in water for three isotherms T = (288.15, 293.15, 298.15) K over a pressure range from p = (0.5–5) MPa and in three imidazolium-based ionic liquids for one isotherm T = 298.15 K at pressures from p = (0.1–5) MPa. When compared to data in the literature, all results are within the reported uncertainties of the measurement techniques involved. The developed analysis method eliminates the need for a lengthy volume or mass calibration of the sample prior to the measurements and, therefore, allows for fast screening of samples, which can help to advance gas separation processes in scientific and industrial applications. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Article
Plasmon-Mediated Oxidation Reaction on Au/p-Cu2O: The Origin of Hot Holes
Physchem 2021, 1(2), 163-175; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1020011 - 27 Jul 2021
Viewed by 405
Abstract
More sustainable solutions are needed to produce chemicals and fuels, mainly to face rising demands and mitigate climate change. Light, as a reagent, has emerged as a route to activate small molecules, e.g., H2O, CO2, N2, and [...] Read more.
More sustainable solutions are needed to produce chemicals and fuels, mainly to face rising demands and mitigate climate change. Light, as a reagent, has emerged as a route to activate small molecules, e.g., H2O, CO2, N2, and make complex chemicals in a process called photocatalysis. Several photosystems have been proposed, with plasmonic technology emerging as one the most promising technologies due to its high optical absorption and hot-carrier formation. However, the lifetime of hot carriers is unsuitable for direct use; therefore, they are normally coupled with suitable charge-accepting materials, such as semiconductors. Herein, a system is reported consisting of Au supported in p-Cu2O. The combination of p-Cu2O intrinsic photoactivity with the plasmonic properties of Au extended the system’s optical absorption range, increasing photocatalytic efficiency. More importantly, the system enabled us to study the underlying processes responsible for hot-hole transfer to p-Cu2O. Based on photocatalytic studies, it was concluded that most of the holes involved in aniline photo-oxidation come from hot-carrier injections, not from the PIRET process. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Article
Adhesion and Structural Changes of PEGylated Lipid Nanocarriers on Silica Surfaces
Physchem 2021, 1(2), 133-151; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1020009 - 15 Jul 2021
Viewed by 442
Abstract
PEGylated lipid nanoparticles have a continuously expanding range of applications, particularly within pharmaceutical areas. Hereby, it is shown with the help of the Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) and other surface sensitive techniques that, at room temperature, PEGylated liposomes and lipodisks [...] Read more.
PEGylated lipid nanoparticles have a continuously expanding range of applications, particularly within pharmaceutical areas. Hereby, it is shown with the help of the Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) and other surface sensitive techniques that, at room temperature, PEGylated liposomes and lipodisks adhere strongly to silica surfaces resulting in the displacement of the hydration layer of silica and the formation of immobilized nanoparticle films. Furthermore, it is shown that drastic changes in the structure of the immobilized films occur if the temperature is increased to >35 °C. Thus, intact immobilized PEGylated liposomes rupture and spread, even in the gel phase state; immobilized lipodisks undergo complete separation of their components (bilayer forming lipids and PEGylated lipids) resulting in a monolayer of adsorbed PEGylated lipids; and PEGylated supported lipid bilayers release part of the water trapped between the lipid membrane and the surface. It is hypothesized that these changes occur mainly due to the changes in the configuration of PEG chains and a drastic decrease of the affinity of the polymer for water. The observed phenomena can be applied, e.g., for the production of defect-free supported lipid bilayers in the gel or liquid ordered phase states. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Article
Methane Production from H2 + CO2 Reaction: An Open Molecular Science Case for Computational and Experimental Studies
Physchem 2021, 1(1), 82-94; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1010006 - 02 Jun 2021
Viewed by 775
Abstract
The article illustrates the synergy between theoretical/computational advances and advanced experimental achievements to pursue green chemistry and circular economy technological implementations. The specific green chemistry focus concerns the production of carbon neutral fuels by converting waste carbon dioxide into methane. Both theoretical-computational and [...] Read more.
The article illustrates the synergy between theoretical/computational advances and advanced experimental achievements to pursue green chemistry and circular economy technological implementations. The specific green chemistry focus concerns the production of carbon neutral fuels by converting waste carbon dioxide into methane. Both theoretical-computational and technological means were adopted to design a functional option implementing a heterogeneous catalysis process (Paul Sabatier (PS) catalytic reduction) to convert carbon dioxide into methane, and to further drive its evolution towards the employment of an alternative homogeneous gas phase plasma assisted technology. The details of both the theoretical and the experimental components of the study are presented and discussed. Future potential developments, including industrial ones, are outlined that are also from innovative collaborative economic prosumer model perspectives. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Article
An Electrochemical Impedance Study of Alkaline Water Splitting Using Fe Doped NiO Nanosheets
Physchem 2021, 1(1), 69-81; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1010005 - 31 May 2021
Viewed by 517
Abstract
Mixed nickel-iron (Ni-Fe) compounds have recently emerged as promising non-precious electrocatalysts for alkaline water splitting. The understanding of the charge-transfer mechanism involved in the multi-step Faradic reaction, however, is still limited for the overall electrochemical process. In this paper, electrochemical impedance spectroscopy (EIS) [...] Read more.
Mixed nickel-iron (Ni-Fe) compounds have recently emerged as promising non-precious electrocatalysts for alkaline water splitting. The understanding of the charge-transfer mechanism involved in the multi-step Faradic reaction, however, is still limited for the overall electrochemical process. In this paper, electrochemical impedance spectroscopy (EIS) measurements of Fe incorporated Ni oxide nanosheets were used to study the reaction kinetics for both hydrogen (HER) and oxygen (OER) evolution reactions in alkaline media. Our results showed that Fe incorporation improves the catalytic property of NiO nanosheets because of the lower reaction resistance and faster intermediate transformations. Detailed EIS modeling enables a separation of the surface coverage relaxation from the charge transfer resistance, with an inductive behavior observed in the low-frequency range for HER, holding important information on the dominating reaction mechanism. For OER, the good agreement between the EIS experimental results and a model with an inductance loop indicated that similar inductive behavior would be determining the EIS response at very low frequencies. The physical significance of the elementary steps gives insight into the governing reaction mechanisms involved in the electron and hole charge transfer, as well as the inherent properties of catalysts and their surface coverage relaxation. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Article
Vibrational Analysis of Benziodoxoles and Benziodazolotetrazoles
Physchem 2021, 1(1), 45-68; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1010004 - 14 May 2021
Viewed by 819
Abstract
Tetrazoles are well known for their high positive enthalpy of formation which makes them attractive as propellants, explosives, and energetic materials. As a step towards a deeper understanding of the stability of benziodazolotetrazole (BIAT)-based materials compared to their benziodoxole (BIO) counterparts, we investigated [...] Read more.
Tetrazoles are well known for their high positive enthalpy of formation which makes them attractive as propellants, explosives, and energetic materials. As a step towards a deeper understanding of the stability of benziodazolotetrazole (BIAT)-based materials compared to their benziodoxole (BIO) counterparts, we investigated in this work electronic structure features and bonding properties of two monovalent iodine precursors: 2-iodobenzoic acid and 5-(2-iodophenyl)tetrazole and eight hypervalent iodine (III) compounds: I-hydroxybenzidoxolone, I-methoxybenziodoxolone, I-ethoxybenziodoxolone, I-iso-propoxybenziodoxolone and the corresponding I-hydroxyben ziodazolotetrazole, I-methoxybenziodazolotetrazole, I-ethoxybenziodazolotetrazole and I-iso- propoxybenziodazolotetrazole. As an efficient tool for the interpretation of the experimental IR spectra and for the quantitative assessment of the I−C, I−N, and I−O bond strengths in these compounds reflecting substituent effects, we used the local vibrational mode analysis, originally introduced by Konkoli and Cremer, complemented by electron density and natural bond orbital analyses. Based on the hypothesis that stronger bonds correlate with increased stability, we predict that, for both series, i.e., substituted benziodoxoles and benziodazolotetrazoles, the stability increases as follows: I-iso-propoxy < I-ethoxy < I-methoxy < I-hydroxy. In particular, the I−N bonds in the benziodazolotetrazoles could be identified as the so-called trigger bonds being responsible for the initiation of explosive decomposition in benziodazolotetrazoles. The new insight gained by this work will allow for the design of new benziodazolotetrazole materials with controlled performance or stability based on the modulation of the iodine bonds with its three ligands. The local mode analysis can serve as an effective tool to monitor the bond strengths, in particular to identify potential trigger bonds. We hope that this article will foster future collaboration between the experimental and computational community being engaged in vibrational spectroscopy. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Review

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Review
Molecular Terms of Dioxygen and Nitric Oxide
Physchem 2021, 1(2), 121-132; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1020008 - 01 Jul 2021
Viewed by 477
Abstract
Molecular terms of dioxygen and nitic oxide are presented. Electron spin resonance spectra of diatomic molecules corresponding to these terms are discussed. Gas-phase ESR can be a convenient method of monitoring paramagnetic pollutants in the atmosphere. We ran additional calculations in molecular physics [...] Read more.
Molecular terms of dioxygen and nitic oxide are presented. Electron spin resonance spectra of diatomic molecules corresponding to these terms are discussed. Gas-phase ESR can be a convenient method of monitoring paramagnetic pollutants in the atmosphere. We ran additional calculations in molecular physics for terms of these molecules and Zeeman transitions. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Review
Net Zero and Catalysis: How Neutrons Can Help
Physchem 2021, 1(1), 95-120; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1010007 - 09 Jun 2021
Viewed by 708
Abstract
Net Zero has the aim of achieving equality between the amount of greenhouse gas emissions produced and the amount removed from the atmosphere. There is widespread acceptance that for Net Zero to be achievable, chemistry, and hence catalysis, must play a major role. [...] Read more.
Net Zero has the aim of achieving equality between the amount of greenhouse gas emissions produced and the amount removed from the atmosphere. There is widespread acceptance that for Net Zero to be achievable, chemistry, and hence catalysis, must play a major role. Most current studies of catalysts and catalysis employ a combination of physical methods, imaging techniques and spectroscopy to provide insight into the catalyst structure and function. One of the methods used is neutron scattering and this is the focus of this Perspective. Here, we show how neutron methods are being used to study reactions and processes that are directly relevant to achieving Net Zero, such as methane reforming, Fischer–Tropsch synthesis, ammonia and methanol production and utilization, bio-mass upgrading, fuel cells and CO2 capture and exploitation. We conclude by describing some other areas that offer opportunities. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Other

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Perspective
Basic Residue Clusters in Intrinsically Disordered Regions of Peripheral Membrane Proteins: Modulating 2D Diffusion on Cell Membranes
Physchem 2021, 1(2), 152-162; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1020010 - 19 Jul 2021
Viewed by 495
Abstract
A large number of peripheral membrane proteins transiently interact with lipids through a combination of weak interactions. Among them, electrostatic interactions of clusters of positively charged amino acid residues with negatively charged lipids play an important role. Clusters of charged residues are often [...] Read more.
A large number of peripheral membrane proteins transiently interact with lipids through a combination of weak interactions. Among them, electrostatic interactions of clusters of positively charged amino acid residues with negatively charged lipids play an important role. Clusters of charged residues are often found in intrinsically disordered protein regions, which are highly abundant in the vicinity of the membrane forming what has been called the disordered boundary of the cell. Beyond contributing to the stability of the lipid-bound state, the pattern of charged residues may encode specific interactions or properties that form the basis of cell signaling. The element of this code may include, among others, the recognition, clustering, and selective release of phosphatidyl inositides, lipid-mediated protein-protein interactions changing the residence time of the peripheral membrane proteins or driving their approximation to integral membrane proteins. Boundary effects include reduction of dimensionality, protein reorientation, biassing of the conformational ensemble of disordered regions or enhanced 2D diffusion in the peri-membrane region enabled by the fuzzy character of the electrostatic interactions with an extended lipid membrane. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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Perspective
The Importance of Interphases in Energy Storage Devices: Methods and Strategies to Investigate and Control Interfacial Processes
Physchem 2021, 1(1), 26-44; https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1010003 - 13 Apr 2021
Viewed by 499
Abstract
Extended interphases are playing an increasingly important role in electrochemical energy storage devices and, in particular, in lithium-ion and lithium metal batteries. With this in mind we initially address the differences between the concepts of interface and interphase. After that, we discuss in [...] Read more.
Extended interphases are playing an increasingly important role in electrochemical energy storage devices and, in particular, in lithium-ion and lithium metal batteries. With this in mind we initially address the differences between the concepts of interface and interphase. After that, we discuss in detail the mechanisms of solid electrolyte interphase (SEI) formation in Li-ion batteries. Then, we analyze the methods for interphase characterization, with emphasis put on in-situ and operando approaches. Finally, we look at the near future by addressing the issues underlying the lithium metal/electrolyte interface, and the emerging role played by the cathode electrolyte interphase when high voltage materials are employed. Full article
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
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