Download or read book Vibrational Dynamics of Aqueous Hydroxide Solutions Studied Using Ultrafast Infrared Spectroscopy written by Aritra Mandal and published by . This book was released on 2015 with total page 217 pages. Available in PDF, EPUB and Kindle. Book excerpt: Liquid water possesses an extended network of hydrogen bonds that is responsible for many of its interesting properties. Mobility of hydroxide ions in aqueous solutions is much higher compared to the ions of similar size and charge density. A proton can efficiently move from a neighboring water molecule to the hydroxide ion due to the presence of hydrogen bonds, resulting fast structural diffusion of the ion. On the other hand, this hydrogen bonding network of water undergoes fluctuations on femtoseconds to picoseconds timescale, influencing the intertwined hydroxide transport process. Studying the influence of water's hydrogen bonding network on the proton transport process in aqueous hydroxide solutions is experimentally challenging, largely due to the lack of a suitable technique that is sensitive to the changes in the system on few tens of femtoseconds timescale. Vibrations in aqueous hydroxide solutions are sensitive to the strength of hydrogen bonding and hence vibrational frequencies, intensities and line shapes are closely associated with the structure and dynamics of the hydroxide ions. In this thesis, we have employed ultrafast infrared spectroscopy in conjunction with theoretical modeling to understand the nature of the vibrations and their dynamics in aqueous hydroxide solutions. The infrared spectra of aqueous solutions of NaOH and other strong bases exhibit a broad continuum absorption for frequencies between 800 and 3500 cm-1, which is attributed to the strong interactions of the hydroxide ion with its solvating water molecules. This continuum absorption has limited distinguishable features whose molecular origin holds the key in explaining the vibrational dynamics. We have performed ultrafast transient absorption and 2DIR experiments on aqueous NaOH solutions, by exciting the O-H stretch vibrations and probing the response from 1350-3800 cm-1, using a newly developed sub-70 fs broadband infrared source. By probing the entire mid-infrared continuum absorption of aqueous hydroxide solutions with ultrafast pulses, the broadband infrared source allows us to monitor time-dependent changes in this broad spectral window. These experiments, in conjunction with harmonic vibrational analysis of OH-(H2O)17 clusters, reveal that O-H stretch vibrations of aqueous hydroxides arise from coupled vibrations of multiple water molecules solvating the ion. These delocalized vibrations cannot be distinguished based on the local structure of the hydroxide ion. However, they can be classified according to the symmetry defined by the relative phase of vibrations of the O-H bonds hydrogen bonded to the ion. In general, we find the asymmetric O-H stretch vibrations to be more intense and shifted to lower frequencies compared to the symmetric ones. Analysis of transient absorption and waiting time dependent 2DIR spectroscopy shows that the vibrations in aqueous hydroxide solutions relax on 100-300 fs timescale. Alongside, the O-H stretch vibrations originating from the bulk-like water molecules as well as the asymmetric O-H stretch vibrations of the water molecules solvating the hydroxide ion lose their frequency memory within 160-180 fs. Such loss in frequency memory on similar timescales is likely to happen through migration of vibrational excitation between two types of O-H stretch vibrations. Spectral features in strongly hydrogen bonded systems like water and aqueous hydroxide solutions are very broad, particularly the induced absorption features in the transient absorption and 2DIR spectra. With the development of broadband mid-infrared pulses, we are able to detect nonlinear response of these systems in the frequency window of 1350-3800 cm-1, observing >1700 cm-1 broad induced absorption features. Qualitatively, strong coupling between intra- and intermolecular vibrations lead to such broadening. In order to explain the experimental results, we have developed a self-consistent phenomenological model that consists of an intramolecular and an intermolecular vibration, with strong nonlinear coupling between them. We find that the experimental results are reproduced when the coupling between the vibrations is strong enough to yield eigenstates with mixed intra- and intermolecular vibrational character. In such scenarios, the identities of individual intra- and intermolecular vibrational modes are lost.
Download or read book Ultrafast Infrared Vibrational Spectroscopy written by Michael D. Fayer and published by CRC Press. This book was released on 2013-03-04 with total page 491 pages. Available in PDF, EPUB and Kindle. Book excerpt: The advent of laser-based sources of ultrafast infrared pulses has extended the study of very fast molecular dynamics to the observation of processes manifested through their effects on the vibrations of molecules. In addition, non-linear infrared spectroscopic techniques make it possible to examine intra- and intermolecular interactions and how such interactions evolve on very fast time scales, but also in some instances on very slow time scales. Ultrafast Infrared Vibrational Spectroscopy is an advanced overview of the field of ultrafast infrared vibrational spectroscopy based on the scientific research of the leading figures in the field. The book discusses experimental and theoretical topics reflecting the latest accomplishments and understanding of ultrafast infrared vibrational spectroscopy. Each chapter provides background, details of methods, and explication of a topic of current research interest. Experimental and theoretical studies cover topics as diverse as the dynamics of water and the dynamics and structure of biological molecules. Methods covered include vibrational echo chemical exchange spectroscopy, IR-Raman spectroscopy, time resolved sum frequency generation, and 2D IR spectroscopy. Edited by a recognized leader in the field and with contributions from top researchers, including experimentalists and theoreticians, this book presents the latest research methods and results. It will serve as an excellent resource for those new to the field, experts in the field, and individuals who want to gain an understanding of particular methods and research topics.
Download or read book Ultrafast Phenomena XVI written by Paul Corkum and published by Springer Science & Business Media. This book was released on 2010-03-23 with total page 1031 pages. Available in PDF, EPUB and Kindle. Book excerpt: Ultrafast Phenomena XVI presents the latest advances in ultrafast science, including both ultrafast optical technology and the study of ultrafast phenomena. It covers picosecond, femtosecond and attosecond processes relevant to applications in physics, chemistry, biology, and engineering. Ultrafast technology has a profound impact in a wide range of applications, amongst them biomedical imaging, chemical dynamics, frequency standards, material processing, and ultrahigh speed communications. This book summarizes the results presented at the 16th International Conference on Ultrafast Phenomena and provides an up-to-date view of this important and rapidly advancing field.
Download or read book Linear and Non linear Vibrational Spectroscopy of Water and Aqueous Solutions written by Jordan R. Schmidt and published by . This book was released on 2006 with total page 196 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Final Technical Report Structural Dynamics in Complex Liquids Studied with Multidimensional Vibrational Spectroscopy written by and published by . This book was released on 2015 with total page 4 pages. Available in PDF, EPUB and Kindle. Book excerpt: This grant supported work in the Tokmakoff lab at the University of Chicago aimed at understanding the fundamental properties of water at a molecular level, and how water participates in proton transport in aqueous media. The physical properties of water and aqueous solutions are inextricably linked with efforts to develop new sustainable energy sources. Energy conversion, storage, and transduction processes, particularly those that occur in biology and soft matter, make use of water for the purpose of storing and moving charge. Water's unique physical and chemical properties depend on the ability of water molecules to participate in up to four hydrogen bonds, and the rapid fluctuations and ultrafast energy dissipation of its hydrogenbonded networks. Our work during the grant period led to advances in four areas: (1) the generation of short pulses of broadband infrared light (BBIR) for use in time-resolved twodimensional spectroscopy (2D IR), (2) the investigation of the spectroscopy and transport of excess protons in water, (3) the study of aqueous hydroxide to describe the interaction of the ion and water and the dynamics of proton transfer, and (4) the coupled motion of water and its hydrogen-bonding solutes.
Download or read book Solvation Dynamics written by Chang Q Sun and published by Springer. This book was released on 2019-07-03 with total page 302 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book highlights the latest advances and outlines future trends in aqueous solvation studies from the perspective of hydrogen bond transition by charge injection, which reconciles the solvation dynamics, molecular nonbond interactions, and the extraordinary functionalities of various solutes on the solution bond network and properties. Focus is given on ionic and dipolar electrostatic polarization, O:H nonbond interaction, anti-HB and super-HB repulsion, and solute-solute interactions. Its target audience includes researchers, scientists, and engineers in chemistry, physics, surface and interface science, materials science and engineering.
Download or read book Ultrafast Vibrational Spectroscopy and Dynamics of Water at Interfaces written by Ali Eftekharibafrooei and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Chemistry
Download or read book Ab Initio Molecular Dynamics written by Dominik Marx and published by Cambridge University Press. This book was released on 2009-04-30 with total page 503 pages. Available in PDF, EPUB and Kindle. Book excerpt: Ab initio molecular dynamics revolutionized the field of realistic computer simulation of complex molecular systems and processes, including chemical reactions, by unifying molecular dynamics and electronic structure theory. This book provides the first coherent presentation of this rapidly growing field, covering a vast range of methods and their applications, from basic theory to advanced methods. This fascinating text for graduate students and researchers contains systematic derivations of various ab initio molecular dynamics techniques to enable readers to understand and assess the merits and drawbacks of commonly used methods. It also discusses the special features of the widely used Car–Parrinello approach, correcting various misconceptions currently found in research literature. The book contains pseudo-code and program layout for typical plane wave electronic structure codes, allowing newcomers to the field to understand commonly used program packages and enabling developers to improve and add new features in their code.
Download or read book Structural Dynamics in Complex Liquids Studied with Multidimensional Vibrational Spectroscopy written by and published by . This book was released on 2013 with total page 8 pages. Available in PDF, EPUB and Kindle. Book excerpt: The development of new sustainable energy sources is linked to our understanding of the molecular properties of water and aqueous solutions. Energy conversion, storage, and transduction processes, particularly those that occur in biology, fuel cells, and batteries, make use of water for the purpose of moving energy in the form of charges and mediating the redox chemistry that allows this energy to be stored as and released from chemical bonds. To build our fundamental knowledge in this area, this project supports work in the Tokmakoff group to investigate the molecular dynamics of water's hydrogen bond network, and how these dynamics influence its solutes and the mechanism of proton transport in water. To reach the goals of this grant, we developed experiments to observe molecular dynamics in water as directly as possible, using ultrafast multidimensional vibrational spectroscopy. We excite and probe broad vibrational resonances of water, molecular solutes, and protons in water. By correlating how molecules evolve from an initial excitation frequency to a final frequency, we can describe the underlying molecular dynamics. Theoretical modeling of the data with the help of computational spectroscopy coupled with molecular dynamics simulations provided the atomistic insight in these studies.
Download or read book Mineral Water Interface Geochemistry written by Michael F. Hochella and published by Walter de Gruyter GmbH & Co KG. This book was released on 2018-12-17 with total page 620 pages. Available in PDF, EPUB and Kindle. Book excerpt: Volume 23 of Reviews in Mineralogy and accompanying MSA short course covers chemical reactions that take place at mineral-water interfaces. We believe that this book describes most of the important concepts and contributions that have driven mineral-water interface geochemistry to its present state. We begin in Chapter 1 with examples of the global importance of mineral-water interface reactions and a brief review of the contents of the entire book. Thereafter, we have divided the book into four sections, including atomistic approaches (Chapters 2- 3), adsorption (Chapters 4-8), precipitation and dissolution (Chapters 9-11), and oxidation-reduction reactions (Chapters 11-14).
Download or read book The Electrodynamics of Water and Ice written by Vasily Artemov and published by Springer Nature. This book was released on 2021-04-20 with total page 231 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book is a research monograph summarizing recent advances related to the molecular structure of water and ice, and it is based on the latest spectroscopic data available. A special focus is given to radio- and microwave frequency regions. Within the five interconnected chapters, the author reviews the electromagnetic waves interaction with water, ice, and moist substances, discussing the microscopic mechanisms behind the dielectric responses. Well-established classic views concerning the structure of water and ice are considered along with new approaches related to atomic and molecular dynamics. Particular attention is given to nanofluidics, atmospheric science, and electrochemistry. The mathematical apparatus, based on diverse approaches employed in condensed matter physics, is widely used and allows the reader to quantitatively describe the electrodynamic response of water and ice in both bulk and confined states. This book is intended for a wide audience covering physicists, electrochemists, geophysicists, engineers, biophysicists, and general scientists who work on the electromagnetic radiation interaction with water and moist substances.
Download or read book Solvation Thermodynamics written by Arieh Y. Ben-Naim and published by Springer Science & Business Media. This book was released on 2013-03-09 with total page 253 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book deals with a subject that has been studied since the beginning of physical chemistry. Despite the thousands of articles and scores of books devoted to solvation thermodynamics, I feel that some fundamen tal and well-established concepts underlying the traditional approach to this subject are not satisfactory and need revision. The main reason for this need is that solvation thermodynamics has traditionally been treated in the context of classical (macroscopic) ther modynamics alone. However, solvation is inherently a molecular pro cess, dependent upon local rather than macroscopic properties of the system. Therefore, the starting point should be based on statistical mechanical methods. For many years it has been believed that certain thermodynamic quantities, such as the standard free energy (or enthalpy or entropy) of solution, may be used as measures of the corresponding functions of solvation of a given solute in a given solvent. I first challenged this notion in a paper published in 1978 based on analysis at the molecular level. During the past ten years, I have introduced several new quantities which, in my opinion, should replace the conventional measures of solvation thermodynamics. To avoid confusing the new quantities with those referred to conventionally in the literature as standard quantities of solvation, I called these "nonconventional," "generalized," and "local" standard quantities and attempted to point out the advantages of these new quantities over the conventional ones.
Download or read book Ionic Liquids II written by Barbara Kirchner and published by Springer. This book was released on 2018-09-03 with total page 289 pages. Available in PDF, EPUB and Kindle. Book excerpt: The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field. The chapters “Ionic Liquid–Liquid Chromatography: A New General Purpose Separation Methodology”, “Proteins in Ionic Liquids: Current Status of Experiments and Simulations”, “Lewis Acidic Ionic Liquids” and "Quantum Chemical Modeling of Hydrogen Bonding in Ionic Liquids" are available open access under a Creative Commons Attribution 4.0 International License via link.springer.com.
Download or read book Hydrogen Bond Networks written by Marie-Claire Bellisent-Funel and published by Springer. This book was released on 2014-03-14 with total page 558 pages. Available in PDF, EPUB and Kindle. Book excerpt: The almost universal presence of water in our everyday lives and the very `common' nature of its presence and properties possibly deflects attention from the fact that it has a number of very unusual characteristics which, furthermore, are found to be extremely sensitive to physical parameters, chemical environment and other influences. Hydrogen-bonding effects, too, are not restricted to water, so it is necessary to investigate other systems as well, in order to understand the characteristics in a wider context. Hydrogen Bond Networks reflects the diversity and relevance of water in subjects ranging from the fundamentals of condensed matter physics, through aspects of chemical reactivity to structure and function in biological systems.
Download or read book Physical Chemistry of Electrolyte Solutions written by Josef Barthel and published by Springer Science & Business Media. This book was released on 1998-04 with total page 434 pages. Available in PDF, EPUB and Kindle. Book excerpt: The aim and purpose of this book is a survey of our actual basic knowledge of electrolyte solutions. It is meant for chemical engineers looking for an introduction to this field of increasing interest for various technologies, and for scientists wishing to have access to the broad field of modern electrolyte chemistry.
Download or read book Chemical Abstracts written by and published by . This book was released on 1990 with total page 2210 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Classical And Quantum Dynamics In Condensed Phase Simulations Proceedings Of The International School Of Physics written by Bruce J Berne and published by World Scientific. This book was released on 1998-06-17 with total page 881 pages. Available in PDF, EPUB and Kindle. Book excerpt: The school held at Villa Marigola, Lerici, Italy, in July 1997 was very much an educational experiment aimed not just at teaching a new generation of students the latest developments in computer simulation methods and theory, but also at bringing together researchers from the condensed matter computer simulation community, the biophysical chemistry community and the quantum dynamics community to confront the shared problem: the development of methods to treat the dynamics of quantum condensed phase systems.This volume collects the lectures delivered there. Due to the focus of the school, the contributions divide along natural lines into two broad groups: (1) the most sophisticated forms of the art of computer simulation, including biased phase space sampling schemes, methods which address the multiplicity of time scales in condensed phase problems, and static equilibrium methods for treating quantum systems; (2) the contributions on quantum dynamics, including methods for mixing quantum and classical dynamics in condensed phase simulations and methods capable of treating all degrees of freedom quantum-mechanically.
