Luận án tiến sĩ nghiên cứu động lực học vi mô của nước - Đại học Sư phạm Hà Nội 2

MINISTRY OF EDUCATION AND TRAINING HA NOI PEDAGOGICAL UNIVERSITY 2 ———————o0o——————– TRAN THI NHAN STUDY ON SOME MICRODYNAMIC BEHAVIORS OF LIQUID WATER DOCTORAL THESIS IN PHYSICS Ha Noi - 2020 luan an MINISTRY OF EDUCATION AND TRAINING HA NOI PEDAGOGICAL UNIVERSITY 2 ———————o0o——————– TRAN THI NHAN STUDY ON SOME MICRODYNAMIC BEHAVIORS OF LIQUID WATER Major: Theoretical Physics and Mathematical Physics Code: 9 44 01 03 DOCTORAL THESIS IN PHYSICS SUPERVISOR: ASSOC. LE TUAN Ha Noi - 2020 luan an DECLARATIONS I declare that is my research under the supervision and direction of Assoc. All results reported in the thesis are original and honest, which have never been published by whomever and in any university thesis, university master thesis, or doctoral thesis. In the process of performing thesis, we have inherited the previous achieve- ments in experimental and theoretical researches with the profound respect and gratitude.

All citations and references have been clearly indicated. Ha Noi, September, 2020 Author Tran Thi Nhan i luan an ACKNOWLEDGMENTS Firstly, I would like to express my sincere gratitude to my supervisor Assoc. Le Tuan for the continuous support of my Ph.D study and related research, for his patience, motivation, and immense knowledge. His guidance helped me in all the time of research and writing of this thesis.

I could not have imagined having a better adviser and mentor for my Ph. I would like to especially thank Prof. Nguyen Ai Viet who inspired me to do research and enlightened me the first glance of research. His hard questions are really helpful to conduct and widen my research from various perspectives.

My sincere thanks also go to professors of Faculty of Physics and Train- ing Department - Hanoi Pedagogical University 2 who gave the author the best conditions to fulfill the thesis. The author would like to thank the leaders of Hanoi University of Industry and all coworkers who have been supporting and encouraging the author during the process performing the doctoral the- sis. Without they precious support it would not be possible to conduct this research. I thank my fellow Ph.D students in for the stimulating discussions and for all the fun we have had in the last four years.

Last but not the least, I would like to thank all members of my extended family for supporting me spiritually throughout writing this thesis and my life in general. Author Tran Thi Nhan ii luan an List of Figures 0.1 Summarizing about collective density oscillation in liquid water 7 1.1 The structure of water molecule .2 Schematic of the tetrahedral coordination of water molecules 21 1.3 Dielectric spectroscopy of liquid water .4 The permittivity relaxation of NaCl solution in the Debye equation .1 Dispersion of PPs for CsI .2 Dispersion of the collective density oscillations in liquid water 48 2.3 Phase and group speeds of liquid water .4 The frequency dependence of the dielectric constant .5 The comparison about dielectric spectroscopy of liquid water 61 2.6 Van’t Hoff plot .1 The AC conductivity at 1 GHz of sodium chloride solution .2 Frequency spectra of the microwave conductivity .3 Temperature dependence of the diffusion coefficient .1 The concentration dependence of the static permittivity .2 The concentration dependence of the Debye screening length 86 4.3 The dependence of the Debye length on the Debye length of liquid water .4 Specific conductivity of dilute solution .5 Specific conductivity of concentrated sodium chloride aque- ous solution. 94 iii luan an List of Tables 1.1 Some basis properties of pure liquid water .1 The value of b. 88 iv luan an Contents INTRODUCTION 5 1.

Objectives and scopes. Mission of research. 13 Chapter 1 PROPERTIES AND COMPLICATED BE- HAVIORS OF WATER 16 1.1 Fundamental physical properties .2 Molecular structure and polarization .5 Dielectric constant of liquid water and aqueous solutions .3 Semi-empirical models for dielectric relaxation .2 Models of non-Debye type relaxation .4 Microscopic theories of permittivity relaxation .2 Kirkwood-Fröhlich equation .5 Static dielectric constant and dielectric constant at low frequencies .6 Diffusion motion in liquid water .7 Plasmon frequency of pure liquid water. 35 Chapter 2 SOME DYNAMIC FEATURES OF LIQUID WATER 38 2.1 Phonon-polariton theory for semiconductors .2 Modified phonon-polariton model for collective density os- cillations in liquid water .3 Dispersion of the two modes in liquid water .4 The regime transformation of the dynamics of liquid water at the onset point .5 Correlation between ultrasonic vibration potential and collec- tive density oscillations .1 Ultrasonic vibration potential .2 Electro-acoustic correlation in liquid water .6 Phase and group velocities of collective density oscillations in liquid water .7 Microscopic approach for dielectric constant of liquid water at low frequencies .8 Water dielectric constant at low frequencies in the model .9 Isopermittive point and van’t Hoff effect.

62 Chapter 3 MICROWAVE ELECTRODYNAMICS OF ELECTROLYTE SOLUTIONS 66 3.2 Jellium theory for electrolyte solutions .3 Drude model for metal dielectric permittivity .4 Drude-jellium model for microwave conductivity dispersion 73 3.5 The diffusion coefficient. 77 2 luan an Chapter 4 NONLINEAR ELECTROSTATICS OF ELEC- TROLYTE SOLUTIONS 79 4.1 Statistic model for the decrease in the static permittivity of electrolyte solutions .2 Statistical model and experimental data .2 The Debye screening length according to the nonlinear decre- ment in static permittivity .1 Debye screening length .2 The Debye screening length versus concentration in the statistical model .3 The Debye screening length upon the Debye screen- ing length of solvent .3 Weak and strong interaction regime of the internal electric field 89 4.4 Simple model for static specific conductivity of electrolyte solutions .1 Static specific conductivity in weak interaction regime 91 4.2 Static specific conductivity according to the strong in- teraction regime. 93 CONCLUSIONS AND FURTHER RESEARCH DIRECTIONS 96 THESIS-RELATED PUBLICATIONS 99 Bibliography. 100 3 luan an Acronyms Symbols Words PP Phonon polariton EM Electromagnetic LO Longitudinal optical TO Transverse optical INS Inelastic neutron scattering IXS Inelastic X-ray scattering IUS Inelastic ultraviolet scattering MD Molecular dynamics D-H Debye-Hückel Eq.

Figure 2SIP Double solvent-separated ion pair SIP Solvent-shared ion pair CIP Contact ion pair 4 luan an INTRODUCTION 1. Motivation The relationship between things in nature, particularly in our environment is implied to be objective, universal, and holistic. It seems to exist the univer- sal relationships and the universal laws behind the richness, the complexity, and the miracles of natural behaviors. These universal natural laws govern and control the physical processes and physical phenomena.

Therefore, they also govern the laws of processes and phenomena in chemistry, biology, etc. People always try to discover the processes and the phenomena of the nat- ural world from many perspectives and by every possible approach. Water is the most studied material on Earth by interdisciplinary science, including physics, chemistry, and biology in such a way. It is well-known that water is the main component of living cell as well as the important solvent in which chemical reactions can happen.

Study of the microdynamic behaviors of the liquid water system related to the interaction between liquid water and EM field is an effective manner to explore several microdynamic behaviors in living cells such as biological information trans- fer, the hydration in biology and chemistry. A careful understanding about the water - EM field interaction is also useful to interpret the dynamical phe- nomena occurring in the ocean, aqueous chemical solution, and biological system. It is difficult to develop application researches in several areas such as food, medical industries, chemical industries, and remote sensing of the ocean without a good knowledge about water microdynamics. There is a great accomplishment with a long history on both the experi- mental and the theoretical sides about water micro dynamics in Vietnam as well as in the world.

However, it is remarkable to find that the microdynamic mechanism responsible for its behavior in relation to the interaction between liquid water system and EM field in different spectrum ranges is not thor- oughly understood. Some explanations of its complex features and behaviors 5 luan an bring a considerable disagreement, needing a further investigation. In ad- dition, many other anomalous properties of water possibly remain to be not discovered. According to the literature, several open topics about micrody- namic behaviors of liquid water for further research could be mentioned in detail as below: A.

The fast sound in liquid water In 1974, using Molecular Dynamics (MD) simulations, A. This simulation work induced a large number of experimental researches such as Inelastic Neutron Scattering (INS) [15, 98, 110, 129, 130], Inelastic X-ray Scattering (IXS) [89, 101, 110, 121, 122], or Inelastic Ultraviolet Scattering (IUS) [116]. In addition, several MD simulations [8, 7, 9, 70, 101, 105, 117, 140] were performed to further clarify the origin of these excitations as well as water complicated dynamical features. The most striking result of these INS, IXS, IUS, and MD simulation studies recognized the coexistence of the two collective density oscillation modes traveling in liquid water.

Two different models, the viscoelastic model (or model of structural relaxation) [101, 119] and the two-mode interaction model [98, 110] were given for description and explanation about the existence of both the modes. In the model of structural relaxation, the different collective oscillation modes propagating in liquid water were interpreted in terms of the relaxation time τF (the time associated with breaking and forming of hydrogen bonds) be- ing longer or shorter than the time scale related to the density fluctuations [89, 101, 109]. This model was successfully applied to explain the pres- sure and temperature dependence of several dynamical parameters [78, 101, 109]. The two-mode interaction model consists of two different dispersion branches originated from the idea that the splitting of the lower branch from 6 luan an Fig.

Summarizing about collective density oscillation in liquid water [109]: The open symbols correspond to the prediction in Ref. [126] whereas the full symbols represent INS experimental data in Ref. The solid lines are fitting according to the fast sound (upper) and ordinary sound (lower). the longitudinal one due to the interaction between elementary excitations of linear dispersion mode and those of the dispersionless mode with energy Ω0 (5−6 meV).

It was suggested that the dispersion relations for both the modes traveling in liquid water with the presence of the coupling coefficient β(Q) between each other. Although the two-mode interaction model is a quite sim- ple, it might make clear some observed features of the dynamic spectra and describes quite well the dispersion of both the modes [110]. In spite of such efforts, the physical origin of the fast mode in liquid water and the splitting of the two modes remains poorly understood. It is necessary to conduct a further investigation for a deeper understanding about the complex mechanisms of liquid water dynamics.

The low-frequency dielectric constant of liquid water A. Uriber [3] (2011) pointed out the temperature de- pendence of the water relative permittivity in the region of low frequency 1000 Hz − 1 MHz with an interesting surprise. They found a special point called the isopermittive point at the frequency ωiso where the water dielec- 7 luan an tric constant does not depend on temperature. Rising temperature makes the dielectric constant of liquid water increase at frequencies below ωiso but de- crease at frequencies above ωiso.

This behavior of the dielectric constant for pure water is similar to that of glycerol-water mixtures [4]. Some theoretical models have been suggested to describe the dielectric spectroscopy behavior of water, such as the models of Debye [34], Onsager [92], and Kirkwood [75]. Nevertheless, it is impossible to apply these models to illuminate the dynamical mechanism behind the behavior of the isopermit- tive point because they are only suitable to interpret effects happening in the frequency range above 1 GHz. The dynamical mechanism that is responsi- ble for the existence of the isopermittive point has just been explained by the phenomenological model [3].

Nowadays, there is lacking a theoretical model for the description about the water dielectric dispersion at low frequencies originated from solid arguments.