In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are c...In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are closely related to the hydrogen bonds(H-bonds)network between water molecules.Therefore,it is crucial to analyze the relationship between these two aspects.In this paper,the infrared spectrum and motion characteristics of the stretching vibrations of the O-H bonds in one-dimensional confined water(1DCW)and bulk water(BW)in(6,6)single-walled carbon nanotubes(SWNT)are studied by molecular dynamics simulations.The results show that the stretching vibrations of the two O-H bonds in 1DCW exhibit different frequencies in the infrared spectrum,while the O-H bonds in BW display two identical main frequency peaks.Further analysis using the spring oscillator model reveals that the difference in the stretching amplitude of the O-H bonds is the main factor causing the change in vibration frequency,where an increase in stretching amplitude leads to a decrease in spring stiffness and,consequently,a lower vibration frequency.A more in-depth study found that the interaction of H-bonds between water molecules is the fundamental cause of the increased stretching amplitude and decreased vibration frequency of the O-H bonds.Finally,by analyzing the motion trajectory of the H atoms,the dynamic differences between 1DCW and BW are clearly revealed.These findings provide a new perspective for understanding the behavior of water molecules at the nanoscale and are of significant importance in advancing the development of infrared spectroscopy detection technology.展开更多
Although there are numerous optical spectroscopy techniques and methods that have been used to extract the fundamental bandgap of a semiconductor,most of them belong to one of these three approaches:(1)the excitonic a...Although there are numerous optical spectroscopy techniques and methods that have been used to extract the fundamental bandgap of a semiconductor,most of them belong to one of these three approaches:(1)the excitonic absorption,(2)modulation spectroscopy,and(3)the most widely used Tauc-plot.The excitonic absorption is based on a many-particle theory,which is physically the most correct approach,but requires more stringent crystalline quality and appropriate sample preparation and experimental implementation.The Tauc-plot is based on a single-particle theo⁃ry that neglects the many-electron effects.Modulation spectroscopy analyzes the spectroscopy features in the derivative spectrum,typically,of the reflectance and transmission under an external perturbation.Empirically,the bandgap ener⁃gy derived from the three approaches follow the order of E_(ex)>E_(MS)>E_(TP),where three transition energies are from exci⁃tonic absorption,modulation spectroscopy,and Tauc-plot,respectively.In principle,defining E_(g) as the single-elec⁃tron bandgap,we expect E_(g)>E_(ex),thus,E_(g)>E_(TP).In the literature,E_(TP) is often interpreted as E_(g),which is conceptual⁃ly problematic.However,in many cases,because the excitonic peaks are not readily identifiable,the inconsistency be⁃tween E_(g) and E_(TP) becomes invisible.In this brief review,real world examples are used(1)to illustrate how excitonic absorption features depend sensitively on the sample and measurement conditions;(2)to demonstrate the differences between E_(ex),E_(MS),and E_(TP) when they can be extracted simultaneously for one sample;and(3)to show how the popular⁃ly adopted Tauc-plot could lead to misleading results.Finally,it is pointed out that if the excitonic absorption is not ob⁃servable,the modulation spectroscopy can often yield a more useful and reasonable bandgap than Tauc-plot.展开更多
基金Supported by the Natural Science Foundation of China(51705326,52075339)。
文摘In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are closely related to the hydrogen bonds(H-bonds)network between water molecules.Therefore,it is crucial to analyze the relationship between these two aspects.In this paper,the infrared spectrum and motion characteristics of the stretching vibrations of the O-H bonds in one-dimensional confined water(1DCW)and bulk water(BW)in(6,6)single-walled carbon nanotubes(SWNT)are studied by molecular dynamics simulations.The results show that the stretching vibrations of the two O-H bonds in 1DCW exhibit different frequencies in the infrared spectrum,while the O-H bonds in BW display two identical main frequency peaks.Further analysis using the spring oscillator model reveals that the difference in the stretching amplitude of the O-H bonds is the main factor causing the change in vibration frequency,where an increase in stretching amplitude leads to a decrease in spring stiffness and,consequently,a lower vibration frequency.A more in-depth study found that the interaction of H-bonds between water molecules is the fundamental cause of the increased stretching amplitude and decreased vibration frequency of the O-H bonds.Finally,by analyzing the motion trajectory of the H atoms,the dynamic differences between 1DCW and BW are clearly revealed.These findings provide a new perspective for understanding the behavior of water molecules at the nanoscale and are of significant importance in advancing the development of infrared spectroscopy detection technology.
基金Supported by Bissell Distinguished Professor Endowment Fund at UNC-Charlotte。
文摘Although there are numerous optical spectroscopy techniques and methods that have been used to extract the fundamental bandgap of a semiconductor,most of them belong to one of these three approaches:(1)the excitonic absorption,(2)modulation spectroscopy,and(3)the most widely used Tauc-plot.The excitonic absorption is based on a many-particle theory,which is physically the most correct approach,but requires more stringent crystalline quality and appropriate sample preparation and experimental implementation.The Tauc-plot is based on a single-particle theo⁃ry that neglects the many-electron effects.Modulation spectroscopy analyzes the spectroscopy features in the derivative spectrum,typically,of the reflectance and transmission under an external perturbation.Empirically,the bandgap ener⁃gy derived from the three approaches follow the order of E_(ex)>E_(MS)>E_(TP),where three transition energies are from exci⁃tonic absorption,modulation spectroscopy,and Tauc-plot,respectively.In principle,defining E_(g) as the single-elec⁃tron bandgap,we expect E_(g)>E_(ex),thus,E_(g)>E_(TP).In the literature,E_(TP) is often interpreted as E_(g),which is conceptual⁃ly problematic.However,in many cases,because the excitonic peaks are not readily identifiable,the inconsistency be⁃tween E_(g) and E_(TP) becomes invisible.In this brief review,real world examples are used(1)to illustrate how excitonic absorption features depend sensitively on the sample and measurement conditions;(2)to demonstrate the differences between E_(ex),E_(MS),and E_(TP) when they can be extracted simultaneously for one sample;and(3)to show how the popular⁃ly adopted Tauc-plot could lead to misleading results.Finally,it is pointed out that if the excitonic absorption is not ob⁃servable,the modulation spectroscopy can often yield a more useful and reasonable bandgap than Tauc-plot.
