Based on our discovery of neutral aluminum molecular rings,we herein introduce rare earth ions into the center of the ring and reveal their structural adaptability.The resulting yoyo-like cationic macrocycles are high...Based on our discovery of neutral aluminum molecular rings,we herein introduce rare earth ions into the center of the ring and reveal their structural adaptability.The resulting yoyo-like cationic macrocycles are highly adaptive to guests,creating unusual supramolecular assemblies.The first category is stacked with singly oriented rhombohedral channels,which exhibit fast and reversible solvent-triggered molecular motions and structural rearrangements.The second type of assembly is that yoyo macrocycles and guest molecules form a nested host-guest sodalite cage supramolecular structure.It is uncommon for guest molecules to be well-defined within cages although caged structures have been well-documented.Their host-guest interaction discussion reveals the self-adaptation and flexibility of the yoyo macrocycles.Considering their good water stability,we investigated their anion exchange properties.The results show that they have significant exchange capacity for KI/I_(2),ReO_(4)^(-),and MnO_(4)^(-),revealing their potential application in water purification and nuclear waste treatment.展开更多
The thermal entanglement in the triangular molecular spin ring with Dzyaloshinskii-Moriya interaction is studied. The concurrences of arbitrary two spins of the triangular molecular spin ring for various cases are eva...The thermal entanglement in the triangular molecular spin ring with Dzyaloshinskii-Moriya interaction is studied. The concurrences of arbitrary two spins of the triangular molecular spin ring for various cases are evaluated. The tendency of the concurrence with Dzyaloshinskii-Moriya interaction and temperature is analysed and discussed. We note that the concurrence arrives at its maximum in the regime with the large Dzyaloshinskii-Moriya interaction and low temperature, and gradually decreases to zero with the increase of temperature. The concurrence has different features for the ferromagnetic and antiferromagnetic cases. For completeness, we also numerically calculate the concurrence of spin rings with N 〉 3 spins and analyse their behaviours.展开更多
The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer mol...The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics(RPMD)method on a full-dimensional potential energy surface(PES).This PES is the most accurate one for the title reaction,as demonstrated by the correct barrier height and reaction energy,compared to the benchmark calculations by the focal point analysis and the high accuracy extrapolated ab initio thermochemistry methods.The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation technique,and some experimental measurements.As has been found in many RPMD applications,quantum effects,including tunneling and zero-point energy effects,can be efficiently and effectively captured by the RPMD method.In addition,the convergence of the results with respect to the number of beads is rapid,which is also consistent with previous RPMD applications.展开更多
Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very g...Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.展开更多
The static and dynamic properties of a system of end-grafted flexible ring polymer chains grafted to a flat substrate and exposed to a good solvent are studied by using a molecular dynamics method. The monomers are de...The static and dynamic properties of a system of end-grafted flexible ring polymer chains grafted to a flat substrate and exposed to a good solvent are studied by using a molecular dynamics method. The monomers are described by a coarse-grained bead-spring model. Varying the grafting density p and the degree of polymerization or chain length N, we obtain the density profiles of monomers, study the structural properties of the chain （radius of gyration, bond orientational parameters, etc.）, and also present the dynamic characteristics such as chain energy and bond force. Compared with a linear polymer brush, the ring polymer brush exhibits different static and dynamic properties for moderate or short chain length, while it behaves like linear polymer brush in the regime of long chain length.展开更多
We investigate global entanglement in the ground state of single-molecular magnet Na9[Cu3Na3（H2O）9（α- AsW9O33）2]-26H2O with an external magnetic field. The concurrence, tangle, and measure function Q, which chara...We investigate global entanglement in the ground state of single-molecular magnet Na9[Cu3Na3（H2O）9（α- AsW9O33）2]-26H2O with an external magnetic field. The concurrence, tangle, and measure function Q, which characterize the pairwise entanglement, 3-party entanglement and total entanglement, respectively, are calculated numerically at zero temperature. The results show that the magnitude and direction of the applied magnetic field play a significant role in the properties of three kinds of entanglement measures. We give a physical interpretation of the variation of the global entanglement with the magnetic field. Finally, the phase diagram of the global entanglement characterized by the critical magnetic fields is presented.展开更多
The phase behaviour of polyethylene knotted ring chains is investigated by using molecular dynamics simulations. In this paper, we focus on the collapse of the polyethylene knotted ring chain, and also present the res...The phase behaviour of polyethylene knotted ring chains is investigated by using molecular dynamics simulations. In this paper, we focus on the collapse of the polyethylene knotted ring chain, and also present the results of linear and ring chains for comparison. At high temperatures, a fully extensive knot structure is observed. The mean-square radius of gyration per bond （S2）/（Nb2） and the shape factor （（δ＊） depend on not only the chain length but also the knot type. With temperature decreasing, chain collapse is observed, and the collapse temperature decreases with the chain length increasing. The actual collapse transition can be determined by the specific heat capacity Cv, and the knotted ring chain undergoes gas-liquid-solid-like transition directly. The phase transition of a knotted ring chain is only one-stage collapse, which is different from the polyethylene linear and ring chains. This investigation can provide some insights into the statistical properties of knotted polymer chains.展开更多
An atmospheric-pressure argon plasma jet with screw ring-ring electrodes in surface dielectric barrier discharge is generated by a sinusoidal excitation voltage at 8 kHz. The discharge characteristics, such as rotatio...An atmospheric-pressure argon plasma jet with screw ring-ring electrodes in surface dielectric barrier discharge is generated by a sinusoidal excitation voltage at 8 kHz. The discharge characteristics, such as rotational and vibrational temperature of nitrogen, electronic excitation temperature, oxygen atomic density, nitrogen molecular density, and average electron density, are estimated. It is found that the rotational temperature of nitrogen is in the range of 352 ～ 392 K by comparing the simulated spectrum with the measured spectrum at the C3Πu → B3Πg （△ν = 2） band transition, the electronic excitation temperature is found to be in the range of 3127 ～ 3230 K by using the Boltzmann plot method, the oxygen atomic and nitrogen molecular density are of the order of magnitude of 1016 cm-3 by the actinometry method, and the average electron density is of the order of magnitude of 1012 cm-3 by the energy balance equation. Besides, the effective power, conduction, and displacement current are measured during the discharge.展开更多
Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by...Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by using bipyridyl ligands based on biphenyl unit and half-sandwich binuclear rhodium(III)/iridium(III) building blocks.The selective synthesis was realized by adjusting the length of dipyridyl arms.The utilization of curved U-shaped bipyridyl ligand L1 led to tweezer-like molecular assemblies.Subsequently,olefinic bonds were introduced to elongate dipyridyl arms obtaining ligand L2.The ligand L2 has two stable conformations,U-shape and Z-shape,which facilitated the formation of different topologies including the tetranuclear macrocycle and Borromean rings with different building blocks in this work.These structures in solid and solution all have been further confirmed by single-crystal X-ray diffraction,NMR analysis,and mass spectrometry.In addition,as an important driving force,π-π stacking interactions not only played a significant role in the stability of structures but also further triggered photothermal conversion in solution.The experimental results demonstrated that compounds 1a and 2 had good NIR photothermal conversion efficiency (11.83% and 17.76%),and further analysis found the photothermal conversion efficiency had a gradual increase in the trend with the π-π stacking interactions increasing.This research expands the application of topological structures in materials science and provides a new idea for the synthesis of novel photothermal conversion materials.展开更多
基金supported by the National Natural Science Foundation of China(92061104,21771181,21935010)the Natural Science Foundation of Fujian Province(2021J06035)the Youth Innovation Promotion Association CAS(2017345,Y2018081)。
文摘Based on our discovery of neutral aluminum molecular rings,we herein introduce rare earth ions into the center of the ring and reveal their structural adaptability.The resulting yoyo-like cationic macrocycles are highly adaptive to guests,creating unusual supramolecular assemblies.The first category is stacked with singly oriented rhombohedral channels,which exhibit fast and reversible solvent-triggered molecular motions and structural rearrangements.The second type of assembly is that yoyo macrocycles and guest molecules form a nested host-guest sodalite cage supramolecular structure.It is uncommon for guest molecules to be well-defined within cages although caged structures have been well-documented.Their host-guest interaction discussion reveals the self-adaptation and flexibility of the yoyo macrocycles.Considering their good water stability,we investigated their anion exchange properties.The results show that they have significant exchange capacity for KI/I_(2),ReO_(4)^(-),and MnO_(4)^(-),revealing their potential application in water purification and nuclear waste treatment.
基金Project supported by the Teaching and Research Foundation for the Outstanding Young Faculty of Southeast University,China
文摘The thermal entanglement in the triangular molecular spin ring with Dzyaloshinskii-Moriya interaction is studied. The concurrences of arbitrary two spins of the triangular molecular spin ring for various cases are evaluated. The tendency of the concurrence with Dzyaloshinskii-Moriya interaction and temperature is analysed and discussed. We note that the concurrence arrives at its maximum in the regime with the large Dzyaloshinskii-Moriya interaction and low temperature, and gradually decreases to zero with the increase of temperature. The concurrence has different features for the ferromagnetic and antiferromagnetic cases. For completeness, we also numerically calculate the concurrence of spin rings with N 〉 3 spins and analyse their behaviours.
基金supported by the National Natural Science Foundation of China(No.21573027)
文摘The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics(RPMD)method on a full-dimensional potential energy surface(PES).This PES is the most accurate one for the title reaction,as demonstrated by the correct barrier height and reaction energy,compared to the benchmark calculations by the focal point analysis and the high accuracy extrapolated ab initio thermochemistry methods.The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation technique,and some experimental measurements.As has been found in many RPMD applications,quantum effects,including tunneling and zero-point energy effects,can be efficiently and effectively captured by the RPMD method.In addition,the convergence of the results with respect to the number of beads is rapid,which is also consistent with previous RPMD applications.
基金supported by the National Natural Science Foundation of China(No.21773251 and No.21973098)the Youth Innovation Promotion Association CAS(No.2018045)the Beijing National Laboratory for Molecular Sciences。
文摘Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 50873083 and 10974162)
文摘The static and dynamic properties of a system of end-grafted flexible ring polymer chains grafted to a flat substrate and exposed to a good solvent are studied by using a molecular dynamics method. The monomers are described by a coarse-grained bead-spring model. Varying the grafting density p and the degree of polymerization or chain length N, we obtain the density profiles of monomers, study the structural properties of the chain （radius of gyration, bond orientational parameters, etc.）, and also present the dynamic characteristics such as chain energy and bond force. Compared with a linear polymer brush, the ring polymer brush exhibits different static and dynamic properties for moderate or short chain length, while it behaves like linear polymer brush in the regime of long chain length.
基金supported by the National Natural Science Foundation of China(Grant No.11274102)the Program for New Century Excellent Talents in Universities,China(Grant No.NCET-11-0960)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No.20134208110001)
文摘We investigate global entanglement in the ground state of single-molecular magnet Na9[Cu3Na3（H2O）9（α- AsW9O33）2]-26H2O with an external magnetic field. The concurrence, tangle, and measure function Q, which characterize the pairwise entanglement, 3-party entanglement and total entanglement, respectively, are calculated numerically at zero temperature. The results show that the magnitude and direction of the applied magnetic field play a significant role in the properties of three kinds of entanglement measures. We give a physical interpretation of the variation of the global entanglement with the magnetic field. Finally, the phase diagram of the global entanglement characterized by the critical magnetic fields is presented.
基金supported by the National Natural Science Foundation of China (Grant Nos. 20574052,20774066,20974081,and 20934004)the Program for New Century Excellent Talents in University of the Ministry of Education of China (Grant No. NCET-05-0538)the Ph.D. Program Foundation of the Ministry of Education of China (Grant No. 20090101110002)
文摘The phase behaviour of polyethylene knotted ring chains is investigated by using molecular dynamics simulations. In this paper, we focus on the collapse of the polyethylene knotted ring chain, and also present the results of linear and ring chains for comparison. At high temperatures, a fully extensive knot structure is observed. The mean-square radius of gyration per bond （S2）/（Nb2） and the shape factor （（δ＊） depend on not only the chain length but also the knot type. With temperature decreasing, chain collapse is observed, and the collapse temperature decreases with the chain length increasing. The actual collapse transition can be determined by the specific heat capacity Cv, and the knotted ring chain undergoes gas-liquid-solid-like transition directly. The phase transition of a knotted ring chain is only one-stage collapse, which is different from the polyethylene linear and ring chains. This investigation can provide some insights into the statistical properties of knotted polymer chains.
基金supported by National Natural Science Foundation of China(No.51177007)Ministry of Science and Technology of China(No.2009AA064101-4)
文摘An atmospheric-pressure argon plasma jet with screw ring-ring electrodes in surface dielectric barrier discharge is generated by a sinusoidal excitation voltage at 8 kHz. The discharge characteristics, such as rotational and vibrational temperature of nitrogen, electronic excitation temperature, oxygen atomic density, nitrogen molecular density, and average electron density, are estimated. It is found that the rotational temperature of nitrogen is in the range of 352 ～ 392 K by comparing the simulated spectrum with the measured spectrum at the C3Πu → B3Πg （△ν = 2） band transition, the electronic excitation temperature is found to be in the range of 3127 ～ 3230 K by using the Boltzmann plot method, the oxygen atomic and nitrogen molecular density are of the order of magnitude of 1016 cm-3 by the actinometry method, and the average electron density is of the order of magnitude of 1012 cm-3 by the energy balance equation. Besides, the effective power, conduction, and displacement current are measured during the discharge.
基金supported by the National Natural Science Foundation of China(Nos.22031003,21720102004)the Shanghai Science Technology Committee(No.19DZ2270100)G.-X.J.thanks the Alexander von Humboldt Foundation for a Humboldt Research Award.
文摘Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by using bipyridyl ligands based on biphenyl unit and half-sandwich binuclear rhodium(III)/iridium(III) building blocks.The selective synthesis was realized by adjusting the length of dipyridyl arms.The utilization of curved U-shaped bipyridyl ligand L1 led to tweezer-like molecular assemblies.Subsequently,olefinic bonds were introduced to elongate dipyridyl arms obtaining ligand L2.The ligand L2 has two stable conformations,U-shape and Z-shape,which facilitated the formation of different topologies including the tetranuclear macrocycle and Borromean rings with different building blocks in this work.These structures in solid and solution all have been further confirmed by single-crystal X-ray diffraction,NMR analysis,and mass spectrometry.In addition,as an important driving force,π-π stacking interactions not only played a significant role in the stability of structures but also further triggered photothermal conversion in solution.The experimental results demonstrated that compounds 1a and 2 had good NIR photothermal conversion efficiency (11.83% and 17.76%),and further analysis found the photothermal conversion efficiency had a gradual increase in the trend with the π-π stacking interactions increasing.This research expands the application of topological structures in materials science and provides a new idea for the synthesis of novel photothermal conversion materials.
