The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of th...The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of the naphthalene-triethylamine system consists of two emission bands, the fluorescence band of naphthalene(band A, 329 nm) and the emission band of the exciplex(band B, 468 nm). The intensities of both the emission bands decrease with increasing the solvent polarity. The intensity of band B also decreases due to the hydrogen-bonding interaction between triethylamine and protic solvent, while that of band A increases. It is thus suggested that the quenching of naphthalene fluorescence by triethylamine in THF occurs through the charge transfer and electron transfer reactions. The spectral changes upon the increase of solvent polarity can be explained by the dependences of the equilibrium constant between exciplex and ion-pair and the rate constant for the electron transfer reaction from triethylamine to the excited naphthalene on the relative permittivity of solvent. It is shown that the formation of intermolecular hydrogen-bonding between triethylamine and protic solvent suppresses the quenching reaction by the decrease in free amine. Acetonitrile has only a polar effect and trichloroacetic acid only a hydrogen-bonding(or protonation) effect, while alcohols have both the effects. The effects of alcohols could be separated into the effects of solvent polarity and intermolecular hydrogen-bonding interaction quantitatively.展开更多
A modified uncertainty principle coupling the intervals of energy and time can lead to the shortest distance attained in course of the excitation process, as well as the shortest possible time interval for that proces...A modified uncertainty principle coupling the intervals of energy and time can lead to the shortest distance attained in course of the excitation process, as well as the shortest possible time interval for that process. These lower bounds are much similar to the interval limits deduced on both the experimental and theoretical footing in the era when the Heisenberg uncertainty principle has been developed. In effect of the bounds existence, a maximal nuclear charge Ze acceptable for the Bohr atomic ion could be calculated. In the next step the velocity of electron transitions between the Bohr orbits is found to be close to the speed of light. This result provides us with the energy spectrum of transitions similar to that obtained in the Bohr’s model. A momentary force acting on the electrons in course of their transitions is estimated to be by many orders larger than a steady electrostatic force existent between the atomic electron and the nucleus.展开更多
The effects of an anti-hydrogen bond on the v1 v12 Fermi resonance （FR） of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, and pyri...The effects of an anti-hydrogen bond on the v1 v12 Fermi resonance （FR） of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, and pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode v1 and triangle mode v12 of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the v1-v12 Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the v1-v12 FR of pyridine. According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the v1 - v12 FR of pyridine is given.展开更多
Definitions of the mechanical parameters entering the Bohr model of the hydrogen atom allowed us to calculate the time intervals connected with the electron transitions between the nearest-neighbouring energy levels i...Definitions of the mechanical parameters entering the Bohr model of the hydrogen atom allowed us to calculate the time intervals connected with the electron transitions between the nearest-neighbouring energy levels in the atom. This is done in a strictly non-probabilistic way. The time results are compared with those derived earlier on the basis of the classical Joule-Lenz law for the energy emission adapted to the case of the electron transfer in the quantum systems. A similar formalism has been next applied to the harmonic oscillator and a particle moving in the one-dimensional potential box.展开更多
A new copper(Ⅱ) complex [Cu(PDA)(H 2O) 2] was synthesized and its structure was determined. Cu(Ⅱ) is five coordinated in a tetragonal pyramid geometry. The two coordinating water molecules are different and t...A new copper(Ⅱ) complex [Cu(PDA)(H 2O) 2] was synthesized and its structure was determined. Cu(Ⅱ) is five coordinated in a tetragonal pyramid geometry. The two coordinating water molecules are different and the two Cu-O bond lengths differ by nearly 0.02 nm. The whole crystal is linked to form a three dimensional network by means of hydrogen bonds. The X band ESR spectrum shows three different g tensors with a well resolved hyperfine structure in the g z signal, giving the ESR parameters g x=2 05, g y =2 065 and g z =2 29. The covalency of the coordinate bonds and the deviation from tetragonal pyramid geometry for the complex are discussed based on the ESR spectra.展开更多
文摘The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of the naphthalene-triethylamine system consists of two emission bands, the fluorescence band of naphthalene(band A, 329 nm) and the emission band of the exciplex(band B, 468 nm). The intensities of both the emission bands decrease with increasing the solvent polarity. The intensity of band B also decreases due to the hydrogen-bonding interaction between triethylamine and protic solvent, while that of band A increases. It is thus suggested that the quenching of naphthalene fluorescence by triethylamine in THF occurs through the charge transfer and electron transfer reactions. The spectral changes upon the increase of solvent polarity can be explained by the dependences of the equilibrium constant between exciplex and ion-pair and the rate constant for the electron transfer reaction from triethylamine to the excited naphthalene on the relative permittivity of solvent. It is shown that the formation of intermolecular hydrogen-bonding between triethylamine and protic solvent suppresses the quenching reaction by the decrease in free amine. Acetonitrile has only a polar effect and trichloroacetic acid only a hydrogen-bonding(or protonation) effect, while alcohols have both the effects. The effects of alcohols could be separated into the effects of solvent polarity and intermolecular hydrogen-bonding interaction quantitatively.
文摘A modified uncertainty principle coupling the intervals of energy and time can lead to the shortest distance attained in course of the excitation process, as well as the shortest possible time interval for that process. These lower bounds are much similar to the interval limits deduced on both the experimental and theoretical footing in the era when the Heisenberg uncertainty principle has been developed. In effect of the bounds existence, a maximal nuclear charge Ze acceptable for the Bohr atomic ion could be calculated. In the next step the velocity of electron transitions between the Bohr orbits is found to be close to the speed of light. This result provides us with the energy spectrum of transitions similar to that obtained in the Bohr’s model. A momentary force acting on the electrons in course of their transitions is estimated to be by many orders larger than a steady electrostatic force existent between the atomic electron and the nucleus.
基金Project supported by the National Natural Science Foundation of China （Grant No. 10974067） and the Graduate Innovation Fund of Jilin University, China （Grant No. 20101055）.
文摘The effects of an anti-hydrogen bond on the v1 v12 Fermi resonance （FR） of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, and pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode v1 and triangle mode v12 of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the v1-v12 Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the v1-v12 FR of pyridine. According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the v1 - v12 FR of pyridine is given.
文摘Definitions of the mechanical parameters entering the Bohr model of the hydrogen atom allowed us to calculate the time intervals connected with the electron transitions between the nearest-neighbouring energy levels in the atom. This is done in a strictly non-probabilistic way. The time results are compared with those derived earlier on the basis of the classical Joule-Lenz law for the energy emission adapted to the case of the electron transfer in the quantum systems. A similar formalism has been next applied to the harmonic oscillator and a particle moving in the one-dimensional potential box.
基金Supported by the National Natural Science Foundation of China(No.2 0 0 710 192 0 0 710 2 0 and5 0 172 0 2 ) and the Re-search Fund for Doctoral Program of Higher Education.
文摘A new copper(Ⅱ) complex [Cu(PDA)(H 2O) 2] was synthesized and its structure was determined. Cu(Ⅱ) is five coordinated in a tetragonal pyramid geometry. The two coordinating water molecules are different and the two Cu-O bond lengths differ by nearly 0.02 nm. The whole crystal is linked to form a three dimensional network by means of hydrogen bonds. The X band ESR spectrum shows three different g tensors with a well resolved hyperfine structure in the g z signal, giving the ESR parameters g x=2 05, g y =2 065 and g z =2 29. The covalency of the coordinate bonds and the deviation from tetragonal pyramid geometry for the complex are discussed based on the ESR spectra.
