The relative conformer energies of glycine are evaluated by using a focal point analysis expressed as（HF→MP2→MP3→CCSD→CCSD（T））.The conformer abundances at various temperatures（298–500 K） are calculated base...The relative conformer energies of glycine are evaluated by using a focal point analysis expressed as（HF→MP2→MP3→CCSD→CCSD（T））.The conformer abundances at various temperatures（298–500 K） are calculated based on the relative energies and Boltzmann statistical thermostatistical analysis with and without considering internal hindered rotations.A comparison between the available Raman spectrum and the electron momentum spectrum confirms that the influence of rigid-rotor hindered rotation on the conformational proportions of glycine is considerable,especially for the IIIp structure.The conformational interconversions are discussed.It is found that with increasing temperature,the mole fraction of IIn keeps constant and Ip structure can convert into IVn and IIIp,leading to the decrease in the weight of Ip and the increase in the weights of IVn and IIIp conformers,which is in accordance with experimental observations.展开更多
The conformational interconversions of polymer chains have been of great interest as a basic scientific issue.Single-molecule force spectroscopy(SMFS)is a powerful tool for molecular manipulation,which enables experim...The conformational interconversions of polymer chains have been of great interest as a basic scientific issue.Single-molecule force spectroscopy(SMFS)is a powerful tool for molecular manipulation,which enables experimental studies on the single-chain behaviors of polymers.The SMFS results show that an individual polymer chain in a liquid environment may have similar properties to an ideal chain,which contradicts the traditional theoretical view.Herein,by taking into account the collisions of solvent molecules,the conformational interconversions of a single polymer chain in a liquid environment have been analyzed.The conformational interconversion frequency of a carbon-carbon bond of an alkane chain can be estimated by establishing the relationship between the internal rotation barriers of small molecules(monomers)and the corresponding macromolecules.Since the time scale of conformational interconversions of the polymer backbone is much shorter than that of SMFS experiments,most polymers with C-C backbones behave as ideal chains in liquid environments.展开更多
基金Project supported by the Young Scientists Funds of the National Natural Science Foundation of China(Grant Nos.11404154 and 11304136)
文摘The relative conformer energies of glycine are evaluated by using a focal point analysis expressed as（HF→MP2→MP3→CCSD→CCSD（T））.The conformer abundances at various temperatures（298–500 K） are calculated based on the relative energies and Boltzmann statistical thermostatistical analysis with and without considering internal hindered rotations.A comparison between the available Raman spectrum and the electron momentum spectrum confirms that the influence of rigid-rotor hindered rotation on the conformational proportions of glycine is considerable,especially for the IIIp structure.The conformational interconversions are discussed.It is found that with increasing temperature,the mole fraction of IIn keeps constant and Ip structure can convert into IVn and IIIp,leading to the decrease in the weight of Ip and the increase in the weights of IVn and IIIp conformers,which is in accordance with experimental observations.
基金This work was supported by the National Natural Science Foundation of China(No.22273079)the Natural Science Foundation of Sichuan Province,China(No.2022NSFSC1204)the Central Government Guiding Local Science and Technology Development Project of Sichuan Province,China(No.2022ZYD0043).
文摘The conformational interconversions of polymer chains have been of great interest as a basic scientific issue.Single-molecule force spectroscopy(SMFS)is a powerful tool for molecular manipulation,which enables experimental studies on the single-chain behaviors of polymers.The SMFS results show that an individual polymer chain in a liquid environment may have similar properties to an ideal chain,which contradicts the traditional theoretical view.Herein,by taking into account the collisions of solvent molecules,the conformational interconversions of a single polymer chain in a liquid environment have been analyzed.The conformational interconversion frequency of a carbon-carbon bond of an alkane chain can be estimated by establishing the relationship between the internal rotation barriers of small molecules(monomers)and the corresponding macromolecules.Since the time scale of conformational interconversions of the polymer backbone is much shorter than that of SMFS experiments,most polymers with C-C backbones behave as ideal chains in liquid environments.
