Experimental vibrational spectra of heavy light XH stretching vibrations of simple molecules have been analyzed using the local mode model.In addition,the bond dipole approach,which assumes that the transition dipole ...Experimental vibrational spectra of heavy light XH stretching vibrations of simple molecules have been analyzed using the local mode model.In addition,the bond dipole approach,which assumes that the transition dipole moment(TDM)of the XH stretching mode is aligned along the XH bond,has helped analyze experimental spectra.We performed theoretical calculations of the XH stretching vibrations of HOD,HND^−,HCD,HSD,HPD^−,and HSiD using local mode model and multi-dimensional normal modes.We found that consistent with previous notions,a localized 1D picture to treat the XH stretching vibration is valid even for analyzing the TDM tilt angle.In addition,while the TDM of the OH stretching fundamental transition tilted away from the OH bond in the direction away from the OD bond,that for the XH stretching fundamental of HSD,HND^−,HPD^−,HCD,and HSiD tilted away from the OH bond but toward the OD bond.This shows that bond dipole approximation may not be a good approximation for the present systems and that the heavy atom X can affect the transition dipole moment direction.The variation of the dipole moment was analyzed using the atoms-in-molecule method.展开更多
Decoupling the complicated vibrational-vibrational （V-V） coupling of a multimode vibrational relaxation remains a challenge for analyzing the sound relaxational absorption in multi-component gas mixtures. In our pre...Decoupling the complicated vibrational-vibrational （V-V） coupling of a multimode vibrational relaxation remains a challenge for analyzing the sound relaxational absorption in multi-component gas mixtures. In our previous work [Acta Phys. Sin. 61 174301 （2012）], an analytical model to predict the sound absorption from vibrational relaxation in a gas medium is proposed. In this paper, we develop the model to decouple the V-V coupled energy to each vibrationaltranslational deexcitation path, and analyze how the multimode relaxations form the peaks of sound absorption spectra in gas mixtures. We prove that a multimode relaxation is the sum of its decoupled single-relaxation processes, and only the decoupled process with a significant isochoric-molar-heat can be observed as an absorption peak. The decoupling model clarifies the essential processes behind the peaks in spectra arising from the multimode relaxations in multi-component gas mixtures. The simulation validates the proposed decoupling model.展开更多
Otamixaban is a potent （Ki=0.5 nM） fXa inhibitor currently in late-stage clinical develop-ment at Sanofi for the management of acute coronary syndrome. Being unproductive in obtaining a suitable crystal of Otamixaba...Otamixaban is a potent （Ki=0.5 nM） fXa inhibitor currently in late-stage clinical develop-ment at Sanofi for the management of acute coronary syndrome. Being unproductive in obtaining a suitable crystal of Otamixaban, the required enantiomeric characterization has been accomplished using vibrational circular dichroism （VCD） spectroscopy. Selected by a spectrum similarity index, the calculated spectra of several higher energy conformers were found to match well with the observed spectra. The characteristic IR bands of these conformers were also identified and attributed to the solvation effect. Combined with both the single crystal x-ray diffraction results for an intermediate and the proton NMR study, the absolute configuration of Otamixaban is unambiguously determined to be （R,R）.展开更多
An iterative procedure is proposed to facilitate the determination of molecular vi-brational force constants from the experimental fundamental frequencies. Proper restrictions are introduced to the force constants ba... An iterative procedure is proposed to facilitate the determination of molecular vi-brational force constants from the experimental fundamental frequencies. Proper restrictions are introduced to the force constants based on physical considerations for getting reasonable results. The experimental data of Coriolis coupling coefficients and isotopic frequency shifts are utilized to reduce the uncertainty of the calculated force constants when they are available. A series of various kinds of molecules have been calculated by this method and the results are satisfactory.展开更多
The (4000), (3100) and (5000) local mode vibrational bands of germane were recorded with high resolution spectroscopy. The anomalous relative intensities of these bands were found and explained with a bond bond coupli...The (4000), (3100) and (5000) local mode vibrational bands of germane were recorded with high resolution spectroscopy. The anomalous relative intensities of these bands were found and explained with a bond bond coupling dipole moment model. The calculated results, which were also compared with those from the former theoretical model, agree well with the experimental data.展开更多
A new mechanism is proposed to implement the synchronization of the four unbalanced rotors in a vibrating system, which consists of a main rigid frame (MRF) and two accessorial rigid frames (ARF). An analytical approa...A new mechanism is proposed to implement the synchronization of the four unbalanced rotors in a vibrating system, which consists of a main rigid frame (MRF) and two accessorial rigid frames (ARF). An analytical approach is developed to study the coupling dynamic characteristics of the four unbalanced rotors, which converts the problem of synchronization of the four unbalanced rotors into the existence and the stability of zero solutions for the non-dimensional differential equations of the angular velocity disturbance parameters (NDDEDP). The stability of zero solutions of the NDDEDP is decomposed into that of its generalized system and a system of the three first order differential equations for the disturbance parameters of the phase differences. The coupling dynamic characteristic of the four unbalanced rotors includes the inertia coupling, the stiffness coupling of angular velocity and the load torque coupling. The non-dimensional inertia coupling matrix is symmetric, the non dimensional matrix of the stiffness coupling of angular velocity is antisymmetric and its diagonal elements are all negative. Hence, the general system of the NDDEDP automatically satisfies the generalized Lyapunov equations when the non-dimensional inertia coupling matrix is positive definite and its elements are all positive. Using Routh-Hurwitz criterion the condition of stability of differential equations for the disturbance parameters of the phase differences is obtained. The load torque coupling makes the vibrating system have the dynamic characteristic of selecting motions and self-synchronization of the four unbalanced rotors arises from the dynamic characteristic of selecting motion of the vibrating system. When the two coefficients of coupling cosine effect of phase angles are all greater than 0 and the three indexes of synchronization are all far greater than 1, the vibrating system can implement an elliptical motion of the main rigid frame required in engineering. Numeric results show that the structural parameters of the pro展开更多
文摘Experimental vibrational spectra of heavy light XH stretching vibrations of simple molecules have been analyzed using the local mode model.In addition,the bond dipole approach,which assumes that the transition dipole moment(TDM)of the XH stretching mode is aligned along the XH bond,has helped analyze experimental spectra.We performed theoretical calculations of the XH stretching vibrations of HOD,HND^−,HCD,HSD,HPD^−,and HSiD using local mode model and multi-dimensional normal modes.We found that consistent with previous notions,a localized 1D picture to treat the XH stretching vibration is valid even for analyzing the TDM tilt angle.In addition,while the TDM of the OH stretching fundamental transition tilted away from the OH bond in the direction away from the OD bond,that for the XH stretching fundamental of HSD,HND^−,HPD^−,HCD,and HSiD tilted away from the OH bond but toward the OD bond.This shows that bond dipole approximation may not be a good approximation for the present systems and that the heavy atom X can affect the transition dipole moment direction.The variation of the dipole moment was analyzed using the atoms-in-molecule method.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 60971009 and 61001011)the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20090142110019)+1 种基金the Natural Science Foundation of Hubei Province, China (Grant No. 2010CDB02701)the Fundamental Research Funds for the Central Universities, China (Grant No. 2012QN083)
文摘Decoupling the complicated vibrational-vibrational （V-V） coupling of a multimode vibrational relaxation remains a challenge for analyzing the sound relaxational absorption in multi-component gas mixtures. In our previous work [Acta Phys. Sin. 61 174301 （2012）], an analytical model to predict the sound absorption from vibrational relaxation in a gas medium is proposed. In this paper, we develop the model to decouple the V-V coupled energy to each vibrationaltranslational deexcitation path, and analyze how the multimode relaxations form the peaks of sound absorption spectra in gas mixtures. We prove that a multimode relaxation is the sum of its decoupled single-relaxation processes, and only the decoupled process with a significant isochoric-molar-heat can be observed as an absorption peak. The decoupling model clarifies the essential processes behind the peaks in spectra arising from the multimode relaxations in multi-component gas mixtures. The simulation validates the proposed decoupling model.
文摘Otamixaban is a potent （Ki=0.5 nM） fXa inhibitor currently in late-stage clinical develop-ment at Sanofi for the management of acute coronary syndrome. Being unproductive in obtaining a suitable crystal of Otamixaban, the required enantiomeric characterization has been accomplished using vibrational circular dichroism （VCD） spectroscopy. Selected by a spectrum similarity index, the calculated spectra of several higher energy conformers were found to match well with the observed spectra. The characteristic IR bands of these conformers were also identified and attributed to the solvation effect. Combined with both the single crystal x-ray diffraction results for an intermediate and the proton NMR study, the absolute configuration of Otamixaban is unambiguously determined to be （R,R）.
基金Project supported by the National Natural Science Foundation of China.
文摘 An iterative procedure is proposed to facilitate the determination of molecular vi-brational force constants from the experimental fundamental frequencies. Proper restrictions are introduced to the force constants based on physical considerations for getting reasonable results. The experimental data of Coriolis coupling coefficients and isotopic frequency shifts are utilized to reduce the uncertainty of the calculated force constants when they are available. A series of various kinds of molecules have been calculated by this method and the results are satisfactory.
文摘The (4000), (3100) and (5000) local mode vibrational bands of germane were recorded with high resolution spectroscopy. The anomalous relative intensities of these bands were found and explained with a bond bond coupling dipole moment model. The calculated results, which were also compared with those from the former theoretical model, agree well with the experimental data.
基金supported by the National Natural Science Foundation of China (Grant No. 50535010)Project of Liaoning Province College Science and Research (Grant No. 2008S095)Program for Changjiang Scholars and Innovative Research Team in University
文摘A new mechanism is proposed to implement the synchronization of the four unbalanced rotors in a vibrating system, which consists of a main rigid frame (MRF) and two accessorial rigid frames (ARF). An analytical approach is developed to study the coupling dynamic characteristics of the four unbalanced rotors, which converts the problem of synchronization of the four unbalanced rotors into the existence and the stability of zero solutions for the non-dimensional differential equations of the angular velocity disturbance parameters (NDDEDP). The stability of zero solutions of the NDDEDP is decomposed into that of its generalized system and a system of the three first order differential equations for the disturbance parameters of the phase differences. The coupling dynamic characteristic of the four unbalanced rotors includes the inertia coupling, the stiffness coupling of angular velocity and the load torque coupling. The non-dimensional inertia coupling matrix is symmetric, the non dimensional matrix of the stiffness coupling of angular velocity is antisymmetric and its diagonal elements are all negative. Hence, the general system of the NDDEDP automatically satisfies the generalized Lyapunov equations when the non-dimensional inertia coupling matrix is positive definite and its elements are all positive. Using Routh-Hurwitz criterion the condition of stability of differential equations for the disturbance parameters of the phase differences is obtained. The load torque coupling makes the vibrating system have the dynamic characteristic of selecting motions and self-synchronization of the four unbalanced rotors arises from the dynamic characteristic of selecting motion of the vibrating system. When the two coefficients of coupling cosine effect of phase angles are all greater than 0 and the three indexes of synchronization are all far greater than 1, the vibrating system can implement an elliptical motion of the main rigid frame required in engineering. Numeric results show that the structural parameters of the pro
