A realistic dynamics simulation study is reported for the trans-cis photoisomerization of azobenzene triggered by the n →π^＊ excitation and the results show that the formation ofcis isomer follows the rotational mo...A realistic dynamics simulation study is reported for the trans-cis photoisomerization of azobenzene triggered by the n →π^＊ excitation and the results show that the formation ofcis isomer follows the rotational motion around the N=N bond. The simulation find that the CNN bond angle bending vibrations also play a significant role in the vibronic coupling between the HOMO and LUMO, which essentially leads a nonadiabatic transition of the molecule to the electronic ground state.展开更多
The photochromic ring-opening reaction of spiropyran（SP） has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF（12 10）/MS-CASPT2 potential energy curves（PECs） of S0–S2....The photochromic ring-opening reaction of spiropyran（SP） has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF（12 10）/MS-CASPT2 potential energy curves（PECs） of S0–S2.The main simulation results show the dominate pathway corresponds to the ringopening process of trans-SP to form the most stable merocyanine（MC） product.These findings provide more important complementarity for interpreting experimental observations.展开更多
Symmetrical quasi-classical （SQC） method based on mapping Hamiltonian is an efficient approach that is potentially useful to treat the nonadiabatic dynamics of very large systems. We try to evaluate the performance ...Symmetrical quasi-classical （SQC） method based on mapping Hamiltonian is an efficient approach that is potentially useful to treat the nonadiabatic dynamics of very large systems. We try to evaluate the performance of this method in the ultrafast electron transfer processes involving a few of electronic states and a large number of vibrational modes. The multilayer multiconfigurational time-dependent Hartree （ML-MCTDH） method was used to get the accurate dynamical results for benchmark. Although the population dynamics in the long- time limit show differences in the ML-MCTDH and SQC calculations, the SQC method gives acceptable results.展开更多
The ring-polymer molecular dynamics(RPMD)was used to calculate the thermal rate coefficients of the multi-channel roaming reaction H+MgH→Mg+H_(2).Two reaction channels,tight and roaming,are explicitly considered.This...The ring-polymer molecular dynamics(RPMD)was used to calculate the thermal rate coefficients of the multi-channel roaming reaction H+MgH→Mg+H_(2).Two reaction channels,tight and roaming,are explicitly considered.This is a pioneering attempt of exerting RPMD method to multichannel reactions.With the help of a newly developed optimization-interpolation protocol for preparing the initial structures and adaptive protocol for choosing the force constants,we have successfully obtained the thermal rate coefficients.The results are consistent with those from other theoretical methods,such as variational transition state theory and quantum dynamics.Especially,RPMD results exhibit negative temperature dependence,which is similar to the results from variational transition state theory but different from the ones from ground state quantum dynamics calculations.展开更多
The nonradiative decay of a n-stacked pair of adenine molecules, one of which was excited by an ultrafast laser pulse, is studied by semiclassical dynamics simulations. This simulation investigation is focused on the ...The nonradiative decay of a n-stacked pair of adenine molecules, one of which was excited by an ultrafast laser pulse, is studied by semiclassical dynamics simulations. This simulation investigation is focused on the effect of the formation of bonded excimer in stacked adenines on the mechanism of ultrafast decay. The simulation finds that the formation of the bond- ed excimer significantly lowers the energy gap between the LUMO and HOMO and consequently facilitates the deactivation of the electronically excited molecule. On the other hand, the formation of the chemical bond between two stacked adenines re- stricts the deformation vibration of the pyrimidine of the excited molecule due to the steric effect. This slows down the formation of the coupling between the HOMO and LUMO energy levels and therefore delays the deactivation process of the excited adenine molecule to the electronic ground state.展开更多
基金supported by the National Natural Science Foundation of China (No.20773168)Natural Science Foundation Project of CQ CSTC (No.2006BB2367 and 2006BB5368)Project of Science Technology Foundation of Chongqing Education Committee (No.KJ070506).
文摘A realistic dynamics simulation study is reported for the trans-cis photoisomerization of azobenzene triggered by the n →π^＊ excitation and the results show that the formation ofcis isomer follows the rotational motion around the N=N bond. The simulation find that the CNN bond angle bending vibrations also play a significant role in the vibronic coupling between the HOMO and LUMO, which essentially leads a nonadiabatic transition of the molecule to the electronic ground state.
基金supported by the National Natural Science Foundation of China (Nos. 21003100 and 21073242)Natural Science Basic Research Plan in Shaanxi Province of China (No. 2011JQ2013)Special Fund of Education Department of Shaanxi Province (No. 12JK0619)
文摘The photochromic ring-opening reaction of spiropyran（SP） has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF（12 10）/MS-CASPT2 potential energy curves（PECs） of S0–S2.The main simulation results show the dominate pathway corresponds to the ringopening process of trans-SP to form the most stable merocyanine（MC） product.These findings provide more important complementarity for interpreting experimental observations.
文摘Symmetrical quasi-classical （SQC） method based on mapping Hamiltonian is an efficient approach that is potentially useful to treat the nonadiabatic dynamics of very large systems. We try to evaluate the performance of this method in the ultrafast electron transfer processes involving a few of electronic states and a large number of vibrational modes. The multilayer multiconfigurational time-dependent Hartree （ML-MCTDH） method was used to get the accurate dynamical results for benchmark. Although the population dynamics in the long- time limit show differences in the ML-MCTDH and SQC calculations, the SQC method gives acceptable results.
基金supported by the National Natural Science Foundation of China(No.21503130 and No.11674212,and No.21603144)supported by the Young Eastern Scholar Program of the Shanghai Municipal Education Commission(QD2016021)+1 种基金the Shanghai Key Laboratory of High Temperature Superconductors(No.14DZ2260700)supported by Shanghai Sailing Program(No.2016YF1408400).
文摘The ring-polymer molecular dynamics(RPMD)was used to calculate the thermal rate coefficients of the multi-channel roaming reaction H+MgH→Mg+H_(2).Two reaction channels,tight and roaming,are explicitly considered.This is a pioneering attempt of exerting RPMD method to multichannel reactions.With the help of a newly developed optimization-interpolation protocol for preparing the initial structures and adaptive protocol for choosing the force constants,we have successfully obtained the thermal rate coefficients.The results are consistent with those from other theoretical methods,such as variational transition state theory and quantum dynamics.Especially,RPMD results exhibit negative temperature dependence,which is similar to the results from variational transition state theory but different from the ones from ground state quantum dynamics calculations.
基金supported by the National Natural Science Foundation of China (21073242)the Natural Science Foundation of Chongqing (cstc2011jjA00009)+1 种基金the Project of Science Technology Foundation of Chongqing Education Committee (KJ100507)the Research Fund of Chongqing University of Posts and Telecommunications (A2009-63,A2010-17)
文摘The nonradiative decay of a n-stacked pair of adenine molecules, one of which was excited by an ultrafast laser pulse, is studied by semiclassical dynamics simulations. This simulation investigation is focused on the effect of the formation of bonded excimer in stacked adenines on the mechanism of ultrafast decay. The simulation finds that the formation of the bond- ed excimer significantly lowers the energy gap between the LUMO and HOMO and consequently facilitates the deactivation of the electronically excited molecule. On the other hand, the formation of the chemical bond between two stacked adenines re- stricts the deformation vibration of the pyrimidine of the excited molecule due to the steric effect. This slows down the formation of the coupling between the HOMO and LUMO energy levels and therefore delays the deactivation process of the excited adenine molecule to the electronic ground state.
