In harmonic approximation,the vibrationally resolved S1?S0 electronic absorption and emission spectra of 7,8-benzoquinoline were simulated using the Franck-Condon approximation including the Herzberg-Teller and Duschi...In harmonic approximation,the vibrationally resolved S1?S0 electronic absorption and emission spectra of 7,8-benzoquinoline were simulated using the Franck-Condon approximation including the Herzberg-Teller and Duschinsky effects,and the results reproduced the experimental spectra very well.Our calculations show that the Herzberg-Teller effect and the Duschinsky mixing play key role in simulating correctly the weak or forbidden transition like the S1?S0 bands of 7,8-benzoquinoline,especially the former.Based on the present theoretical results,we tentatively assigned a few bands which were not unambiguously marked in the experimental spectra.Comparing the vibrationally resolved electronic spectra of 7,8-benzoquinoline with that of phenanthrene simulated in the previous study,the increased vibronic activity of 7,8-benzoquinoline is due to the symmetry break,which is caused by the introduction of N-heteroatom into the aromatic ring of phenanthrene.展开更多
In the present work, through the path integral of Gaussian type correlation function, a new formalism based on Fermi-Golden Rule for calculating the rate constant of nonradiative decay process with Duschinsky rotation...In the present work, through the path integral of Gaussian type correlation function, a new formalism based on Fermi-Golden Rule for calculating the rate constant of nonradiative decay process with Duschinsky rotation effect in polyatomic molecules is developed. The advantage of the present path-integral formalism is promoting-mode free. In order to get the rate constant, a "transition rate matrix" needs to be calculated. The rate constant calculated previously is only an approximation of diagonal elements of our "transition rate matrix " . The total rate should be the summation over all the matrix elements.展开更多
基金supported by the National Natural Science Foundation of China(91741105)Chongqing Municipal Natural Science Foundation(cstc2018jcyj AX0625)
文摘In harmonic approximation,the vibrationally resolved S1?S0 electronic absorption and emission spectra of 7,8-benzoquinoline were simulated using the Franck-Condon approximation including the Herzberg-Teller and Duschinsky effects,and the results reproduced the experimental spectra very well.Our calculations show that the Herzberg-Teller effect and the Duschinsky mixing play key role in simulating correctly the weak or forbidden transition like the S1?S0 bands of 7,8-benzoquinoline,especially the former.Based on the present theoretical results,we tentatively assigned a few bands which were not unambiguously marked in the experimental spectra.Comparing the vibrationally resolved electronic spectra of 7,8-benzoquinoline with that of phenanthrene simulated in the previous study,the increased vibronic activity of 7,8-benzoquinoline is due to the symmetry break,which is caused by the introduction of N-heteroatom into the aromatic ring of phenanthrene.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 10425420, 20433070 and 90503013)
文摘In the present work, through the path integral of Gaussian type correlation function, a new formalism based on Fermi-Golden Rule for calculating the rate constant of nonradiative decay process with Duschinsky rotation effect in polyatomic molecules is developed. The advantage of the present path-integral formalism is promoting-mode free. In order to get the rate constant, a "transition rate matrix" needs to be calculated. The rate constant calculated previously is only an approximation of diagonal elements of our "transition rate matrix " . The total rate should be the summation over all the matrix elements.
基金the National Natural Science Foundation of China(No.11674003,No.21873003,No.21503003,No.11704004,and No.61475001)Anhui Natural Science Foundation(No.1908085QA17)+1 种基金support from Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund(the second phase)(No.U1501501)Super Computation Center of Shenzhen。
