Development, benchmarking and application of improved quantum-classical trajectory surface-hopping methods for the ab initio simulation of photoinduced hydrogen-atom transfer reactions and the computation of time-resolved spectroscopic signals
Final Report Abstract
In the first funding period of this project, a pragmatic quasi-classical trajectory surfacehopping algorithm based on the Belyaev-Lebedev formula for the nonadiabatic transition probability was developed and implemented with the ADC(2) ab initio electronic-structure method. In the first project of second funding period, the capabilities of this efficient dynamics simulation method were exploited to develop insight into the microscopic reaction mechanisms of photocatalytic water splitting with graphitic carbon nitrides, which are polymeric organic photocatalytic materials of high current interest in solar energy conversion research. The time scales and branching ratios of the electron and proton transfer reactions involved in the oxidation of water and the evolution of hydrogen were explored in hydrogenbonded complexes of heptazine, the building block of polymeric carbon nitrides, with protic substrate molecules, such as water or phenol. In the second project, the computational efficiency of the Belyaev-Lebedev surface-hopping algorithm was exploited for the simulation of femtosecond time-resolved nonlinear spectra in the so-called doorway-window approximation. The formalism and the computer codes were developed for transient absorption pump-probe spectroscopy and for electronic two-dimensional spectroscopy and were applied for the ab initio calculation of the corresponding time- and frequency-resolved signals for the pyrazine molecule. These are the first ab initio calculations of femtosecond time-resolved optical spectra with quasi-classical trajectories in which the duration and spectral shapes of the laser pulses are consistently and non-empirically taken into account.
Publications
- Ab initio nonadiabatic surface-hopping trajectory simulations of photocatalytic water oxidation and hydrogen evolution with the heptazine molecule. J. Phys. Chem. A 125, 9917 (2021)
X. Huang and W. Domcke
(See online at https://doi.org/10.1021/acs.jpca.1c08291) - Ab initio quasiclassical simulation of femtosecond time-resolved two-dimensional electronic spectra of pyrazine. J. Phys. Chem. Lett. 12, 11736 (2021)
X. Huang, W. Xie, N. Došlić, M. F. Gelin and W. Domcke
(See online at https://doi.org/10.1021/acs.jpclett.1c03589) - Ab initio surface-hopping simulation of femtosecond transient absorption pump-probe signals of nonadiabatic excited-state dynamics using the doorway-window representation. J. Chem. Theory Comput. 17, 2394 (2021)
M. F. Gelin, X. Huang, W. Xie, L. Chen, N. Došlić and W. Domcke
(See online at https://doi.org/10.1021/acs.jctc.1c00109) - Ab initio trajectory surface-hopping dynamics studies of excited-state proton-coupled electron transfer reactions in trianisole-phenol complexes. Phys. Chem. Chem. Phys. 24, 15925 (2022)
X. Huang and W. Domcke
(See online at https://doi.org/10.1039/D2CP01262F)
