On-the-fly Symmetrical Quasi-classical Dynamics with Meyer-Miller Mapping Hamiltonian for the Treatment of Nonadiabatic Dynamics at Conical Intersections

Author(s):  
Deping Hu ◽  
Yu Xie ◽  
Jiawei Peng ◽  
Zhenggang Lan

The ‘on-the-fly’ version of the symmetrical quasi-classical dynamics method based on the Meyer-Miller mapping Hamiltonian (SQC/MM) is implemented to study the nonadiabatic dynamics at conical intersections of polyatomic systems. The current ‘on-the-fly’ implementation of the SQC/MM method is based on the adiabatic representation and the dressed momentum. To include the zero-point energy (ZPE) correction of the electronic mapping variables, we employed both the γ-adjusted and γ-fixed approaches. Nonadiabatic dynamics of the methaniminium cation (CH2NH2+) and azomethane are simulated using the on-the-fly SQC/MM method. For CH2NH2+, both two ZPE correction approaches give reasonable and consistent results. However, for azomethane, the γ-adjusted version of the SQC/MM dynamics behaves much better than the γ-fixed version. The further analysis indicates that it is always recommended to use the γ-adjusted SQC/MM dynamics in the on-the-fly simulation of photoinduced dynamics of polyatomic systems, particularly when the excited-state is well separated from the ground state in the Frank-Condon region. This work indicates that the on-the-fly SQC/MM method is a powerful simulation protocol to deal with the nonadiabatic dynamics of realistic polyatomic systems.

2020 ◽  
Author(s):  
Deping Hu ◽  
Yu Xie ◽  
Jiawei Peng ◽  
Zhenggang Lan

The ‘on-the-fly’ version of the symmetrical quasi-classical dynamics method based on the Meyer-Miller mapping Hamiltonian (SQC/MM) is implemented to study the nonadiabatic dynamics at conical intersections of polyatomic systems. The current ‘on-the-fly’ implementation of the SQC/MM method is based on the adiabatic representation and the dressed momentum. To include the zero-point energy (ZPE) correction of the electronic mapping variables, we employed both the γ-adjusted and γ-fixed approaches. Nonadiabatic dynamics of the methaniminium cation (CH2NH2+) and azomethane are simulated using the on-the-fly SQC/MM method. For CH2NH2+, both two ZPE correction approaches give reasonable and consistent results. However, for azomethane, the γ-adjusted version of the SQC/MM dynamics behaves much better than the γ-fixed version. The further analysis indicates that it is always recommended to use the γ-adjusted SQC/MM dynamics in the on-the-fly simulation of photoinduced dynamics of polyatomic systems, particularly when the excited-state is well separated from the ground state in the Frank-Condon region. This work indicates that the on-the-fly SQC/MM method is a powerful simulation protocol to deal with the nonadiabatic dynamics of realistic polyatomic systems.


2021 ◽  
Author(s):  
Deping Hu ◽  
Yu Xie ◽  
Jiawei Peng ◽  
Zhenggang Lan

The on-the-fly version of the symmetrical quasi-classical dynamics method based on the Meyer-Miller mapping Hamiltonian (SQC/MM) is implemented to study the nonadiabatic dynamics at conical intersections of polyatomic systems. The current on-the-fly implementation of the SQC/MM method is based on the adiabatic representation and the dressed momentum. To include the zero-point energy (ZPE) correction of the electronic mapping variables, we employ both the γ-adjusted and γ-fixed approaches. Nonadiabatic dynamics of the methaniminium cation (CH2NH2+) and azomethane are simulated using the on-the-fly SQC/MM method. For CH2NH2+, both two ZPE correction approaches give reasonable and consistent results. However, for azomethane, the γ-adjusted version of the SQC/MM dynamics behaves much better than the γ-fixed version. The further analysis indicates that it is always recommended to use the γ-adjusted SQC/MM dynamics in the on-the-fly simulation of photoinduced dynamics of polyatomic systems, particularly when the excited-state is well separated from the ground state in the Franck-Condon region. This work indicates that the on-the-fly SQC/MM method is a powerful simulation protocol to deal with the nonadiabatic dynamics of realistic polyatomic systems.<br>


2011 ◽  
Vol 20 (02) ◽  
pp. 557-564 ◽  
Author(s):  
A. BARAN ◽  
A. STASZCZAK ◽  
W. NAZAREWICZ

Nuclear fission barriers, mass parameters and spontaneous fission half lives of fermium isotopes calculated in a framework of the Skyrme Hartree-Fock-Bogoliubov model with the SkM* force are discussed. Zero-point energy corrections in the ground state are determined for each nucleus using the Gaussian overlap approximation of the generator coordinate method and in the cranking formalism. Results of spontaneous fission half lives are compared to experimental data.


The excimer fluorescence spectra of pure single pyrene crystals were observed from 4 to 353 °K. The data are analysed to determine the vibrational zero-point energy of the excimer (= 90 cm -1 ), the force constants of the excited state (= 1.93 x 10 5 dyn/cm) and ground state (= 3.25 x 10 5 dyn/cm) of the dimer, and the equilibrium intermolecular separation (= 3.34 Å) of the excimer. The repulsive intermolecular potential, the excimer energy, and the attractive excimer interaction potential, V' = 51330 - 1.136 x 10 6 / r 3 (cm -1 ) are determined as functions of the intermolecular separation r (Å). V' is shown to be consistent with an exciton resonance state originating from the 1 B a state of the pyrene molecule.


2016 ◽  
Vol 18 (36) ◽  
pp. 24835-24840 ◽  
Author(s):  
Chen Qu ◽  
Joel M. Bowman

We report a full-dimensional, permutationally invariant potential energy surface (PES) for the cyclic formic acid dimer.


2002 ◽  
Vol 116 (20) ◽  
pp. 9005-9013 ◽  
Author(s):  
H. F. Busnengo ◽  
C. Crespos ◽  
W. Dong ◽  
J. C. Rayez ◽  
A. Salin

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