Calculation of One-Electron Wave Functions and Energy Levels of N-Butane Molecule on the Basis of Slater Atomic Orbitals

It is known that the application of the group theory greatly simplifies the problems of polyatomic systems possessing to any space symmetry. The symmetry properties of such systems are their most important characteristics. In such systems, the Hamilton operator is invariant under unitary symmetry transformations and rearrangements of identical particles in the coordinate system. This allows to obtain information about the character of one-electron wave functions — molecular orbitals — the considered system, i.e. to symmetrise the original wave functions without solving the Schrödinger equation.

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

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>

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

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.

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

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.