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In this paper, we developed a nonadiabatic molecular dynamics method based on Su-Schriffer-Heeger (SSH) Hamiltonian. The nonadiabatic molecular dynamics method based on SSH Hamiltonian is widely used to study the photoexcitation dynamics and polaron motion in conjugated polymers. However, in this method, the time-dependent Schrödinger equation is so far solved under diabatic representation, also named site representation. In order to provide a deeper insight on the nonadiabatic molecular dynamics method, we solve the time-dependent Schrödinger equation under adiabatic representation. The new method can directly provide the important information on the strength of nonadiabatic couplings between different molecular orbitals during the excited-state relaxation process, helping us to predict the electron and energy transfer within or between polymer chains.
Solving the time-dependent Schrödinger equation under adiabatic representation is much more complicated, mainly because we need to calculate the nonadiabatic couplings between different molecular orbitals. In this paper, we gave detailed formula deductions and practical calculation procedures of the nonadiabatic molecular dynamics method with adiabatic representation. Using this new method, we simulated three photoexcitation processes in a conjugated polymer chain, HOMO→LUMO, HOMO-1→LUMO+1 and HOMO-2→LUMO+2. We analyzed in detail the time evolution of lattice configuration for these three photoexcitation processes, and compared these results to those obtained by diabatic representation (site representation). The results obtained by the two representations are consistent.
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Keywords:
- nonadiabatic molecular dynamics /
- adiabatic representation /
- conjugated polymer /
- SSH model
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