Based on spin-unrestricted hartree fock theory, we present the spin unrestricted multi- configuration time dependent hartree lock theory （UMCTDHF） to describe the electron correlation dynamics of systems interacting...Based on spin-unrestricted hartree fock theory, we present the spin unrestricted multi- configuration time dependent hartree lock theory （UMCTDHF） to describe the electron correlation dynamics of systems interacting with laser field. The positive spin orbitals and the negative spin orbitals are propagated in their own subspace respectively. The spin orbital in the spin-down subspace acts with that in the spin-up subspace by the reduced density matrix and mean field operator. The ground energy is acquired by propagating the trial wave function in the imaginary time by using spin-restricted MCTDHF （RMCTDHF） and UMCTDHF respectively. Then the ionization probabilities and the electrons energies are calculated by using RMCTDHF and UMCTDHF when the laser field is present. The ionization probability calculated with UMCTDHF agrees with the previous theoretical reports very well. The UMCTDHF method is accurate and applicable for open shell system beyond the capability of the RMCTDHF method.展开更多
The geometrical and electronic properties of the anionic and neutral V2O6 clusters were studied with the spin unrestricted hybrid density functional B3LYP method. The calculated ground states of both clusters are diff...The geometrical and electronic properties of the anionic and neutral V2O6 clusters were studied with the spin unrestricted hybrid density functional B3LYP method. The calculated ground states of both clusters are different from the previous theoretical results. The ground state of V2O6^- is found to be a doublet with C2v symmetry, while a doublet with D2h symmetry was previously obtained by Vyboishchikov and Sauer. For neutral V206, the ground state is an open-shell singlet with D2h symmetry whose energy is very close to that of the triplet state. In contrast, a closed-shell singlet with D2h symmetry was obtained by Vyboishchikov and Sauer, and Calatayud et al. found a triplet ground state with Cs symmetry. Moreover, the calculated adiabatic and vertical detachment energies of the anion cluster are in much better agreement with the experimental results of photoelectron spectroscopy than previous theoretical values.展开更多
文摘Based on spin-unrestricted hartree fock theory, we present the spin unrestricted multi- configuration time dependent hartree lock theory （UMCTDHF） to describe the electron correlation dynamics of systems interacting with laser field. The positive spin orbitals and the negative spin orbitals are propagated in their own subspace respectively. The spin orbital in the spin-down subspace acts with that in the spin-up subspace by the reduced density matrix and mean field operator. The ground energy is acquired by propagating the trial wave function in the imaginary time by using spin-restricted MCTDHF （RMCTDHF） and UMCTDHF respectively. Then the ionization probabilities and the electrons energies are calculated by using RMCTDHF and UMCTDHF when the laser field is present. The ionization probability calculated with UMCTDHF agrees with the previous theoretical reports very well. The UMCTDHF method is accurate and applicable for open shell system beyond the capability of the RMCTDHF method.
基金Ⅴ. ACKN0WLEDGEMENTS This work was supported by the National Project for the Development of Key Fhndamental Sciences in China （G1999075305）, the National Natural Science Foundation of China （50121202, 10474087）, the USTCHP HPC project, and the SCCAS.
文摘The geometrical and electronic properties of the anionic and neutral V2O6 clusters were studied with the spin unrestricted hybrid density functional B3LYP method. The calculated ground states of both clusters are different from the previous theoretical results. The ground state of V2O6^- is found to be a doublet with C2v symmetry, while a doublet with D2h symmetry was previously obtained by Vyboishchikov and Sauer. For neutral V206, the ground state is an open-shell singlet with D2h symmetry whose energy is very close to that of the triplet state. In contrast, a closed-shell singlet with D2h symmetry was obtained by Vyboishchikov and Sauer, and Calatayud et al. found a triplet ground state with Cs symmetry. Moreover, the calculated adiabatic and vertical detachment energies of the anion cluster are in much better agreement with the experimental results of photoelectron spectroscopy than previous theoretical values.
