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Pseudopotentials (PP) are extensively used in electronic structure calculations, particularly for molecules containing heavy elements. Parameters in PPs are mainly determined from ab initio results, and errors of such PPs in density functional theory (DFT) calculations have been studied previously. However, PP errors on results with spin–orbit coupling and those in time-dependent DFT (TDDFT) calculations have not been reported previously. In this work, we investigate the error of the small-core energy-consistent Stuttgart/Koln pseudopotentials in DFT and TDDFT calculations with and without spin–orbit coupling. Ground state bond lengths, harmonic frequencies, dissociation energies, and vertical excitation energies for a series of closed-shell diatomic heavy and superheavy p-block molecules are calculated using several popular exchange-correlation functionals. PP errors are estimated by comparing with results using the all-electron Dirac–Coulomb (-Gaunt) Hamiltonian. Our results show that the difference between ground state properties and most excitation energies in scalar-relativistic calculations with the PP and those of all-electron calculations is quite small. This difference becomes somewhat larger when spin–orbit coupling (SOC) is present, especially for properties that are affected by SOC to some extent. In addition, the errors of the PPs are insensitive to the employed exchange-correlation functionals in most cases. Our results indicate that reasonable DFT and TDDFT results can be obtained using the small-core energy-consistent Stuttgart/Koln pseudopotentials for heavy and super-heavy p-block molecules. [ABSTRACT FROM AUTHOR]

The intermediate Hamiltonian Fock-space coupled-cluster methods at the singles and doubles level (IHFSCCSD) for excitation energies in the (1p, 1h) sector, double ionization potentials in the (0p, 2h) sector, and double electron attachments in the (2p, 0h) sector of the Fock space are implemented based on the CCSD method with spin–orbit coupling (SOC) included in the post-Hartree–Fock treatment using a closed-shell reference in this work. The active space is chosen to contain those orbitals that have the largest contribution to principal ionized or electron-attached states obtained from the equation-of-motion coupled-cluster calculations. Both time-reversal symmetry and spatial symmetry are exploited in the implementation. Our results show that the accuracy of IHFSCCSD results is closely related to the active space, and the sufficiency of the active space can be assessed from the percentage of transitions within the active space. In addition, unreasonable results may be encountered when the ionized or electron-attached states with a somewhat larger contribution from double excitations are included to determine the active space and cluster operators in the (0p, 1h) or (1p, 0h) sector of the Fock space. A larger active space may be required to describe SO splitting reliably than that in the scalar-relativistic calculations in some cases. The IHFSCCSD method with SOC developed in this work can provide reliable results for heavy-element systems when a sufficient active space built upon the principal ionization potential/electron affinity states is adopted. [ABSTRACT FROM AUTHOR]

Abstract: Tunable third-harmonic and fourth-harmonic generations of pulsed CO2 laser radiation in a GaSe crystal were demonstrated. The optical properties of GaSe and phase-matching conditions in harmonic generations were investigated. The output peak powers for 3.2μm and 2.4μm were measured to be 1500W and 320W, with corresponding conversion efficiency from 9.6μm of 0.1% and 0.02%, respectively. [Copyright &y& Elsevier]

Abstract: Coherent terahertz pulses have been generated at a range of 236.3–1104.5μm (0.27–1.3THz) by one CO2 laser with dual-wavelength output based on collinearly phase-matched different frequency generation (DFG) in a GaSe crystal. This source has the advantages of compact and simplicity for tuning. The output power of the THz pulse and phase-matching conditions were investigated. The maximum single pulse energy of 11nJ was generated at a frequency of 1.23THz (243.6μm), corresponding to a peak output power 182mW. [Copyright &y& Elsevier]