Amsterdam Density Functional Program Package Research Articles

Calculating Molecular Polarizabilities Using Exact Frozen Density Embedding with External Orthogonality.

Frozen density embedding (FDE) with freeze-thaw cycles is a formally exact embedding scheme. In practice, this method is limited to systems with small density overlaps when approximate nonadditive kinetic energy functionals are used. It has been shown that the use of approximate nonadditive kinetic energy functionals can be avoided when external orthogonality (EO) is enforced, and FDE can then generate exact results even for strongly overlapping subsystems. In this work, we present an implementation of exact FDEc-EO (coupled FDE TDDFT with EO) for the calculation of polarizabilities in the Amsterdam density functional program package. EO is enforced using the level-shift projection operator method, which ensures that orbitals between fragments are orthogonal. For pure functionals, we show that only the symmetric EO contributions to the induced density matrix are needed. This leads to a simplified implementation for the calculation of polarizability that can exactly reproduce the supermolecular TDDFT results. We further discuss the limitation of exact FDEc-EO in interpreting subsystem polarizabilities due to the nonunique partitioning of the total density. We show that this limitation is due to the fact that subsystem polarizability partitioning is dependent on how the subsystems are initially polarized. As supermolecular virtual orbitals are exactly reproduced, this dependence is attributed to the description of the occupied orbitals. In contrast, for excitations of subsystems that are localized within one subsystem, we show that the excitation energies are stable with respect to the order of polarization. This observation shows that impacts from the nonunique nature of exact FDE on subsystem properties can be minimized by better fragmentation of the supermolecular systems if the property is localized. For global properties like polarizability, this is not the case, and nonuniqueness remains independent of the fragmentation used.

Frozen Density Embedding with External Orthogonality in Delocalized Covalent Systems.

Frozen density embedding (FDE) has become a popular subsystem density functional theory (DFT) method for systems with weakly overlapping charge densities. The failure of this method for strongly interacting and covalent systems is due to the approximate kinetic energy density functional (KEDF), although the need for approximate KEDFs may be eliminated if each subsystem's Kohn-Sham (KS) orbitals are orthogonal to the other, termed external orthogonality (EO). We present an implementation of EO into the FDE framework within the Amsterdam density functional program package, using the level-shift projection operator method. We generalize this method to remove the need for orbital localization schemes and to include multiple subsystems, and we show that the exact KS-DFT energies and densities may be reproduced through iterative freeze-and-thaw cycles for a number of systems, including a charge delocalized benzene molecule starting from atomic subsystems. Finally, we examine the possibility of a truncated basis for systems with and without charge delocalization, and found that subsystems require a basis that allows them to correctly describe the supermolecular delocalized orbitals.

Surface-enhanced Raman scattering of trans-1,2-bis (4-pyridyl)-ethylene on silver by theory calculations

Surface-enhanced Raman spectra of trans-1,2-bis (4-pyridyl)-ethylene (t-BPE) on silver foil were detected at laser line of 514.5, 633, 785 and 1064 nm, respectively. The structure of Ag–t-BPE, Ag 4–t-BPE, Ag 6–t-BPE, Ag 10–t-BPE and Ag 20–t-BPE complexes has been calculated using a local version of the Amsterdam density functional program package. The Raman spectra and electronic polarizability of t-BPE–Ag at 514.5, 633, 785 and 1064 nm excitation lines were calculated. The Raman bands of t-BPE were assigned according to the calculation of potential energy distribution. The experimental and calculated Raman spectra of t-BPE–Ag at 514.5, 633, 785 and 1064 nm were compared. The relative Raman intensities change at different excitation lines were discussed based on the Raman enhanced mechanism and surface selection rules.

Analysis of the nitrogen K-edge x-ray absorption spectra of Zn-porphyrin/C70-fulleren complex for solar cells

The atomic structure models of Zn-porphyrin/C70 multilayer for solar cells were examined. The local atomic structure of the Zn-porphyrin/C70 complex was refined with the use of previously published results [1]. Since near-edge spectral region (XANES) is sensitive to the three-dimensional atomic geometry, the theoretical analysis of the experimental XANES was performed on the basis of finite difference method (FDMnes 2008 program code). Some electronic properties of the complex were obtained from the DFT calculations performed by means of Amsterdam Density Functional program package.

The calculation of excitation energies based on the relativistic two-component zeroth-order regular approximation and time-dependent density-functional with full use of symmetry

In the present work, we propose a relativistic time-dependent density-functional theory (TDDFT) based on the two-component zeroth-order regular approximation and a noncollinear exchange-correlation (XC) functional. This two-component TDDFT formalism has the correct nonrelativistic limit and affords the correct threefold degeneracy of triplet excitations. The relativistic TDDFT formalism is implemented into the AMSTERDAM DENSITY FUNCTIONAL program package for closed-shell systems with full use of double-group symmetry to reduce the computational effort and facilitate the assignments. The performance of the formalism is tested on some closed-shell atoms, ions, and a few diatomic molecules containing heavy elements. The results show that the fine structure of the excited states for most atoms and ions studied here can be accurately accounted for with a proper XC potential. For the excitation energies of the molecules studied here, the present formalism shows promise and the error encountered is comparable to that of nonrelativistic TDDFT calculations on light elements.

Chiroptical properties from time-dependent density functional theory. II. Optical rotations of small to medium sized organic molecules

We report an implementation for the computation of optical rotations within the Amsterdam Density Functional program package. The code is based on time-dependent density functional response theory. Optical rotations have been calculated for a test set of 36 organic molecules with various density functionals, and employing basis sets of different quality. The results obtained in this work with nonhybrid functionals are comparable in quality to those recently reported by other authors for the B3LYP hybrid functional, but show a somewhat larger tendency to produce outlyers. The median error is approximately 20°/(dm g/cm3) for specific rotations [α]D as compared to experimental data (approximately 30% median deviation from experimental values). Thereby it is demonstrated that density functional computations can be employed to assist with the solution of stereochemical problems in case the specific rotations of the species involved are not small and their structures are rigid. Recent newly developed functionals are investigated with respect to their applicability in computations of optical rotations.

An implementation of the coupled perturbed Kohn-Sham equations: perturbation due to nuclear displacements

The Coupled Perturbed Kohn-Sham equations have been implemented in the Amsterdam Density Functional program package. Our implementation differs from previous ones in many ways. This program uses density fitting to calculate the Coulomb and exchange integrals. Further, all matrix elements of the Fock type matrix and its derivatives are calculated by numerical integration. The frozen core approximation is also implemented. Our implementation is approximately 10 times faster than a finite difference algorithm, and the absolute CPU times also compare favorably with other reported implementations.