On the degeneracy of atomic states within exact-exchange (spin-) density functional theory

The problem of degenerate ground states of open-shell atoms is investigated in spin-restricted and spin-unrestricted density functional theories using the exact-exchange energy functional. For the spin-unrestricted case, spurious energy splittings of the order of 2-3 kcal/mol are found for atoms of the second and third periods which are larger than the splittings obtained from recently proposed approximate exchange functionals depending explicitly on the current density. In remarkable contrast, for spin-restricted calculations the degeneracy of different atomic ground states is recovered to within less than 0.6 kcal/mol.     

Basis set effects on the energy and hardness profiles of the hydrogen fluoride dimer

In earlier work, the present authors have shown that hardness profiles are less dependent on the level of calculation than energy profiles for potential energy surfaces (PESs) having pathological behaviors. At variance with energy profiles, hardness profiles always show the correct number of stationary points. This characteristic has been used to indicate the existence of spurious stationary points on the PESs. In the present work, we apply this methodology to the hydrogen fluoride dimer, a classical difficult case for the density functional theory methods.     

Application of London-type dispersion corrections to the solid-state density functional theory simulation of the terahertz spectra of crystalline pharmaceuticals

The effects of applying an empirical dispersion correction to solid-state density functional theory methods were evaluated in the simulation of the crystal structure and low-frequency (10 to 90 cm(-1)) terahertz spectrum of the non-steroidal anti-inflammatory drug, naproxen. The naproxen molecular crystal is bound largely by weak London force interactions, as well as by more prominent interactions such as hydrogen bonding, and thus serves as a good model for the assessment of the pair-wise dispersion correction term in systems influenced by intermolecular interactions of various strengths. Modifications to the dispersion parameters were tested in both fully optimized unit cell dimensions and those determined by X-ray crystallography, with subsequent simulations of the THz spectrum being performed. Use of the unmodified PBE density functional leads to an unrealistic expansion of the unit cell volume and the poor representation of the THz spectrum. Inclusion of a modified dispersion correction enabled a high-quality simulation of the THz spectrum and crystal structure of naproxen to be achieved without the need for artificially constraining the unit cell dimensions.     

Can TD‐DFT calculations accurately describe the excited states behavior of stacked nucleobases? The cytosine dimer as a test case

By using calculations rooted in the time dependent density functional theory (TD-DFT) we have investigated how the lowest energy excited states of a face-to-face pi-stacked cytosine dimer vary with the intermonomer distance (R). The perfomances of different density functionals have been compared, focussing mainly on the lowest energy single excited state of the dimer (S(1))(2). TD-PBE0, TD-LC-omegaPBE, and TD-M05-2X provide a picture very similar to that obtained at the CASPT2 level by Merchan et al. (J Chem Phys 2006, 125, 231102), predicting that (S(1))(2) has a minimum for R approximately 3 A, with a binding energy of approximately 0.5 eV, whereas TD-B3LYP, TD-CAM-B3LYP, and TD-PBE understimate the binding energy. However, independently of the functional employed, no low-energy spurious charge transfer transitions are predicted by TD-DFT calculations, also when a nonsymmetric dimer is investigated, providing encouraging indications for the use of TD-DFT for studying the excited state of pi-stacked nucleobases.     

Time-dependent density functional theory description of on-site electron repulsion and ligand field effects in the optical spectrum of hexaaquoruthenium(II) in solution

Time-dependent density functional theory (TDDFT) and density functional-based molecular dynamics were used to simulate the finite temperature t(2g)5 e(g) <-- t(2g)6 absorption band of the Ru2+ hexahydrate coordination complex in aqueous solution. The (1)T1 <-- (1)A1 and (1)T2 <-- (1)A1 molecular term splitting of this transition, which is not accounted for by the Kohn-Sham excitation spectrum, is shown to be satisfactorily reproduced by TDDFT at the BLYP/ALDA level of theory. Comparison to the spectrum of the Ru2+ (H2O)6 complex in vacuo computed by similar density functional classical molecular dynamics methods leads to the observation that bulk solvation has a negligible effect on the position and the shape of the absorption profile.     

Optimized effective potential from a correlated wave function: optimized effective potential-generalized valence bond (OEP-GVB)

The optimized effective potential (OEP) method allows orbital-dependent functionals to be used in density functional theory. Traditionally the orbital-dependent functional of interest has been the Hartree-Fock energy, leading to exact exchange density functional theory. Here we present results that use a generalized valence-bond (GVB) wave function, a multiconfigurational wave function that includes static correlation and dissociates to the proper limits. We demonstrate the effectiveness of the OEP-GVB method by showing the dissociation of H2 and the excitation spectrum of He.     

线性缀加平面波法计算掺杂钨和钒锐钛矿二氧化钛的电子结构

利用基于密度泛函理论的线性缀加平面波(LAPW)法, 计算未掺杂和掺杂钨和钒的锐钛矿TiO₂晶体的能带和电子态密度. 计算结果表明, 钨和钒的掺杂能够使锐钛矿TiO₂的能带明显变窄.     

High resolution spectroscopy for the A (2)A(1) state of CH(3)I(+) by mass-analyzed threshold ionization/photodissociation

Photodissociation of CH(3)I(+) in the ground vibronic state generated by mass-analyzed threshold ionization resulted in a superb spectrum for the first excited electronic state (A (2)A(1)) with hardly any spurious peak. Rotational structure in the spectrum could be resolved by using a single mode laser. This structure for one vibronic band, 2(1)3(1)6(1), was analyzed with the assumption of Hund's case (a) scheme both in the ground and excited electronic states.     

2-(N'-乙基咔唑-3'-烯基)-8-羟基喹啉的合成及理论研究

设计合成了2-(N'-乙基咔唑-3'-烯基)-8-羟基喹啉. 以UV-Vis, ¹H NMR, FT-IR, 元素分析和MS进行了结构表征, 并测定了产物的光致发光(PL)性质. 运用Gaussian98量子化学程序包, 采用B3LYP密度泛函(DFT)的方法, 在6-31G(d,p)水平上对分子的几何构型进行结构优化; 预测目标产物的振动光谱, 结果表明与实验值相符.     

Molecular conformations and harmonic force field of 1,3,5-benzenetriol molecule from ab initio and density functional theory investigations

The molecular conformers of the molecule 1,3,5-benzenetriol have been studied by ab initio and density functional methods to determine optimized equilibrium geometries, harmonic vibrational frequencies and relative stability. The results of the quantum-chemical calculations have been used to investigate the functional theory-infrared (FT-IR) spectrum of the 1,3,5-benzenetriol vapors trapped in Ar matrix at 12 K.     

Low-frequency modes of the benzoic acid dimer in chloroform observed by the optical Kerr effect

The low frequency Raman spectral density associated with the intermolecular hydrogen-bonding interaction of benzoic acid in chloroform was investigated through the ultrafast optically-heterodyne-detected optical Kerr effect. The low-frequency solute Raman spectrum was obtained by Fourier transform analysis and subtraction of the solvent spectrum from the solution spectrum. The resulting difference spectrum has a broad band below 150 cm(-1) with a peak at around 80 cm(-1). Previous studies of aromatic liquids suggest that the origin of such a low-frequency band is librational motion, although intermolecular hydrogen-bonding modes in benzoic acid may also contribute. To clarify these contributions to the low-frequency band, methyl benzoate was used to estimate the librational component; its structure is similar to benzoic acid, but it forms no intermolecular hydrogen bonds. Both librational and intermolecular modes were found to contribute to the low-frequency Raman spectrum of the dimer and thus can be separated. These experimental results were compared with the results of density functional theory calculations. In addition, the effect of deuteration on the Raman spectrum was also investigated.     

Evaluation of range-separated hybrid density functionals for the prediction of vibrational frequencies, infrared intensities, and Raman activities

We present an assessment of different density functionals, with emphasis on range-separated hybrids, for the prediction of fundamental and harmonic vibrational frequencies, infrared intensities, and Raman activities. Additionally, we discuss the basis set convergence of vibrational properties of H2O with long-range corrected hybrids. Our results show that B3LYP is the best functional for predicting vibrational frequencies (both fundamental and harmonic); the screened-PBE hybrid (HSE) density functional works best for infrared intensities, and the long-range corrected PBE (LC-omegaPBE), M06-HF, and M06-L density functionals are almost as good as MP2 for predicting Raman activities. We show the predicted Raman spectrum of adenine as an example of a medium-size molecule where a DFT/Sadlej pVTZ calculation is affordable and compare our results against the experimental spectrum.     

Effects of an electric field on interaction of aromatic systems

The effect of uniform external electric field on the interactions between small aromatic compounds and an argon atom is investigated using post‐HF (MP2, SCS‐MP2, and CCSD(T)) and density functional (PBE0‐D3, PBE0‐TS, and vdW‐DF2) methods. The electric field effect is quantified by the difference of interaction energy calculated in the presence and absence of the electric field. All the post‐HF methods describe electric field effects accurately although the interaction energy itself is overestimated by MP2. The electric field effect is explained by classical electrostatic models, where the permanent dipole moment from mutual polarization mainly determines its sign. The size of π‐conjugated system does not have significant effect on the electric field dependence. We found out that PBE0‐based methods give reasonable interaction energies and electric field response in every case, while vdW‐DF2 sometimes shows spurious artifact owing to its sensitivity toward the real space electron density. © 2015 Wiley Periodicals, Inc.     

Optical excitations of defects in realistic nanoscale silica clusters: comparing the performance of density functional theory using hybrid functionals with correlated wavefunction methods

Optical excitations of low energy silica (SiO(2))(4) clusters obtained by global optimization, as opposed to constructed by hand, are studied using a range of theoretical methods. By focusing on the lowest energy silica clusters we hope to capture at least some of the characteristic ways by which the dry surfaces of silica nanosystems preferentially terminate. Employing the six lowest energy (SiO(2))(4) cluster isomers, we show that they exhibit a surprisingly wide range of geometries, defects, and associated optical excitations. Some of the clusters show excitations localized on isolated defects, which are known from previous studies using hydrogen-terminated versions of the defect in question. Other clusters, however, exhibit novel charge-transfer excitations in which an electron transfers between two spatially separated defects. In these cases, because of the inherent proximity of the constituent defects due to the small cluster dimensions, the excitation spectrum is found to be very different from that of the same defects in isolation. Excitation spectra of all clusters were calculated using time-dependent density functional theory (TD-DFT) and delta-SCF DFT (DeltaDFT) methods employing two different hybrid density functionals (B3LYP and BB1K) differing essentially in the amount of incorporated Hartree-Fock-like exchange (HFLE). In all cases the results were compared with CASPT2 calculated values which are taken as a benchmark standard. In line with previous work, the spatially localized excitations are found to be well described by TD-DFT/B3LYP but which gives excitation energies that are significantly underestimated in the case of the charge-transfer excitations. The TD-DFT/BB1K combination in contrast is found to give generally good excitation energies for the lowest excited states of both localized and charge-transfer excitations. Finally, our calculations suggest that the increased quality of the predicted excitation spectra by adding larger amounts of HFLE is mainly due to an increased localization of the excited state associated with the elimination of spurious self-interaction inherent to (semi-)local DFT functionals.     

Association of bromate ion in nonaqueous solutions of alkali metal salts

Manifestations of ion association of lithium cation with BrO₃ ^- ion in the vibrational spectrum have been studied by IR spectroscopy. The microstructure of the bromate ion with lithium cation in a contact ion pair in an aprotic solvent has been determined by the density functional theory method in the B3LYP/cc-pVTZ approximation, and the vibrational spectrum of coordinated bromate ion has been calculated.     

Density functional calculations for4He droplets

A novel density functional, which accounts correctly for the equation of state, the static response function and the phonon-roton dispersion in bulk liquid helium, is used to predict static and dynamic properties of helium droplets. The static density profile is found to exhibit significant oscillations, which are accompanied by deviations of the evaporation energy from a liquid drop behaviour in the case of small droplets. The connection between such oscillations and the structure of the static response function in the liquid is explicitly discussed. The energy and the wave function of excited states are then calculated in the framework of time dependent density functional theory. The new functional, which contains backflow-like effects, is expected to yield quantitatively correct predictions for the excitation spectrum also in the roton wave-length range.     

Theoretical analysis of the terahertz spectrum of the high explosive PETN.

The experimental solid-state terahertz (THz) spectrum (3 to 120 cm(-1)) of the high explosive pentaerythritol tetranitrate (PETN, C(5)H(6)N(4)O(12)) has been modeled using solid-state density functional theory (DFT) calculations. Solid-state DFT, employing the BP density functional, is in best qualitative agreement with the features in the previously reported THz spectrum. The crystal environment of PETN includes numerous intermolecular hydrogen-bonding interactions that contribute to large (up to 80 cm(-1)) calculated shifts in molecular normal-mode positions in the solid state. Comparison of the isolated-molecule and solid-state normal-mode calculations for a series of density functionals reveals the extent to which the inclusion of crystal-packing interactions and the relative motions between molecules are required for correctly reproducing the vibrational structure of solid-state THz spectra. The THz structure below 120 cm(-1) is a combination of both intermolecular (relative rotations and translations) and intramolecular (torsions, large amplitude motions) vibrational motions. Vibrational-mode analyses indicate that the first major feature (67.2 cm(-1)) in the PETN THz spectrum contains all of the optical rotational and translational cell modes and no internal (molecular) vibrational modes.