The authors propose a new route to vibrational Raman intensities based on analytical derivatives of a fully variational polarizability Lagrangian. The Lagrangian is constructed to recover the negative frequency-dependent polarizability of time-dependent Hartree-Fock or adiabatic (hybrid) density functional theory at its stationary point. By virtue of the variational principle, first-order polar...

Using the long-range corrected (LC) density functional theory (DFT) scheme introduced by Iikura et al. [J. Chem. Phys. 115, 3540 (2001)] and the Coulomb-attenuating model (CAM-B3LYP) of Yanai et al. [Chem. Phys. Lett. 393, 51 (2004)], we have calculated the longitudinal dipole moments and static electronic first hyperpolarizabilities of increasingly long polymehtineimine oligomers. For comparis...

Ti(+) is known to react with acetone (CH(3)COCH(3)) to produce TiO(+) and CH(2)CHCH(3) as products, but the detailed reaction mechanism and the most favorable reaction pathway have not yet been elucidated. Here, we investigate the doublet and quartet potential-energy surfaces associated with the gas-phase reaction between Ti(+) and acetone for three plausible pathways, (i) direct metal-ion inse...

Electronic structures of doped NaTaO3 compounds are of significant interest to visible light photocatalysis. This work involves the study of the band gap, band edge potentials, and thermodynamic stability of certain mono-doped and co-doped NaTaO3 systems, using DFT-PBE as well as hybrid (PBE0) functional calculations. Doping of certain non-magnetic cations (Ti, V, Cu, Zn, W, In, Sn, Sb, Ce, and...

In this paper we evaluate the performance of density functional theory with the B3LYP functional for calculations on ceria (CeO(2)) and cerium sesquioxide (Ce(2)O(3)). We demonstrate that B3LYP is able to describe CeO(2) and Ce(2)O(3) reasonably well. When compared to other functionals, B3LYP performs slightly better than the hybrid functional PBE0 for the electronic properties but slightly wor...

The third member of the series of imidoselenium(II) chlorides ClSe[N(tBu)Se]nCl (n = 3) (9) has been isolated from the cyclocondensation reaction of tBuNH2 and SeCl2 in THF in a molar ratio of ca. 3:1 and characterized in the form of two polymorphs 9a and 9b by single crystal X-ray analysis. The unusual structural features of this nine-atom chain are explained satisfactorily in terms of a bondi...

Benchmark calculations of proton affinities and gas-phase basicities of molecules most relevant to biological phosphoryl transfer reactions are presented and compared with available experimental results. The accuracy of proton affinity and gas-phase basicity results obtained from several multi-level model chemistries (CBS-QB3, G3B3, and G3MP2B3) and density-functional quantum models (PBE0, B1B9...

The preparation of Os2(TiPB)4Cl2 (1; TiPB = 2,4,6-triisopropylbenzoate) and Os2(TiPB)2(OAc)2Cl2 (2) by carboxylate exchange reactions with Os2(OAc)4Cl2 is reported. The structure of 1 has been determined by single-crystal X-ray studies, and shows a paddlewheel arrangement of the ligands about the triply bonded diosmium core. Both compounds have magnetic moments at room temperature that are cons...

Materials with van der Waals-bonding are known to exhibit quantum confinement effect, in which the electronic bandgap of three-dimensional (3D) realization a material is lower than that its two-dimensional (2D) counterpart. However, possibility an anomalous effect (AQCE) exists, where trend reversed. In this work, we computationally identify materials for such AQCE occurs. Using density functio...

Using a set of oscillator strengths and excited-state dipole moments near full configuration interaction (FCI) quality determined for small compounds, we benchmark the performances several single-reference wave function methods (CC2, CCSD, CC3, CCSDT, ADC(2), ADC(3/2)) time-dependent density-functional theory (TD-DFT) with various functionals (B3LYP, PBE0, M06-2X, CAM-B3LYP, $\omega$B97X-D). We...