Relativistic Effects in Ligand Field Theory (I): Optical Properties of d Atoms in Symmetry.

Ligand field theory, which explains the splitting of degenerate d atomic orbitals due to static electric fields from point-charge ligands, is rederived using Dirac orbitals instead of Schrödinger orbitals, specifically using the d and d spinors. This formalism is, to some extent, equivalent to incorporating the spin-orbit interaction either in the d atomic orbitals or in the ligand field orbitals (e.g.

Multidirectional Angular Electronic Flux during Adiabatic Attosecond Charge Migration in Excited Benzene.

Recently, adiabatic attosecond charge migration (AACM) has been monitored and simulated for the first time, with application to the oriented iodoacetylene cation where AACM starts from the initial superposition of the ground state (φ0) and an electronic excited state (φ1). Here, we develop the theory for electronic fluxes during AACM in ring-shaped molecules, with application to oriented benzene prepared in the superposition of the ground and first excited singlet states. The initial state and its time evolution are analogous to coherent tunneling where φ0 and φ1 have different meanings; however, they denote the wave functions of the lowest tunneling doublet.

Quantum theory of concerted electronic and nuclear fluxes associated with adiabatic intramolecular processes.

An elementary molecular process can be characterized by the flow of particles (i.e., electrons and nuclei) that compose the system.

Imaging the Ultrafast Photoelectron Transfer Process in Alizarin-TiO2.

In this work, we adopt a quantum mechanical approach based on time-dependent density functional theory (TDDFT) to study the optical and electronic properties of alizarin supported on TiO2 nano-crystallites, as a prototypical dye-sensitized solar cell. To ensure proper alignment of the donor (alizarin) and acceptor (TiO2 nano-crystallite) levels, static optical excitation spectra are simulated using time-dependent density functional theory in response. The ultrafast photoelectron transfer from the dye to the cluster is simulated using an explicitly time-dependent, one-electron TDDFT ansatz.

Dissociating H₂⁺(²Σg⁺,JM=00) ion as an exploding quantum bubble.

The nuclear and electronic probability and flux densities for a vibrating and dissociating H2(+) molecular ion in the electronic and rotational ground state (corresponding to the quantum numbers ²Σ(g)⁺,JM=00) are calculated. As a consequence of the isotropy of the scenario, the vibrating H2(+) appears as a pulsating quantum bubble, while the dissociating H2(+) appears as an exploding quantum bubble. The dissociating part is represented by a discretization of the continuum through use of £2 integrable B-spline basis set.

Vibrating H2(+)((2)Σg(+), JM = 00) ion as a pulsating quantum bubble in the laboratory frame.

We present quantum dynamics simulations of the concerted nuclear and electronic densities and flux densities of the vibrating H2(+) ion with quantum numbers (2)Σg(+), JM = 00 corresponding to the electronic and rotational ground state, in the laboratory frame. The underlying theory is derived using the nonrelativistic and Born–Oppenheimer approximations. It is well-known that the nuclear density of the nonrotating ion (JM = 00) is isotropic.

Nuclear fluxes in diatomic molecules deduced from pump-probe spectra with spatiotemporal resolutions down to 5 pm and 200 asec.

When molecules move, their nuclei flow. The corresponding quantum observable, i.e.