electrons, that is, an “open-shell doublet.” Although low-spin, open-shell states occur in molecules containing transition metals, the ground states of organic molecules are rarely of this type. Organic biradicals can have open-shell singlet ground states, depending on the orbital structure, but DMX is the first example of an organic triradical with an open-shell doublet ground state. Qualitati...

Due to the frequent presence of a Berry phase, in most cases of dynamical JahnTeller systems the symmetry of the ground state is the same as that of the electronic state. However, the H ⊗ h icosahedral case, relevant for the physics of fullerene ions, provides a first example of linear coupling leading, at strong coupling, to a change in symmetry of the ground state to a totally symmetric nonde...

Photodissociation dynamics for various tryptophan chromophores was studied at 193 or 248 nm using multimass ion imaging techniques. The competition between internal conversion to the ground electronic state and dissociation from the repulsive excited state reveals size-dependent photostability for these amino acid chromophores. As the size of chromophore increases, internal conversion to the gr...

Carbocations are traditionally thought to be closed-shell electrophiles featuring an empty orbital rich in p character. Here, density functional theory computations indicate that when strong π donors are not placed in direct conjugation with benzylic-type cations, alternative diradical configurations that resemble non-Kekulé diradicals are possible. For certain donor-acceptor frameworks, an ope...

Gold monosulfide, AuS, has been detected and characterized in the gas phase using optical spectroscopy. The symmetries of the ground and low-lying electronic excited states have been determined by application of a synergy of hot and cold laser excitation techniques. The electronic spectra are assigned to progressions in four band systems associated with excitations from the X(2)Πi ((2σ)(2)(2π)(...

We provide a priori error estimates for the spectral and pseudospectral Fourier (also called planewave) discretizations of the periodic ThomasFermi-von Weizsäcker (TFW) model and for the spectral discretization of the Kohn-Sham model, within the local density approximation (LDA). These models allow to compute approximations of the ground state energy and density of molecular systems in the cond...

The enthalpies of formation of transition metals diborides in various structures have been obtained from density functional theory (DFT) calculations in order to determine the ground state at T = 0 K and p = 0. The evolution of the enthalpies of formation along the 3D, 4D, and 5D series has been correlated to the considered crystal structures. In the whole, the calculated values of the enthalpi...

We have recorded laser excitation spectra of transitions from the ground X(1)Sigma(+) state of gaseous gold fluoride (AuF) into three excited electronic states in the visible region. We prepared the sample in a dc electric discharge by flowing a dilute mixture of SF(6) in argon through a hollow gold cathode. Two of these electronic states give rise to the previously reported yellow bands of the...

Laser pulse control of the photoinduced 90 fs charge injection from perylene into the conduction band of TiO2 is studied theoretically. The approach accounts for the electronic-ground state of the dye, the first excited state, the ionized state formed after charge injection, and the continuum of the electronic states in the conduction band, all defined vs a single reaction coordinate. To addres...