Non-adiabatic Effects in the Dissociation of Oxygen Molecules at the Al(111) Surface

The measured low initial sticking probability of oxygen molecules at the Al(111) surface that had puzzled the field for many years was recently explained in a non-adiabatic picture invoking spin-selection rules [J. Behler et al., Phys. Rev. Lett. 94, 036104 (2005)]. These selection rules tend to conserve the initial spin-triplet character of the free O2 molecule during the molecule's approach to the surface. A new locally-constrained density-functional theory approach gave access to the corresponding potential-energy surface (PES) seen by such an impinging spin-triplet molecule and indicated barriers to dissociation which reduce the sticking probability. Here, we further substantiate this non-adiabatic picture by providing a detailed account of the employed approach. Building on the previous work, we focus in particular on inaccuracies in present-day exchange-correlation functionals. Our analysis shows that small quantitative differences in the spin-triplet constrained PES obtained with different gradient-corrected functionals have a noticeable effect on the lowest kinetic energy part of the resulting sticking curve.Comment: 17 pages including 11 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Theoretical study of molecular electronic excitations and optical transitions of C60

We report results on ab initio calculations of excited states of the fullerene molecule by using configuration interaction (CI) approach with singly excited determinants (SCI). We have used both the experimental geometry and the one optimized by the density functional method and worked with basis sets at the cc-pVTZ and aug-cc-pVTZ level. Contrary to the early SCI semiempirical calculations, we find that two lowest $^1 T_{1u} \leftarrow {}^1 A_g$ electron optical lines are situated at relatively high energies of ~5.8 eV (214 nm) and ~6.3 eV (197 nm). These two lines originate from two $^1 T_{1u} \leftarrow {}^1 A_g$ transitions: from HOMO to (LUMO+1) ($6h_u \to 3t_{1g}$) and from (HOMO--1) to LUMO ($10h_g \to 7t_{1u}$). The lowest molecular excitation, which is the $1 ^3 T_{2g}$ level, is found at ~2.5 eV. Inclusion of doubly excited determinants (SDCI) leads only to minor corrections to this picture. We discuss possible assignment of absorption bands at energies smaller than 5.8 eV (or $\lambda$ larger than 214 nm).Comment: 6 pages, 1 figure, 9 Table

On the mutual polarization of two He-4 atoms

We propose a simple method based on the standard quantum-mechanical perturbation theory to calculate the mutual polarization of two atoms He^4.Comment: 9 pages, 1 table; the article is revised and the calculation is essentially refined; v4: final version, the Introduction is delete

Resonant ion-pair formation in electron recombination with HF^+

The cross section for resonant ion-pair formation in the collision of low-energy electrons with HF^+ is calculated by the solution of the time-dependent Schrodinger equation with multiple coupled states using a wave packet method. A diabatization procedure is proposed to obtain the electronic couplings between quasidiabatic potentials of ^1Sigma^+ symmetry for HF. By including these couplings between the neutral states, the cross section for ion-pair formation increases with about two orders of magnitude compared with the cross section for direct dissociation. Qualitative agreement with the measured cross section is obtained. The oscillations in the calculated cross section are analyzed. The cross section for ion-pair formation in electron recombination with DF^+ is calculated to determine the effect of isotopic substitution.Comment: 12 pages, 12 figure

Ultralow-power local laser control of the dimer density in alkali-metal vapors through photodesorption

Ultralow-power diode-laser radiation is employed to induce photodesorption of cesium from a partially transparent thin-film cesium adsorbate on a solid surface. Using resonant Raman spectroscopy, we demonstrate that this photodesorption process enables an accurate local optical control of the density of dimer molecules in alkali-metal vapors.Comment: 4 pages, 4 figure

Strong fragmentation of low-energy electromagnetic excitation strength in 117^{117}Sn

Results of nuclear resonance fluorescence experiments on $^{117}$Sn are reported. More than 50 $\gamma$ transitions with $E_{\gamma} < 4$ MeV were detected indicating a strong fragmentation of the electromagnetic excitation strength. For the first time microscopic calculations making use of a complete configuration space for low-lying states are performed in heavy odd-mass spherical nuclei. The theoretical predictions are in good agreement with the data. It is concluded that although the E1 transitions are the strongest ones also M1 and E2 decays contribute substantially to the observed spectra. In contrast to the neighboring even $^{116-124}$Sn, in $^{117}$Sn the $1^-$ component of the two-phonon $[2^+_1 \otimes 3^-_1]$ quintuplet built on top of the 1/2$^+$ ground state is proved to be strongly fragmented.Comment: 4 pages, 3 figure

Using Molecules to Measure Nuclear Spin-Dependent Parity Violation

Nuclear spin-dependent parity violation arises from weak interactions between electrons and nucleons, and from nuclear anapole moments. We outline a method to measure such effects, using a Stark-interference technique to determine the mixing between opposite-parity rotational/hyperfine levels of ground-state molecules. The technique is applicable to nuclei over a wide range of atomic number, in diatomic species that are theoretically tractable for interpretation. This should provide data on anapole moments of many nuclei, and on previously unmeasured neutral weak couplings

Excited states of the water molecule : Analysis of the valence and Rydberg character

The excited states of the water molecule have been analyzed by using the extended quantum-chemical multistate CASPT2 method, namely, MS-CASPT2, in conjunction with large one-electron basis sets of atomic natural orbital type. The study includes 13 singlet and triplet excited states, both valence and 3s-, 3p-, and 3d-members of the Rydberg series converging to the lowest ionization potential and the 3s- and 3p-Rydberg members converging to the second low-lying state of the cation, 1 math. The research has been focused on the analysis of the valence or Rydberg character of the low-lying states. The computation of the 1 math state of water at different geometries indicates that it has a predominant 3s-Rydberg character at the equilibrium geometry of the molecule but it becomes progressively a valence state described mainly by the one-electron 1b1→4a1 promotion, as expected from a textbook of general chemistry, upon elongation of the O–H bonds. The described valence-Rydberg mixing is established to be originated by a molecular orbital (MO) Rydbergization process, as suggested earlier by R. S. Mulliken [Acc. Chem. Res. 9, 7 (1976)] . The same phenomenon occurs also for the 1 math state whereas a more complex behavior has been determined for the 2 math state, where both MO Rydbergization and configurational mixing take place. Similar conclusions have been obtained for the triplet states of the [email protected] [email protected] [email protected]

A theory of intense-field dynamic alignment and high harmonic generation from coherently rotating molecules and interpretation of intense-field ultrafast pump-probe experiments

A theory of ultra-fast pump-probe experiments proposed by us earlier [F.H.M. Faisal et al., Phys. Rev. Lett. 98, 143001 (2007) and F.H.M. Faisal and A. Abdurrouf, Phys. Rev. Lett. 100, 123005 (2008)] is developed here fully and applied to investigate the phenomena of dynamic alignment and high harmonic generation (HHG) from coherently rotating linear molecules. The theory provides essentially analytical results for the signals that allow us to investigate the simultaneous dependence of the HHG signals on the two externally available control parameters, namely, the relative angle between the polarizations, and the delay-time between the two pulses. It is applied to investigate the characteristics of high harmonic emission from nitrogen and oxygen molecules that have been observed experimentally in a number of laboratories. The results obtained both in the time-domain and in the frequency-domain are compared with the observed characteristics as well as directly with the data and are found to agree remarkably well. In addition we have predicted the existence of a "magic" polarization angle at which all modulations of the harmonic emission from nitrogen molecule changes to a steady emission at the harmonic frequency. Among other things we have also shown a correlation between the existence of the "magic" or critical polarization angles and the symmetry of the active molecular orbitals, that is deemed to be useful in connection with the "inverse problem" of molecular imaging from the HHG data.Comment: 31 pages, 22 figures, and 140 equation