A simple approach to the correlation of rotovibrational states in four-atomic molecules

The problem of correlation between quantum states of four-atomic molecules in different geometrical configurations is reviewed in detail. A general, still simple rule is obtained which allows one to correlate states of a linear four-atomic molecule with those of any kind of non-linear four-atomic molecule.Comment: 16 pages (+8 figures), Postscript (ready to print!

Counting statistics of tunneling through a single molecule: effect of distortion and displacement of vibrational potential surface

We analyze the effects of a distortion of the nuclear potential of a molecular quantum dot (QD), as well as a shift of its equilibrium position, on nonequilibrium-vibration-assisted tunneling through the QD with a single level ($\epsilon_d$) coupled to the vibrational mode. For this purpose, we derive an explicit analytical expression for the Franck-Condon (FC) factor for a displaced-distorted oscillator surface of the molecule and establish rate equations in the joint electron-phonon representation to examine the current-voltage characteristics and zero-frequency shot noise, and skewness as well. Our numerical analyses shows that the distortion has two important effects. The first one is that it breaks the symmetry between the excitation spectra of the charge states, leading to asymmetric tunneling properties with respect to $\epsilon_d>0$ and $\epsilon_d<0$. Secondly, distortion (frequency change of the oscillator) significantly changes the voltage-activated cascaded transition mechanism, and consequently gives rise to a different nonequilibrium vibrational distribution from that of the case without distortion. Taken in conjunction with strongly modified FC factors due to distortion, this results in some new transport features: the appearance of strong NDC even for a single-level QD with symmetric tunnel couplings; a giant Fano factor even for a molecule with an extremely weak electron-phonon interaction; and enhanced skewness that can have a large negative value under certain conditions.Comment: 29 pages, 11 figures, published versio

Excited-state Forces within a First-principles Green's Function Formalism

We present a new first-principles formalism for calculating forces for optically excited electronic states using the interacting Green's function approach with the GW-Bethe Salpeter Equation method. This advance allows for efficient computation of gradients of the excited-state Born-Oppenheimer energy, allowing for the study of relaxation, molecular dynamics, and photoluminescence of excited states. The approach is tested on photoexcited carbon dioxide and ammonia molecules, and the calculations accurately describe the excitation energies and photoinduced structural deformations.Comment: 2 figures and 2 table

Non-extensive study of Rigid and Non-rigid Rotators

The isotropic rigid and non-rigid rotators in the framework of Tsallis statistics are studied in the high and low temperature limits. The generalized partition functions, internal energies and heat capacities are calculated. It has been found that results are in well agreement with the classical Boltzmann-Gibbs statistics in the limiting Tsallis index. It has also been observed that nonextensivity parameter q behaves like a scale parameter in the low temperature regime.Comment: 11 Pages, 3 Figures, Late

Quantum resonance, Anderson localisation and selective manipulations in molecular mixtures by ultrashort laser pulses

We demonstrate that the current laser technology used for field-free molecular alignment via a cascade of Raman rotational transitions allows for observing long-discussed non-linear quantum phenomena in the dynamics of the periodically kicked rotor. This includes the scaling of the absorbed energy near the conditions of quantum resonance and Anderson-like localisation in the angular momentum. Based on these findings, we suggest a novel approach to tunable selective rotational excitation and alignment in a molecular mixture, using trains of short laser pulses. We demonstrate the efficiency of this approach by applying it to a mixture of two nitrogen isotopologues (14N2 and 15N2), and show that strong selectivity is possible even at room temperature

Excitation and emission spectra of rubidium in rare-gas thin-films

To understand the optical properties of atoms in solid state matrices, the absorption, excitation and emission spectra of rubidium doped thin-films of argon, krypton and xenon were investigated in detail. A two-dimensional spectral analysis extends earlier reports on the excitation and emission properties of rubidium in rare-gas hosts. We found that the doped crystals of krypton and xenon exhibit a simple absorption-emission relation, whereas rubidium in argon showed more complicated spectral structures. Our sample preparation employed in the present work yielded different results for the Ar crystal, but our peak positions were consistent with the prediction based on the linear extrapolation of Xe and Kr data. We also observed a bleaching behavior in rubidium excitation spectra, which suggests a population transfer from one to another spectral feature due to hole-burning. The observed optical response implies that rubidium in rare-gas thin-films is detectable with extremely high sensitivity, possibly down to a single atom level, in low concentration samples.Comment: 7 pages, 5 figure

Anisotropy induced Feshbach resonances in a quantum dipolar gas of magnetic atoms

We explore the anisotropic nature of Feshbach resonances in the collision between ultracold magnetic submerged-shell dysprosium atoms, which can only occur due to couplings to rotating bound states. This is in contrast to well-studied alkali-metal atom collisions, where most Feshbach resonances are hyperfine induced and due to rotation-less bound states. Our novel first-principle coupled-channel calculation of the collisions between open-4f-shell spin-polarized bosonic dysprosium reveals a striking correlation between the anisotropy due to magnetic dipole-dipole and electrostatic interactions and the Feshbach spectrum as a function of an external magnetic field. Over a 20 mT magnetic field range we predict about a dozen Feshbach resonances and show that the resonance locations are exquisitely sensitive to the dysprosium isotope.Comment: 5 pages, 4 figure

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

Reactions of C2_2({\it a}3Piu^3Pi_u) with selected saturated alkanes: A temperature dependence study

We present a temperature dependence study on the gas phase reactions of the C$_2$({\it a}$^3Pi_u$) radical with a selected series of saturated alkanes (C$_2$H$_6$, C$_3$H$_8$, n-C$_4$H$_10$, i-C$_4$H$_10$, and n-C$_6$H$_14$) by means of pulsed laser photolysis/laser-induced fluorescence technique. The bimolecular rate constants for these reactions were obtained between 298 and 673 K. A pronounced negative temperature effect was observed for n-C$_4$H$_10$, i-C$_4$H$_10$, and n-C$_6$H$_14$ and interpreted in terms of steric hindrance of the more reactive secondary or tertiary C-H bonds by less reactive CH$_3$ groups. Detailed analysis of our experimental results reveals quantitatively the temperature dependence of reactivities for the primary, secondary, and tertiary C-H bonds in these saturated alkanes and further lends support to a mechanism of hydrogen abstraction.Comment: 26 pages, 8 figures, 1 table, 30 references; accepted to JC

C_2 in Peculiar DQ White Dwarfs

White dwarfs (WDs) with carbon absorption features in their optical spectra are known as DQ WDs. The subclass of peculiar DQ WDs are cool objects (T_eff<6000 K) which show molecular absorption bands that have centroid wavelengths ~100-300 Angstroms shortward of the bandheads of the C_2 Swan bands. These "peculiar DQ bands" have been attributed to a hydrocarbon such as C_2H. We point out that C_2H does not show strong absorption bands with wavelengths matching those of the peculiar DQ bands and neither does any other simple molecule or ion likely to be present in a cool WD atmosphere. The most straightforward explanation for the peculiar DQ bands is that they are pressure-shifted Swan bands of C_2. While current models of WD atmospheres suggest that, in general, peculiar DQ WDs do not have higher photospheric pressures than normal DQ WDs do, that finding requires confirmation by improved models of WD atmospheres and of the behavior of C_2 at high pressures and temperatures. If it is eventually shown that the peculiar DQ bands cannot be explained as pressure-shifted Swan bands, the only explanation remaining would seem to be that they arise from highly rotationally excited C_2 (J_peak>45). In either case, the absorption band profiles can in principle be used to constrain the pressure and the rotational temperature of C_2 in the line-forming regions of normal and peculiar DQ WD atmospheres, which will be useful for comparison with models. Finally, we note that progress in understanding magnetic DQ WDs may require models which simultaneously consider magnetic fields, high pressures and rotational excitation of C_2.Comment: ApJ in press. 8 pages emulateapj style, 1 figur