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!

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

Quantum initial condition sampling for linearized density matrix dynamics: Vibrational pure dephasing of iodine in krypton matrices

This paper reviews the linearized path integral approach for computing time dependent properties of systems that can be approximated using a mixed quantum-classical description. This approach is applied to studying vibrational pure dephasing of ground state molecular iodine in a rare gas matrix. The Feynman-Kleinert optimized harmonic approximation for the full system density operator is used to sample initial conditions for the bath degrees of freedom. This extremely efficient approach is compared with alternative initial condition sampling techniques at low temperatures where classical initial condition sampling yields dephasing rates that are nearly an order of magnitude too slow compared with quantum initial condition sampling and experimental results.Comment: 20 pages and 8 figure

Detection of interstellar CH_3

Observations with the Short Wavelength Spectrometer (SWS) onboard the {\it Infrared Space Observatory} (ISO) have led to the first detection of the methyl radical ${\rm CH_3}$ in the interstellar medium. The $\nu_2$ $Q-$branch at 16.5 $\mu$m and the $R$(0) line at 16.0 $\mu$m have been unambiguously detected toward the Galactic center SgrA$^*$. The analysis of the measured bands gives a column density of (8.0$\pm$2.4)$\times10^{14}$ cm$^{-2}$ and an excitation temperature of $(17\pm 2)$ K. Gaseous ${\rm CO}$ at a similarly low excitation temperature and ${\rm C_2H_2}$ are detected for the same line of sight. Using constraints on the ${\rm H_2}$ column density obtained from ${\rm C^{18}O}$ and visual extinction, the inferred ${\rm CH_3}$ abundance is $(1.3{{+2.2}\atop{-0.7}}) \times 10^{-8}$. The chemically related ${\rm CH_4}$ molecule is not detected, but the pure rotational lines of ${\rm CH}$ are seen with the Long Wavelength Spectrometer (LWS). The absolute abundances and the ${\rm CH_3/CH_4}$ and ${\rm CH_3/CH}$ ratios are inconsistent with published pure gas-phase models of dense clouds. The data require a mix of diffuse and translucent clouds with different densities and extinctions, and/or the development of translucent models in which gas-grain chemistry, freeze-out and reactions of ${\rm H}$ with polycyclic aromatic hydrocarbons and solid aliphatic material are included.Comment: 2 figures. ApJL, Accepte

A geometrical approach to the dynamics of spinor condensates I: Hydrodynamics

In this work, we derive the equations of motion governing the hydrodynamics of spin-F spinor condensates. We pursue a description based on standard physical variables (total density and superfluid velocity), alongside 2F `spin-nodes': unit vectors that describe the spin F state, and also exhibit the point-group symmetry of a spinor condensate's mean-field ground state. The hydrodynamic equations of motion consist of a mass continuity equation, 2F Landau-Lifshitz equations for the spin-nodes, and a modified Euler equation. In particular, we provide a generalization of the Mermin-Ho relation to spin one, and find an analytic solution for the skyrmion texture in the incompressible regime of a spin-half condensate. These results exhibit a beautiful geometrical structure that underlies the dynamics of spinor condensates.Comment: 12 pages. First paper in two-part serie

Relaxation paths for single modes of vibrations in isolated molecules

A numerical simulation of vibrational excitation of molecules was devised, and used to excite computational models of common molecules into a prescribed, pure, normal vibration mode in the ground electronic state, with varying, controlable energy content. The redistribution of this energy (either non-chaotic or irreversible IVR) within the isolated, free molecule is then followed in time with a view to determining the coupling strength between modes. This work was triggered by the need to predict the general characters of the infrared spectra to be expected from molecules in interstellar space, after being excited by photon absorption or reaction with a radical. It is found that IVR from a pure normal mode is very "restricted" indeed at energy contents of one mode quantum or so. However, as this is increased, or when the excitation is localized, our approach allows us to isolate, describe and quantify a number of interesting phenomena, known to chemists and in non-linear mechanics, but difficult to demonstrate experimentally: frequency dragging, mode locking or quenching or, still, instability near a potential surface crossing, the first step to generalized chaos as the energy content per mode is increased.Comment: 25 pages, 15 figures; accepted by J. Atom. Phys.

Quantum theory of an atom laser originating from a Bose-Einstein condensate or a Fermi gas in the presence of gravity

We present a 3D quantum mechanical theory of radio-frequency outcoupled atom lasers from trapped atomic gases in the presence of the gravitational force. Predictions for the total outcoupling rate as a function of the radio-frequency and for the beam wave function are given. We establish a sum rule for the energy integrated outcoupling, which leads to a separate determination of the coupling strength between the atoms and the radiation field. For a non-interacting Bose-Einstein condensate analytic solutions are derived which are subsequently extended to include the effects of atomic interactions. The interactions enhance interference effects in the beam profile and modify the outcoupling rate of the atom laser. We provide a complete quantum mechanical solution which is in line with experimental findings and allows to determine the validity of commonly used approximative methods. We also extend the formalism to a fermionic atom laser and analyze the effect of superfluidity on the outcoupling of atoms.Comment: 13 pages, 8 figures, slightly expanded versio

Dynamics of Bulk vs. Nanoscale WS_2: Local Strain and Charging Effects

We measured the infrared vibrational properties of bulk and nanoparticle WS$_2$ in order to investigate the structure-property relations in these novel materials. In addition to the symmetry-breaking effects of local strain, nanoparticle curvature modifies the local charging environment of the bulk material. Performing a charge analysis on the \emph{xy}-polarized E$_{1u}$ vibrational mode, we find an approximate 1.5:1 intralayer charge difference between the layered 2H material and inorganic fullerene-like (IF) nanoparticles. This effective charge difference may impact the solid-state lubrication properties of nanoscale metal dichalcogenides.Comment: 6 pages, 5 figure

Exact Coupling Coefficient Distribution in the Doorway Mechanism

In many--body and other systems, the physics situation often allows one to interpret certain, distinct states by means of a simple picture. In this interpretation, the distinct states are not eigenstates of the full Hamiltonian. Hence, there is an interaction which makes the distinct states act as doorways into background states which are modeled statistically. The crucial quantities are the overlaps between the eigenstates of the full Hamiltonian and the doorway states, that is, the coupling coefficients occuring in the expansion of true eigenstates in the simple model basis. Recently, the distribution of the maximum coupling coefficients was introduced as a new, highly sensitive statistical observable. In the particularly important regime of weak interactions, this distribution is very well approximated by the fidelity distribution, defined as the distribution of the overlap between the doorway states with interaction and without interaction. Using a random matrix model, we calculate the latter distribution exactly for regular and chaotic background states in the cases of preserved and fully broken time--reversal invariance. We also perform numerical simulations and find excellent agreement with our analytical results.Comment: 22 pages, 4 figure

A Spectroscopic Survey of Electronic Transitions of C6_6H, 13^{13}C6_6H, and C6_6D

Electronic spectra of C$_6$H are measured in the $18\,950-21\,100$ cm$^{-1}$ domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)bands of C$_6$H are presented, all probing the vibrational manifold of the B$^2\Pi$ electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for $^{13}$C$_6$H and C$_6$D), predictions from ab initio calculations as well as rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the $0_0^0$ origin band, three non-degenerate stretching vibrations along the linear backbone of the C$_6$H molecule are assigned: the $\nu_6$ mode associated with the C-C bond vibration and the $\nu_4$ and $\nu_3$ modes associated with C$\equiv$C triple bonds. For the two lowest $\nu_{11}$ and $\nu_{10}$ bending modes, a Renner-Teller analysis is performed identifying the $\mu^2\Sigma$($\nu_{11}$) and both $\mu^2\Sigma$($\nu_{10}$) and $\kappa^2\Sigma$($\nu_{10}$) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as $\mu^2\Sigma$($\nu_9$) and $\mu^2\Sigma$($\nu_8$) levels. In the excitation region below the first non-degenerate vibration ($\nu_6$), some $^2\Pi-^{2}\Pi$ transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a $^2\Pi-^{2}\Pi$ transition found above the $\nu_6$ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B$^2\Pi$ state of C$_6$H is derived and presented.Comment: Accepted for publication in The Journal of Physical Chemistry A (26 July 2016