No Arabic abstract
Quantum reactive scattering calculations on the vibrational quenching of HD due to collisions with H were carried out employing an accurate potential energy surface. The state-to-state cross sections for the chemical reaction HD ($v=1, j=0$) + H $rightarrow$ D + H$_2$ ($v=0, j$) at collision energies between 1 and 10,000 cm$^{-1}$ are presented, and a Feshbach resonance in the low-energy regime, below the reaction barrier, is observed for the first time. The resonance is attributed to coupling with the vibrationally adiabatic potential correlating to the $v=1, j=1$ level of the HD molecule, and it is dominated by the contribution from a single partial wave. The properties of the resonance, such as its dynamic behavior, phase behavior, and lifetime, are discussed.
For localized and oriented vibrationally excited molecules, the one-body probability density of the nuclei (one-nucleus density) is studied. Like the familiar and widely used one-electron density that represents the probability of finding an electron at a given location in space, the one-nucleus density represents the probability of finding a nucleus at a given position in space independent of the location of the other nuclei. In contrast to the full many-dimensional nuclear probability density, the one-nucleus density contains less information and may thus be better accessible by experiment, especially for large molecules. It also provides a quantum-mechanical view of molecular vibrations that can easily be visualized. We study how the nodal structure of the wavefunctions of vibrationally excited states translates to the one-nucleus density. It is found that nodes are not necessarily visible: Already for relatively small molecules, only certain vibrational excitations change the one-nucleus density qualitatively compared to the ground state. It turns out that there are some simple rules for predicting the shape of the one-nucleus density from the normal mode coordinates, and thus for predicting if a vibrational excitation is visible in a corresponding experiment.
Rotational spectra in four new excited vibrational levels of the linear carbon chain radical C$_4$H radical were observed in the millimeter band between 69 and 364 GHz in a low pressure glow discharge, and two of these were observed in a supersonic molecular beam between 19 and 38 GHz. All have rotational constants within 0.4% of the $^2Sigma^+$ ground vibrational state of C$_4$H and were assigned to new bending vibrational levels, two each with $^2Sigma$ and $^2Pi$ vibrational symmetry. The new levels are tentatively assigned to the $1 u_6$ and $1 u_5$ bending vibrational modes (both with $^2Pi$ symmetry), and the $1 u_6 + 1 u_7$ and $1 u_5 + 1 u_6$ combination levels ($^2Sigma$ symmetry) on the basis of the derived spectroscopic constants, relative intensities in our discharge source, and published laser spectroscopic and quantum calculations. Prior spectroscopic constants in the $1 u_7$ and $2 u_7$ levels were refined. Also presented are interferometric maps of the ground state and the $1 u_7$ level obtained with the SMA near 257 GHz which show that C$_4$H is present near the central star in IRC+10216. We found no evidence with the SMA for the new vibrationally excited levels of C$_4$H at a peak flux density averaged over a $3^{primeprime}$ synthesized beam of $ge 0.15$ Jy/beam in the 294-296 and 304-306 GHz range, but it is anticipated that rotational lines in the new levels might be observed in IRC+10216 when ALMA attains its full design capability.
Neutral molecules, isolated in the gas-phase, can be prepared in a long-lived excited state and stored in a trap. The long observation time afforded by the trap can then be exploited to measure the radiative lifetime of this state by monitoring the temporal decay of the population in the trap. This method is demonstrated here and used to benchmark the Einstein $A$-coefficients in the Meinel system of OH. A pulsed beam of vibrationally excited OH radicals is Stark decelerated and loaded into an electrostatic quadrupole trap. The radiative lifetime of the upper $Lambda$-doublet component of the $X ^2Pi_{3/2}, v=1, J=3/2$ level is determined as $59.0 pm 2.0$ ms, in good agreement with the calculated value of $57.7 pm 1.0$ ms.
A high-dimensional potential energy surface (PES) for CO interaction with the Au(111) surface is developed using a machine-learning algorithm. Including both molecular and surface coordinates, this PES enables the simulation of the recent experiment on scattering of vibrationally excited CO from Au(111). Trapping in a physisorption well is observed to increase with decreasing incidence energy. While energy dissipation of physisorbed CO is slow, due to weak coupling with both the phonons and electron-hole pairs, its access to the chemisorption well facilitates fast vibrational relaxation of CO through nonadiabatic coupling with surface electron-hole pairs.
Fundamental entanglement related challenges have prevented quantum interference-based control (i.e. coherent control) of collisional cross sections from being implemented in the laboratory. Here, differential cross sections for reactive scattering at low temperatures are shown to provide a unique opportunity to display such interference-based control by forming coherent superpositions of degenerate rotational states of reactant molecules |jmi with different m. In particular, we identify and quantify a unique signature of coherent control in reactive scattering with applications to F + H2 ! H + HF and HF + D F + HD ! HD + F at 11 K. Control is shown to be extensive.