Search results for " molecule"
showing 10 items of 1523 documents
Alignment-orientation conversion in molecules in an external magnetic field caused by a hyperfine structure
2000
The paper presents a discussion on the problem of alignment-orientation conversion in an excited state of molecules. It is shown that a rather strong alignment-orientation conversion effect in the excited molecular state can be caused by a joint action of an external magnetic field and hyperfine interaction. The orientation thus created is transverse, i.e. perpendicular to the direction of the external magnetic field. The magnitude of this effect is analyzed as dependent on molecular parameters.
Photoelectron spectra from first principles: from the many-body to the single-particle picture
2008
We derive a many-body method to evaluate photoelectron spectra of atoms, molecules and clusters from first principles. The excitation energies and the spectroscopic factors are calculated from the linear-response time-dependent density functional theory. The method is applied to noble metal anions, anionic clusters and to neutral small molecules. Our approach shows significant improvement over a simple single-particle treatment and gives an insight into the necessary conditions under which the single-particle picture holds. The consideration of the spectroscopic factor is shown to be crucial for the correct description of inner valence photoelectron peaks.
Quantum chemical simulations of hole self-trapping in semi-ionic crystals
1994
A novel formalism is presented for reliable calculations of the energetics of hole self-trapping in semi-ionic solids with mixed valence bands. Unlike previous model-Hamiltonian-type approaches, it is based on self-consistent quantum chemical INDO simulations of the atomistic and electronic structure of a self-trapped hole, making no a priori assumptions about a particular form of its localization (if any). This formalism is applied to the problem of hole self-trapping in corundum crystals (a -A1203). The hole self-trapping is found to be energetically favorable in the form of a diatomic 02 molecule with strong covalent bonding quite similar to the self-trapped hole (VK-center) in alkali ha…
Dynamical Processes in Open Quantum Systems from a TDDFT Perspective: Resonances and Electron Photoemission
2015
We present a review of different computational methods to describe time-dependent phenomena in open quantum systems and their extension to a density-functional framework. We focus the discussion on electron emission processes in atoms and molecules addressing excited-state lifetimes and dissipative processes. Initially we analyze the concept of an electronic resonance, a central concept in spectroscopy associated with a metastable state from which an electron eventually escapes (electronic lifetime). Resonances play a fundamental role in many time-dependent molecular phenomena but can be rationalized from a time-independent context in terms of scattering states. We introduce the method of c…
Purely long-range polar molecules composed of identical lanthanide atoms
2019
International audience; Doubly polar molecules, possessing an electric dipole moment and a magnetic dipole moment, can strongly couple to both an external electric field and a magnetic field, providing unique opportunities to exert full control of the system quantum state at ultracold temperatures. We propose a method for creating a purely long-range doubly polar homonuclear molecule from a pair of strongly magnetic lanthanide atoms, one atom being in its ground level and the other in a superposition of quasi-degenerate opposite-parity excited levels [Phys. Rev. Lett. 121, 063201 (2018)]. The electric dipole moment is induced by coupling the excited levels with an external electric field. W…
High-resolution study of some doubly excited vibrational states of PH2D: the m1 + m2, m2 + m5, m2 + m3, and m2 + m6 bands
2004
Abstract The absorption bands ν 1 + ν 2 , ν 2 + ν 3 , and ν 2 + ν 6 of PH 2 D have been recorded for the first time using a high-resolution Bruker 120 HR interferometer, and rotationally analyzed. Some transitions belonging to the very weak band ν 2 + ν 5 and enhanced in intensity by strong interactions with the ν 1 + ν 2 band were also assigned. Sets of parameters obtained from the fit reproduce experimental line position of the bands ν 1 + ν 2 and ν 2 + ν 3 with about the experimental accuracy. The residuals of the ro-vibrational energies of the ν 2 + ν 6 band are about 10 times larger. Reasons for the poorer reproduction of the latter data are given.
Field-free molecular alignment for measuring ionization probability
2007
International audience; We have shown in a recent letter (Loriot et al 2006 Opt. Lett. 31 2897) the possibility of determining the ionization probability of linear molecules by using an all-optical technique that takes advantage of post-pulse molecular alignment. To that end, we have implemented a ‘cross-defocusing' technique producing a signal sensitive to both alignment and ionization. The analysis of the signal provides a quantitative measurement of the ionization probability calibrated with molecular alignment. In the present work, the method is discussed in more detail and applied to the measurement of the ionization probability of N2 as well as to the determination of the ionization r…
Analyzing observations of molecules in the ISM: Theoretical and experimental studies of energy transfer
2012
Our laboratories have recently calculated a set of collision coefficients characterizing the efficiency of energy transfer between helium and/or hydrogen and a large variety of interstellar molecules. We have considered with molecules ranging from light hydrides, observed by the Herschel Space Observatory, to medium size molecules, observed by mm antennas, to heavy complex organic molecules, observed also in the cm range. We present a review of recent theoretical results obtained in our laboratories, for various kinds of commonly observed molecules.
Direct theoretical evidence of nuclear motion in H+2by means of high harmonic generation
2007
The numerical solution of the time-dependent Schro ̈dinger equation for vibrating hydrogen molecular ions in many-cycle laser pulses shows that high- order harmonic generation is sensitive to laser-induced molecular vibrations. In particular, the odd harmonic lines in the emitted spectra are surrounded by additional regular peaks whose spacing is given by the vibrational frequency of the nuclei motion. Analytical theory relates these satellite peaks to the molecular vibrations in terms of an approximated effective potentials. These results are not affected by the dimensionality of the system.
Control of the high harmonic generation spectra by changing the molecule-laser field relative orientation
2010
The time dependent Schrodinger equation of a homonuclear diatomic molecule in the presence of a linearly polarized laser field is numerically solved by means of a split-operator parallel code. The calculations are carried out by assuming a single active electron model with fixed nuclei; a simplified two-dimensional model of the system is used. The highly nonlinear response of the electron wave function to the laser electric field stimulates the molecule to emit electromagnetic radiation consisting of a wide plateau of odd harmonics of the laser field. It is shown that the emitted spectrum can be finely controlled by changing the angle between the laser electric field and the molecular axis;…