2009 Vol. 22, No. 2

Article
Content
2009, 22(2): 0-0. doi: 10.1088/1674-0068/22/2/0-0
Preface
2009, 22(2): 0-0. doi: 10.1088/1674-0068/22/2/0-0
ZrO3 and HfO3 molecules were prepared via reactions of metal monoxides with dioxygen in solid argon and were characterized using matrix isolation infrared absorption spectroscopy as well as theoretical calculations. Unlike the titanium monoxide molecule, which reacted spontaneously with dioxygen to form TiO3, the ZrO and HfO molecules reacted with dioxygen to give the ZrO3 and HfO3 molecules only under visible light irradiation. Density functional calculations predicted that both the ZrO3 and HfO3 molecules possess a closed-shell singlet ground state with a non-planar Cs geometry, in which the side-on coordinated O2 falls into the peroxide category.
Radiofrequency (rf) trapped ions are versatile candidates for a large panel of applicationsranging from quantum information to the creation of cold molecules. Sample size can range from a single to 10^6 ions, and the internal and external energy states of the atoms can be controlled with high precision. In the experiment, we focus on different protocols related to frequency metrology using rf trapped Ca+.
We present quantum mechanical vibrational computations beyond the harmonic approximation from effective second order perturbative and variation perturbation treatments defined as static approaches, as well as vibrational analysis from density functional theory molecular dynamics trajectories at 300 and 600 K. The four schemes are compared in terms of prediction of fundamental transitions, and simulation of the corresponding medium infrared spectrum at the same level of theory using the B3LYP/6-31+G(d,p) description of the electronic structure. We summarize conclusions about advantages and drawbacks of these twoapproaches and report the main results obtained for semi-rigid and flexible molecules.
Elementary cholesterol was analyzed with IR laser desorption/tunable synchrotron vacuum ultraviolet photoionization mass spectrometry. An exclusive molecular ion of cholesterol is observed by near threshold single-photon ionization with high effciency. Fragments are yielded with the increase of photon energy. The structures of various fragments are determined with commercial electron ionization time-of-flight mass spectrometry. Dominant fragmentation pathways are discussed in detail with the aid of ab initio calculations.
The environmentally important free radical reaction of chlorinated methyl CHCl2 with NO2was investigated by step-scan time-resolved FTIR (TR-FTIR) emission spectroscopy. Vibrationally excited products of CHClO, NO, CO, and HCl are observed in the high-resolution IR emission spectra and three possible reaction channels are therefore elucidated. In particular,the product CO is newly detected and the product HCl is identified explicitly as a yield from the CHCl2+NO2 reaction, taking advantage of the sensitive detection of HCl and CO with TR-FTIR. These results are of particular interests to understand the related realistic chemical processes including atmospheric photochemistry, biofuel combustion, waste destruction,and smoking fire.
FeAs- single layer is tested as a simple model for LaFeAsO and BaFe2As2 based on firstprinciples calculations using generalized gradient approximation (GGA) and GGA+U. The calculated single-layer geometric and electronic structures are inconsistent with that of bulk materials. The bulk collinear antiferromagnetic ground state failed to be obtained in the FeAs- single layer. The monotonous behavior of the Fe-As distance in z direction upon electron or hole doping is also in contrast with bulk materials. The results indicate that, in LaFeAsO and BaFe2As2, interactions between FeAs layer and other layers beyond simple charge doping are important, and a single FeAs layer may not represent a good model for Fe based superconducting materials.
The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers,4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory.The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.
The use of a broadband, frequency shaped femtosecond laser on translationally cold cesium molecules has recently demonstrated to be a very efficient method of cooling also the vibrational degree of freedom. A sample of cold molecules, initially distributed over several vibrational levels, has thus been transfered into a single selected vibrational level of the singlet X1∑g ground electronic state. Our method is based on repeated optical pumping by laser light with a spectrum broad enough to excite all populated vibrational levels but limited in its frequency bandwidth with a spatial light modulator. In such a way we are able to eliminate transitions from the selected level, in which molecules accumulate. In this paper we briefly report the main experimental results and then address, in a detailed way by computer simulations, the perspectives for a “complete”cooling of the molecules, including also the rotational degree of freedom. Since the pumping process strongly depends on the relative shape of the ground and excited potential curves, ro-vibrational cooling through di?erent excited states is theoretically compared.
High resolution laser induced fluorescence spectra of IrN in the spectral region between 394 and 520 nm were recorded using laser vaporization/reaction free jet expansion and laser induced fluorescence spectroscopy. Seven new vibronic transition bands were observed and analyzed. Two Ω=1 and five Ω=0 new states were identified. Least squares fit of rotationally resolved transition lines yielded accurate molecular constants for the upper states. Spectra of isotopic molecules were observed, which provided confirmation for the vibrational assignment. Comparison of the observed electronic states of IrB, IrC, and IrN provides a good understanding of the chemical bonding of this group of molecules.
The evolution of a molecular system excited above its ionization threshold depends on a number of parameters that include the nature of the excited states and their couplings to the various continua. The general nature of the processes governing this evolution depends also essentially on the complexity of the molecule, more precisely on its size, density of states,and strength of the couplings among the various internal degrees of freedom. In this paper we address the question of the transition between autoionization that prevails in small molecules, and delayed ionization occurring in larger molecules or clusters. This transition is illustrated by autoionization of Na2 Rydberg states on one hand, delayed ionization in fullerene C60, and delayed detachment in small cluster anions on the other hand. All processes are studied in the case of nanosecond laser excitation, corresponding to a rather slow deposition of the internal energy.
Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions (MFPADs). We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the I(χ,θe, φe) MFPADs, whereχis the orientation of the molecular axis with respect to the light quantization axis and (θe,φe) the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization (DPI) of D2 at two photon excitation energies, hⅴ=19 eV, where direct PI is the only channel opened, and hⅴ=32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.
The electronic states of molecules made of electropositive and electronegative components result from the interference between the covalent configurations and the ionic configurations.This work shows complex aspects of these ionic-covalent couplings in small molecules such as Li2H, Li2F, and Li4F. The extension of this type of analysis to the adsorption of the electrophilic molecules on the metal clusters or on the metal surfaces is supposed to lead to a radically new interpretation of the observed physical and chemical properties.
Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected by (2+1) resonance enhanced multiphoton ionization via the D2∑- electronic state. The total kinetic energy spectra of the OH+NO2 channel from the photolysis of HONO2 show that both NO2(X 2A1) and NO2(? 2B2) channels are present,suggesting that both 11 A" and 21 A" excited electronic states of HONO2 are involved in the excitation. The parallel angular distributions suggest that the dissociation of the nitric acid is a fast process in comparison with the rotational period of the HNO3 molecule. The anisotropy parameter ? for the hydroxyl elimination channel is found to be dependent on the OH product rotational state as well as the photolysis energy.
The constructive or destructive spectral interference between the molecular groups oriented up and down at the interface in the sum-frequency generation (SFG) spectra provides a direct measurement of the absolute orientation of these molecular groups. This simple approach can be employed to interrogate absolute molecular orientations other than using the complex absolute phase measurement in the SFG studies. We used the -CN group in the p-cyanophenol (PCP) molecule as the internal phase standard, and we measured the phases of the SFG fields of the ?CN groups in the 3,5-dimethyl-4-hydroxy-benzonitrile (35DMHBN) and 2,6-dimethyl-4-hydroxy-benzonitrile (26DMHBN) at the air/water interface by measuring the SFG spectra of the aqueous surfaces of the mixtures of the PCP, 35DMHBN, and 26DMHBN solutions. The results showed that the 35DMHBN had its -CN group pointing into the aqueous phase; while the 26DMHBN, similar to the PCP, had its -CN group pointing away from the aqueous phase. The tilt angles of the -CN group for both the 35DMHBN and 26DMHBN molecules at the air/water interface were around 25o-45o from the interface normal. These results provided insights on the understanding of the detailed balance of the competing factors, such as solvation of the polar head groups, hydrogen bonding and hydrophobic effects, etc., on influencing the absolute molecular orientation at the air/water interface.
The pyrolysis of pyridine (5.26% pyridine in argon) was performed with tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry technique atthe temperature range of 1255-1765 K at 267 Pa. About 20 products and intermediates,containing major species H2, HCN, C2H2, C5H3N, C4H2, and C3H3N, were identified by near-threshold measurements of photoionization mass spectra and their mole fractions vs.temperatures were estimated. The major reaction pathways are analyzed based on theexperimental observations
The Gaussian weighted trajectory method (GWTM) is a practical implementation of classical S matrix theory (CSMT) in the random phase approximation, CSMT being the first and simplest semi-classical approach of molecular collisions, developped in the early seventies. Though very close in spirit to the purely classical description, GWTM accounts to some extent for the quantization of the different degrees-of-freedom involved in the processes.While CSMT may give diverging final state distributions, in relation to the rainbow effect of elastic scattering theory, GWTM has never led to such a mathematical catastrophe. The goal of the present note is to explain this finding.