Solvation of triplet Rydberg states of molecular hydrogen in superfluid helium

We report ab initio interaction potentials, transition dipole moments, and radiative lifetimes for the four lowest triplet states of ${\mathrm{H}}_{2}:$ $b$ ${}^{3}{\ensuremath{\Sigma}}_{u}^{+},$ $c$ ${}^{3}{\ensuremath{\Pi}}_{u},$ $a$ ${}^{3}{\ensuremath{\Sigma}}_{g}^{+},$ and $e$ ${}^{3}{\ensuremath{\Sigma}}_{u}^{+},$ and their response to the perturbation due to approaching ground state He atom. Hybrid density functional\char21{}quantum Monte Carlo calculations employing the ab initio interaction potentials are then used for calculating the liquid structure around the molecular excimers in bulk superfluid ${}^{4}\mathrm{He}.$ Calculations demonstrate a wide variety of possible solvation …

Electronic Spectroscopy of C2 in Solid Rare Gas Matrixes

Electronic spectroscopy of the C(2) molecule is investigated in Ar, Kr, and Xe matrixes in the 150-500 nm range. In the Ar matrix, the D ((1)Sigma(u)(+)) <-- ((1)Sigma(g)(+)) Mulliken band near 240 nm is the sole absorption in the UV range, whereas in the Kr matrix additional bands in the 188-209 nm range are assigned to the Kr(n)()(+)C(2)(-) <-- Kr(n)()C(2) charge-transfer absorptions. Because of the formation of a bound C(2)Xe species, the spectral observations in the Xe matrix differ dramatically from the lighter rare gases: the Mulliken band is absent and new bands appear near 300 and 423 nm. The latter is assigned to the forbidden B'((1)Sigma(g)(+)) <-- X ((1)Sigma(g)(+)) transition, b…

Effects of static and dynamic perturbations on isotropic hyperfine coupling constants in some quinone radicals.

The effects of solvent dielectric response on the isotropic hyperfine coupling constants of the 1,4-benzoquinone, 1,4-naphthoquinone and 9,10-anthraquinone anions and 1,4-naphthalenediol cation radicals were studied by electron spin resonance (ESR) spectroscopy and by the theoretical density functional method within the polarizable continuum model. Experimental results demonstrate that the isotropic hyperfine coupling constants can be obtained with high accuracy and that the effects of solvent impurities can be minimized by careful sample preparation. The results obtained correlate well with theoretical predictions from density functional theory calculations. For 1,4-naphthalenediol both th…

EPR Studies of Atomic Impurities in Rare Gas Matrices

In this article we give an overview of the matrix isolation technique combined with electron paramagnetic resonance (EPR) detection for embedded atomic impurities in solid rare gases. A special emphasis is put on impurity – matrix coupling effects combining both experimental and theoretical approaches.

Electronic Absorption Spectra of HXeCl, HXeBr, HXeI, and HXeCN in Xe Matrix

The electronic UV absorption spectra of thermal reaction products H−Xe−Y (Y= Cl, Br, I, or CN) have been measured in solid Xe at 12 K. The spectra are obtained after the annealing of an extensively...

Efficient numerical method for simulating static and dynamic properties of superfluid helium

Density functional theory (DFT) offers computationally affordable way of describing static and dynamic properties of superfluid 4He. In general, the DFT models yield single particle-like Schrodinger equations with a nonlinear potential term that accounts for all the many-body interactions. The resulting equations can be solved for small amplitude plane wave excitations in the bulk whereas fully numerical solution must be sought in more complicated cases. In this paper we propose a numerical method that can be used in solving the time-dependent nonlinear Schrodinger equation in both real and imaginary times. The method is based on operator splitting technique where each component operator is…

From a fixed bed Ag–alumina catalyst to a modified reactor design: how to enhance the crucial heterogeneous–homogeneous reactions in HC-SCR

Abstract A highly active Ag/alumina catalyst for continuous reduction of NO to nitrogen with n-octane under lean conditions was prepared. It was observed in the reactor set-up experiments for optimization of the converter, that surface generated gas phase species are crucial for obtaining high conversion. EPR and matrix isolated FTIR studies at low temperature (10–18 K) were performed for identification of the radicals. Experimental data, observed at steady state conditions in the temperature range 300–550 °C, was used to produce an artificial neural network model of the catalytic converter with four catalyst beds.

EPR and MO calculation studies on α-aminoanthraquinone anion radicals in aprotic solvents

Molecular orbital study of conformational isomers and rotational barriers of methyl substituted hydroquinone cation radicals

Abstract The torsional potential energy curve of the hydroxyl group of hydroquinone and tetramethyl-hydroquinone cation radicals were explored with various ab initio methods. The minimum and the torsional transition state geometries and energies were computed by using high accuracy density functional methods yielding the rotation barrier height and the energy difference between the cis- and trans-isomers. The obtained minimum energy geometry for the hydroquinone cation radical indicates that the CO bond has shortened when compared to the neutral species. We attribute this to the increased double-bond character of this bond. The energy minima were located for methyl-hydroquinone, 2,3-dimeth…

Charge transfer states of C2 in Kr clusters

Abstract Ab initio and diatomics-in-ionic-systems (DIIS) calculations are carried out for the C 2 –Kr pair and C 2 –Kr n clusters, respectively. Energetics and transition dipole moments between the ground and excited states are obtained from the calculations. This data is then used to predict the UV charge transfer absorption spectrum of C 2 embedded in Kr n clusters with n  = 1, 12, and 224. The results reveal discrete structure in the computed UV spectrum, which is mainly related to the spin–orbit splitting of Kr + .

Effect of ischaemic preconditioning, cardiopulmonary bypass and myocardial ischaemic/reperfusion on free radical generation in CABG patients.

Abstract Objective: To investigate the free radicals (FR) generation after ischaemic preconditioning and cardiopulmonary bypass and during reperfusion in CABG patients, and the role of ischaemic preconditioning. Methods: Forty-three CABG patients were randomised into an ischaemic preconditioning and a control group. The protocol for ischaemic preconditioning was two cycles of 2-min ischaemia followed by 3-min reperfusion. Free radicals were measured using electron spin resonance spectroscopy. Global and right heart functions were collected. Results: The free radicals generation in coronary sinus blood in the ischaemic preconditioning group was 9.7 and 16.6% after the ischaemic preconditioni…

Comparison of spin density calculation methods for various alkyl-substituted 9,10-anthraquinone anion radicals in the solution phase

EPR and ENDOR spectra were recorded for 2-methyl-9,10-anthraquinone (2-methylAQ), 2-ethylAQ, 2-tertbutylAQ and 2,3-dimethylAQ anion radicals in the solution phase. The EPR spectra were simulated with the help of ENDOR data. The experimental isotropic hyperfine coupling constants (IHFCs) were compared with calculated values from semi-empirical INDO, spin-restricted AM1/CI and B3PW91 density-functional methods. The best computational methods for the IHFCs were the semi-empirical AM1/CI method and the B3PW91 density-functional method with a large basis set.

Rotation of methyl radicals in molecular solids.

Electron spin resonance (ESR) measurements were carried out to study the rotation of methyl radicals (CH(3)) in solid carbon monoxide, carbon dioxide, and nitrogen matrices. The radicals were produced by dissociating methane by plasma bursts generated by a focused 193 nm ArF excimer laser radiation during the gas condensation on the substrate. The ESR spectra exhibit anisotropic features that persist over the temperature range examined, and in most cases this indicates a restriction of rotation about the C(2) symmetry axis. A nonrotating CH(3) was also observed in a CO(2) matrix. The intensity ratio between the symmetric (A) and antisymmetric (E) nuclear spin states was recorded as a functi…

Solution of time-independent Schrödinger equation by the imaginary time propagation method

Numerical solution of eigenvalues and eigenvectors of large matrices originating from discretization of linear and non-linear Schrodinger equations using the imaginary time propagation (ITP) method is described. Convergence properties and accuracy of 2nd and 4th order operator-splitting methods for the ITP method are studied using numerical examples. The natural convergence of the method is further accelerated with a new dynamic time step adjustment method. The results show that the ITP method has better scaling with respect to matrix size as compared to the implicitly restarted Lanczos method. An efficient parallel implementation of the ITP method for shared memory computers is also demons…

EPR, ENDOR and TRIPLE resonance of amino-substituted 9,10-anthraquinone radicals and the rotation of the amino groups in the solution phase

EPR, ENDOR and TRIPLE resonance spectra were recorded for 1-amino-9,10-anthraquinone (1-aminoAQ), 2-aminoAQ, 1,2-diaminoAQ, 1.4-diaminoAQ, 1,5-diaminoAQ and 2,6-diaminoAQ anion radicals in the solution phase. The rotation of the amino groups is discussed with reference to the experimental data. Rotation barrier calculations were carried out using B3PW91/3-21G* density functional method. The amino groups at positions 1, 4, 5, 8 were found not to be in rotational movement up to the EPR time-scale.

Ab initio study of halogenated diphenyl ethers. NMR chemical shift prediction

Rotation of methyl radicals in a solid krypton matrix

Electron spin resonance (ESR) measurements were carried out to study the rotation of methyl radicals (CH(3)) in a solid krypton matrix at 17-31 K temperature range. The radicals were produced by dissociating methane by plasma bursts generated by a focused 193 nm excimer laser radiation during the krypton gas condensation on the substrate. The ESR spectrum exhibits only isotropic features at the temperature range examined, and the intensity ratio between the symmetric (A) and antisymmetric (E) spin state lines exhibits weaker temperature dependence than in a solid argon matrix. However, the general appearance of the methyl radical spectrum depends strongly on temperature due to the pronounce…

HC-SCR of NOx over Ag/alumina: a combination of heterogeneous and homogeneous radical reactions?

Matrix isolation combined with EPR and FT-IR technique at low temperature has been used to study the gas phase species involved in HC-SCR over a highly active Ag/alumina catalyst. A combination of heterogeneous and homogeneous (radical) reactions is proposed to take place over a Ag/alumina catalyst during HC-SCR. Radicals of low molecular weight were trapped in a growing argon matrix behind the Ag/alumina catalyst. In the same matrix, cyanogen isocyanate was detected and is suggested to be a key intermediate for the formation of amines and ammonia via the hydrolysis of isocyanate species.

Time-domain analysis of electronic spectra in superfluid 4He

Abstract Electronic absorption spectra of impurities in superfluid helium is developed in time domain, using time-dependent density functional theory to describe liquid 4 He and time-dependent perturbation theory to describe the electronic degrees of freedom of the impurity. Angularly isotropic potentials are used to describe the molecule–helium interactions in the ground and excited electronic states. The calculations rationalize experimentally observed phonon side-bands in 4 He droplets and in bulk helium, and allow assignments of spectral features to specific motions of the liquid.

Trapping of laser-vaporized alkali metal atoms in rare-gas matrices

Abstract Alkali metal atoms prepared by laser ablation of solid Li and Na are trapped in Ar, Kr, and Xe matrices and studied by electron paramagnetic resonance spectroscopy (EPR) at 15 K. Evidence for tight trapping sites, not observed for atoms generated by conventional Knudsen oven techniques, is presented. The novel tight trapping sites are characterized by a large increase in the isotropic hyperfine coupling constant and a simultaneous decrease in the isotropic g -value. Based on the EPR data, it is suggested that the observed tight trapping corresponds to single substitution of lattice atoms in Ar, Kr, and Xe matrices.

Temperature dependence of the isotropic hyperfine coupling constants in 1,4-hydroquinone and 1,4-dihydroxynaphthalene cation radicals

Injection of atoms and molecules in a superfluid helium fountain: Cu and Cu2He(n) (n = 1, ..., ∞).

We introduce an experimental platform designed around a thermomechanical helium fountain, which is aimed at investigating spectroscopy and dynamics of atoms and molecules in the superfluid and at its vapor interface. Laser ablation of copper, efficient cooling and transport of Cu and Cu(2) through helium vapor (1.5 K < T < 20 K), formation of linear and T-shaped Cu(2)-He complexes, and their continuous evolution into large Cu(2)-He(n) clusters and droplets are among the processes that are illustrated. Reflection is the dominant quantum scattering channel of translationally cold copper atoms (T = 1.7 K) at the fountain interface. Cu(2) dimers mainly travel through the fountain unimpeded. How…