Structure,rotational dynamics,and superfluidity of small OCS-doped He clusters

The structural and dynamical properties of carbonyl sulfide (OCS) molecules solvated in helium clusters are studied using reptation quantum Monte Carlo, for cluster sizes n=3-20 He atoms. Computer simulations allow us to establish a relation between the rotational spectrum of the solvated molecule and the structure of the He solvent, and of both with the onset of superfluidity. Our results agree with a recent spectroscopic study of this system and provide a more complex and detailed microscopic picture of this system than inferred from experiments.     

Dipole moments of molecules solvated in helium nanodroplets

Stark spectra are reported for hydrogen cyanide and cyanoacetylene solvated in helium nanodroplets. The goal of this study is to understand the influence of the helium solvent on measurements of the permanent electric dipole moment of a molecule. We find that the dipole moments of the helium solvated molecules, calculated assuming the electric field is the same as in vacuum, are slightly smaller than the well-known gas-phase dipole moments of HCN and HCCCN. A simple elliptical cavity model quantitatively accounts for this difference, which arises from the dipole-induced polarization of the helium.     

Transition from molecular complex to quantum solvation in 4HeNOCS

We present fully quantum calculations of the rotational energy levels and spectroscopic rotational constants of the linear OCS molecule in variable size clusters of 4He. The rotational constants of OCS are found to decrease monotonically from the gas phase value as the number of helium atoms increases to N=6, after which the average constant increases to saturation at the large droplet value by N=20. The minimum is shown to indicate a transition from a molecular complex to a quantum solvated molecule, with the former characterized by floppy but near rigid behavior, while the latter is characterized by nonzero permutation exchanges and a smaller extent of rigid coupling.     

Satellite band in the rovibrational spectrum of CO2 in helium droplets

Pulsed infrared (nu approximately 2350 cm(-1)) laser excitation spectra of CO2 molecules embedded in helium droplets are reported. The spectra exhibit a sharp R(0) rovibrational line accompanied by a weak broader (deltanu approximately 10 cm(-1)) satellite band, which is shifted by 14 cm(-1) towards higher frequencies. We assign this satellite band to a simultaneous rovibrational excitation of a molecule and its helium solvation shell. The results are rationalized within a model, which includes coupling of the rotational states of a molecule and a ring of He atoms.     

Nonclassical rotations of single molecules in small helium and hydrogen clusters: Manifestation of “microscopic superfluidity”

The studies of small helium clusters (up to 100 atoms) and molecular-hydrogen clusters (up to 20 molecules) that are formed in a supersonic gas jet and are coupled by the weak van der Waals interaction with a linear chromophore molecule are reviewed The shift of the frequency of the fundamental vibration of the chromophore, as well as a change in the moment of inertia of a cluster with its growth, has been detected by their rotational and vibrational-rotational spectra. A nonclassical behavior of the moment of inertia manifested in its decrease beginning with a certain number of attached He atoms (H₂ molecules) has been revealed. This behavior indicates that a part of a cluster is decoupled from the rotational motion of a molecule. The key question of these studies is whether such behavior of the moment of inertia is the manifestation of the super-fluidity of helium and hydrogen at microscopic level. The results are compared to the spectroscopy of molecules and hydrogen clusters in liquid-helium nanodroplets.     

Index of refraction for cold lithium- and diatomic sodium waves traveling through cold noble gases

In the present paper we propose to measure the index of refraction for diatomic sodium molecules traveling through a cold helium gas. Theoretical calculations of the index of refraction for this system are presented as a function of the molecule velocity and atom gas temperature. Whereas previous theoretical efforts to compute the refractive index have been concerned with atomic systems and atomic matter waves, we extend the investigation to diatomic molecules in the present work. To enable such calculations the potential energy surface for the atom-molecule interaction is calculated ab initio, along with the long range dispersion coefficients for the atom-molecule system. The full close-coupled equations, describing the atom-molecule collisions, are solved numerically to work out the influence of the collisions on the matter waves. We investigate the sensitivity of the results upon changes and inaccuracies in the potential energy surface. Several molecular rotational levels are included in the present study, and the index of refraction is found to depend on the rotational state. In addition, the index of refraction for atomic lithium matter waves traveling through the cold noble gases helium and argon are computed, motivated by a recent experiment with atomic lithium matter waves. Different resonances (glory- and scattering resonances) are identified from the results. Such resonances offer an important opportunity for the comparison of experiment and theory.     

Role of boson-fermion statistics on the Raman spectra of Br2(X) in helium clusters

The role played by the bosonic or fermionic character of He atoms surrounding a Br2(X) molecule is analyzed through vibrotational Raman spectra simulations. Quantum chemistry-type calculations reveal the spin multiplicity to be chiefly responsible for the drastic difference observed by Grebenev et al. [Science 279, 2083 (1998)]] in the rotational structure of molecules embedded in helium droplets.     

Dynamics of orientation of adsorbed polar molecules in static electric and laser field

The rotational states of adsorbed polar molecule in the presence of static electric and laser field are investigated. In this study, we have taken two types of polar molecules, namely, one with large dipole moment and moderate rotational constant (LiCl), and the other with moderate dipole moment and large rotational constant (HBr). The adsorbed molecule is considered as rigid rotor in finite conical potential well. The eigenvalues are calculated by numerically solving the Schrödinger equation. We have shown that various properties of rotational states of the molecules are significantly influenced by the static electric field, laser field, conical potential well height and the hindrance angle. Also the use of two different polar molecules for the investigation is justified by the variation in various properties due to change in molecule.     

Spectroscopic studies of quantum solvation in 4HeN-N2O clusters

High resolution microwave and infrared spectra of He(N)-N2O clusters were studied in the range N=3 to 12. The apparent cluster moments of inertia increase from N=3 to 6, but then decrease, showing oscillatory behavior for N=7 to 12. This provides direct experimental evidence for the decoupling of helium atoms from the rotation of the dopant molecule in this size regime, signaling the transition from a molecular complex to a quantum solvated system and directly exploring the microscopic evolution of "molecular superfluidity."     

Buoyancy corrections for the potential of an impurity in a 4He nanodroplet

This paper presents correction terms for the effective potential for the translation and rotation of an impurity atom or molecule solvated in a helium nanodroplet that were previously published (Lehmann, K. K., 1999, Molec. Phys., 97, 645). The correction arises from changes in the total He-He potential energy of the displaced liquid as a function of the solute position within the droplet. For the alkali atoms, this buoyancy type correction removes the large barrier to ejection of the atom from the droplets, which is predicted if this term is neglected.     

Onset of superfluidity in small CO2(4He)N clusters

We provide definitive theoretical evidence for the onset of superfluidity in small helium clusters doped with molecules at less than one solvation shell, with quantitative analysis of spectroscopic constants for CO2 in (4)He(N) in terms of nonclassical rotational inertia and helium superfluidity calculated by path integral methods. We find a significant superfluid response for N>/=5, with essentially unit response to rotations around the CO2 axis and partial response to rotations about an axis perpendicular to the CO2 axis for N>/=6. This anisotropic superfluid response is shown to be responsible for the N dependence of measured CO2 rotational spectra in (4)He(N).     

Bridging the gap between small clusters and nanodroplets: spectroscopic study and computer simulation of carbon dioxide solvated with helium atoms

High resolution infrared spectra of He(N)-CO2 clusters with N up to 17 have been studied in the region of the CO2 nu(3) fundamental band. The B rotational constant initially drops as expected for a normal molecule, reaching a minimum for N=5. Its subsequent rise for N=6 to 11 can be interpreted as the transition from a normal (though floppy) molecule to a quantum solvation regime. For N>13, the B value becomes approximately constant with a value about 17% larger than that measured in much larger helium nanodroplets. Quantum Monte Carlo calculations of pure rotational spectra are in excellent agreement with the measured B in this size range and complement the experimental study with detailed structural information. For a larger cluster size (N=30-50) the simulations show a clear sign of convergence towards the nanodroplet B value.     

Rotational and vibrational excitation of sputtered diatomic molecules

The rotational and vibrational level population distributions of ground and electronically excited states of several homonuclear and heteronuclear molecules are calculated for direct ejection, association, and associative ionization mechanisms of molecule sputtering. The cascade properties, formation mechanism, initial atom separation, and axis orientation to the surface are clearly reflected in the sputtered molecule distributions. In general, extensive non-Boltzmann rotational and vibrational distributions are predicted. The probability that an atom pair survives the ejection, for typical sputtering parameters, is high; approximately 50% for homonuclear molecules to near 100% for hydrides. The predictions are compared with experimental optical emission spectra in the accompanying paper.     

Computer simulation of the hydrophobic hydration of convex surfaces of large radius

Three hemispherical objects of radius 6.5, 9.3 and 12.2 Å were constructed from tessellated icosahedra where the vertices were hydrophobic ‘atoms’. These objects were hydrated and molecular dynamics simulations were performed on the solvated system. Analysis of the trajectories demonstrated that water molecules around convex solutes possess different configurations and exhibit different translational and rotational dynamics from water molecules in the bulk region. No qualitative difference was observed in the alteration of these structural and dynamic properties as the hemispheres became larger.     

The Properties of Different Synthetic Active Silicas Measured in the Near Infra Red

Rotationally resolved gas-phase absorption spectra of partially and fully deuterated linear seven-carbon chain radicals are presented in this article. The carbon-based molecules are generated in a supersonically expanding planar plasma by discharging a gas mixture of acetylene and deuterium-enriched acetylene in helium and argon. Spectra are recorded in direct absorption using cavity ring-down spectroscopy. The rotational analyses of the present experimental spectra allow to determine both ground and excited state rotational constants, as well as the upper state band origins of the two deuterated species.     

Detection and imaging of He2 molecules in superfluid helium

We present data that show a cycling transition can be used to detect and image metastable He2 triplet molecules in superfluid helium. We demonstrate that limitations on the cycling efficiency due to the vibrational structure of the molecule can be mitigated by the use of repumping lasers. Images of the molecules obtained using the method are also shown. This technique gives rise to a new kind of ionizing radiation detector. The use of He2 triplet molecules as tracer particles in the superfluid promises to be a powerful tool for visualization of both quantum and classical turbulence in liquid helium.     

Kinetic theory of rotating molecule interaction with a solid surface

A kinetic theory of interaction between molecules with rotational degrees of freedom and a solid surface for arbitrary ratios among the times of molecule rotation, flight through the region of surface forces, and relaxation of a molecular ensemble due to phonons has been developed. A kinetic equation for an ensemble of molecules residing in the field of surface forces has been derived from the equation for the one-particle distribution function of molecules by averaging it along the dynamical trajectories in the region of surface force action. A simple analytic expression for the probability of trapping a molecule with rotational degrees of freedom has been obtained. Experimental data on rotational cooling and rotational polarization of desorbed molecules are discussed. Zh. éksp. Teor. Fiz. 113, 1350–1363 (April 1998)     

Qualitative assessment of ultra-fast non-Grotthuss proton dynamics in S<Subscript>1</Subscript> excited state of liquid H<Subscript>2</Subscript>O from ab initio time-dependent density functional theory

We study qualitatively ultra-fast proton transfer (PT) in the first singlet (S₁) state of liquid water (absorption onset) through excited-state dynamics by means of time-dependent density functional theory and ab initio Born-Oppenheimer molecular dynamics. We find that after the initial excitation, a PT occurs in S₁ in form of a rapid jump to a neighboring water molecule, on which the proton either may rest for a relatively long period of time (as a consequence of possible defect in the hydrogen bond network) followed by back and forth hops to its neighboring water molecule or from which it further moves to the next water molecule accompanied by back and forth movements. In this way, the proton may become delocalized over a long water wire branch, followed again by back and forth jumps or short localization on a water molecule for some femtoseconds. As a result, the mechanism of PT in S₁ is in most cases highly non-Grotthuss-like, delayed and discrete. Furthermore, upon PT an excess charge is ejected to the solvent trap, the so-called solvated electron. The spatial extent of the ejected solvated electron is mainly localized within one solvent shell with overlappings on the nearest neighbor water molecules and delocalizing (diffuse) tails extending beyond the first solvent sphere. During the entire ultra-short excited-state dynamics the remaining OH radical from the initially excited water molecule exhibits an extremely low mobility and is non-reactive.     

Rotational parity and separation of water molecules into spin isomers

A theoretical explanation is proposed for the effect of variations in concentration of water molecule spin isomers in the gas phase during the interaction of molecules with a solid adsorbent surface. The explanation is based on antisymmetric (AS) correlation between proton spin moments and molecule rotation. A new AS correlation occurs during the interaction of the molecule with a dc electric field near the surface. Due to the new (external) AS correlation, ortho-and parawater molecules are formed; separation into spin modifications occurs over degenerate states of each rotational level of the molecule. Water molecule separation into spin modifications at the previous (internal) AS correlation occurs over rotational levels of molecules. The ratio of ortho-and parawater concentrations in the gas phase at the external AS correlation is compared with experimental data on chromatographic separation of water spin isomers. Quantitative agreement is observed between the calculated ratio and the ratio measured for water molecules at the final separation stage.