Optimal covering of C(60) fullerene by rare gases

Putative global energy minima of clusters formed by the adsorption of rare gases on a C(60) fullerene molecule, C(60)X(N) (X=Ne, Ar, Kr, Xe; N ≤ 70), are found using basin-hopping global optimization in an empirical potential energy surface. The association energies per rare gas atom as a function of N present two noticeable minima for Ne and Ar and just one for Kr and Xe. The minimum with the smallest N is the deepest one and corresponds to an optimal packing monolayer structure; the other one gives a monolayer with maximum packing. For Kr and Xe, optimal and maximum packing structures coincide. By using an isotropic average form of the X-C(60) interaction, we have established the relevance of the C(60) surface corrugation on the cluster structures. Quantum effects are relevant for Ne clusters. The adsorption of these rare gases on C(60) follows patterns that differ significantly from the ones found recently for He by means of experimental and theoretical methods.     

Theoretical studies for structures and energetics of Rgn-N2O (Rg=He, Ne, Ar) clusters

Minimum-energy structures of the Rg(2)-N(2)O (Rg=He, Ne, Ar) clusters have been determined with ab initio MP2 optimization, whereas the minimum-energy structures of the Rg(n)-N(2)O clusters with n = 3-7 have been obtained with the pairwise additive potentials. Interaction energies and nonadditive three-body effects of the Rg(2)-N(2)O ternary complex have been calculated using supermolecule method at MP4 and CCSD(T) levels. It was found from the calculations that there are two minima corresponding to one distorted tetrahedral structure and one planar structure for the ternary complex. The nonadditive three-body effects were found to be small for Rg(2)-N(2)O complexes. Our calculations also indicated that, for He(n)-N(2)O and Ne(n)-N(2)O clusters, the first six He and Ne atoms form the first solvation ring around the middle nitrogen of the N(2)O monomer, while for Ar(n)-N(2)O, the first five Ar atoms form the first solvation ring.     

Laser induced fluorescence spectroscopy of tetracene with large Ar, Ne, and H2 clusters in superfluid He nanodroplets

Clusters of tetracene molecules with different numbers of attached (Ar)(N), (Ne)(N) and (H(2))(N) particles (N = 1-2000) are assembled inside superfluid He nanodroplets and studied via laser-induced fluorescence. The frequency shift of the fluorescence spectrum of the tetracene molecules is studied as a function of cluster size and pickup order of tetracene and cluster species. For (Ar)(N) and (Ne)(N) clusters, our results indicate that the tetracene molecules reside inside the clusters when tetracene is captured by the He nanodroplet before the cluster species; conversely, the tetracene molecules stay on the surface of the clusters when tetracene is captured after the cluster species. In the case of (H(2))(N) clusters, however, tetracene molecules reside inside the (H(2))(N) clusters irrespective of the pickup order. We conclude that (Ar)(N) and (Ne)(N) clusters are rigid at T = 0.38 K, while (H(2))(N) clusters of up to N = 2000 remain fluxional at the same temperature. The results may also indicate the occurrence of heterogeneous nucleation of the (H(2))(N) clusters, which is induced by the interaction with tetracene chromophore molecules.     

Electron spin resonance g tensors for complexes of Ne and Ar with AlO: theoretical studies related to the large matrix effect observed for AlO

For Ne(n)-AlO (n=2, 4, 6, 8, 10) and Ar(n)-AlO clusters (n=2, 4, 6, 8), the perpendicular (relative to AlO) component of the g tensor was calculated by second-order perturbation theory, using multireference configuration-interaction wave functions. The rare-gas (Rg) atoms were placed axially and/or off axially (one or two rings of four Rg atoms each), and the distance of the Rg atoms from the Al and O atoms, or from the AlO axis, was varied from 4 to 12 bohrs. Rg atoms placed axially mostly increase g(perpendicular), whereas off-axially placed ones lower it below the gas-phase value of AlO. The largest deviations from g(perpendicular) of isolated AlO occur at Ne-Al,O distances of 5-6 bohrs, and Ar-Al,O distances of 6-9 bohrs, with maximal lowerings of about 1600 ppm for Ne and about 2200 ppm (estimated) for Ar in the case of two axial and eight off-axial Rg atoms. Electron spin resonance studies by Knight and Weltner found large matrix effects for AlO, with downshifts of g(perpendicular) observed to be about 450 and 1150 ppm in Ne and Ar matrices, respectively.     

Infrared spectra of Rh atom reaction products with C2H2: the HRhCCH, RhCCH, RhCCH2, and Rh-η2-C2H2 molecules

Laser-ablated Rh atoms react with C(2)H(2) upon co-condensation in excess argon and neon to form the insertion product HRhCCH, the alkyne RhCCH, the vinylidene RhCCH(2), and the metallacycle complex Rh-η(2)-(C(2)H(2)). These species are identified through (13)C(2)H(2), C(2)D(2), and mixed C(2)HD isotopic substitutions and density functional theory isotopic frequency calculations. The HRhCCH molecule is characterized by the CH stretching mode at 3306.2 cm(-1) (Ar) and 3310.9 cm(-1) (Ne), the Rh-H stretching mode at 2090.8 cm(-1) (Ar) and 2111.0 cm(-1) (Ne), and two CCH deformation modes at 584.3 and 573.3 cm(-1) (Ar) and 587.1 and 580.3 cm(-1) (Ne). The absorptions for the vinylidene RhCCH(2) complex are observed at 3150.9 (Ar), 3147.2 (Ne) (CH stretching), 1690.1 (Ar), 1694.3 (Ne) (CC stretching), and 804.9 (Ar), 810.5 cm(-1) (Ne) (CCH deformation). The metallacycle Rh-η(2)-(C(2)H(2)) complex is also identified through CC stretching and CCH deformation modes. The insertion reaction of ground Rh atom to the C-H bond is spontaneous on the basis of the growth of HRhCCH absorptions upon annealing in both solid neon and argon. Here, we show that atomic Rh can convert acetylene to the simple Rh vinylidene complex, analogous to that found for ligand-supported Rh complexes.     

Design and application of a multicoefficient correlation method for dispersion interactions

A new multicoefficient correlation method (MCCM) is presented for the determination of accurate van der Waals interactions. The method utilizes a novel parametrization strategy that simultaneously fits to very high-level binding, Hartree-Fock and correlation energies of homo- and heteronuclear rare gas dimers of He, Ne, and Ar. The decomposition of the energy into Hartree-Fock and correlation components leads to a more transferable model. The method is applied to the krypton dimer system, rare gas-water interactions, and three-body interactions of rare gas trimers He3, Ne3, and Ar3. For the latter, a very high-level method that corrects the rare-gas two-body interactions to the total binding energy is introduced. A comparison with high-level CCSD(T) calculations using large basis sets demonstrates the MCCM method is transferable to a variety of systems not considered in the parametrization. The method allows dispersion interactions of larger systems to be studied reliably at a fraction of the computational cost, and offers a new tool for applications to rare-gas clusters, and the development of dispersion parameters for molecular simulation force fields and new semiempirical quantum models.     

Tuning of the internal energy and isomer distribution in small protonated water clusters H(+)(H2O)(4-8): an application of the inert gas messenger technique

Infrared spectroscopy of gas-phase hydrated clusters provides us much information on structures and dynamics of water networks. However, interpretation of spectra is often difficult because of high internal energy (vibrational temperature) of clusters and coexistence of many isomers. Here we report an approach to vary these factors by using the inert gas (so-called "messenger")-mediated cooling technique. Protonated water clusters with a messenger (M), H(+)(H(2)O)(4-8)·M (M = Ne, Ar, (H(2))(2)), are formed in a molecular beam and probed with infrared photodissociation spectroscopy in the OH stretch region. Observed spectra are compared with each other and with bare H(+)(H(2)O)(n). They show clear messenger dependence in their bandwidths and relative band intensities, reflecting different internal energy and isomer distribution, respectively. It is shown that the internal energy follows the order H(+)(H(2)O)(n) > H(+)(H(2)O)(n)·(H(2))(2) > H(+)(H(2)O)(n)·Ar > H(+)(H(2)O)(n)·Ne, while the isomer-selectivity, which changes the isomer distribution in the bare system, follows the order H(+)(H(2)O)(n)·Ar > H(+)(H(2)O)(n)·(H(2))(2) > H(+)(H(2)O)(n)·Ne ~ (H(+)(H(2)O)(n)). Although the origin of the isomer-selectivity is unclear, comparison among spectra measured with different messengers is very powerful in spectral analyses and makes it possible to easily assign spectral features of each isomer.     

Model potential calculations for the excited states of the Ar*+He,Ar*+Ne molecular systems. Interpretation of thermal energy collisions involving Ar*(3p 54p) and Ne*(2p 53p)

The method developed by Hennecart and Masnou-Seeuws (1985) for the Ne*+He and Ne*+Ne systems is applied to the calculation of the molecular potential curves of the Ar*+He and Ar*+Ne systems that are correlated to the levels of the 3p ⁵ 4s and 3p ⁵ 4p configurations of the Ar atom. The computed potential curves and dynamical coupling matrix elements are next used in the framework of a two-state quantal calculation to determine the temperature variation of a few population transfer cross sections. A simple interpretation is proposed for Ar*+He and Ne*+He collisions using the Nikitin's exponential model, and it is shown that in many cases the cross sections can be predicted correctly by a two-state model.     

Basis set limits of the second order Moller-Plesset correlation energies of water, methane, acetylene, ethylene, and benzene

We report second order Moller-Plesset (MP2) and MP2-F12 total energies on He, Ne, Ar, H(2)O, CH(4), C(2)H(2), C(2)H(4), and C(6)H(6), using the correlation consistent basis sets, aug-cc-pVXZ (X=D-7). Basis set extrapolation techniques are applied to the MP2 and MP2-F12/B methods. The performance of the methods is tested in the calculations of the atoms, He, Ne, and Ar. It is indicated that the two-point extrapolation of MP2-F12/B with the basis sets (X=5,6) is the most reliable. Similar accuracy is obtained using two-point extrapolated conventional MP2 with the basis sets (X=6,7). For the molecules investigated the valence MP2 correlation energy is estimated within 1 mE(h).     

Growth dynamics and intracluster reactions in Ni+(CO2)n complexes via infrared spectroscopy

Ni(+)(CO(2))(n), Ni(+)(CO(2))(n)Ar, Ni(+)(CO(2))(n)Ne, and Ni(+)(O(2))(CO(2))(n) complexes are generated by laser vaporization in a pulsed supersonic expansion. The complexes are mass-selected in a reflectron time-of-flight mass spectrometer and studied by infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy. Photofragmentation proceeds exclusively through the loss of intact CO(2) molecules from Ni(+)(CO(2))(n) and Ni(+)(O(2))(CO(2))(n) complexes, and by elimination of the noble gas atom from Ni(+)(CO(2))(n)Ar and Ni(+)(CO(2))(n)Ne. Vibrational resonances are identified and assigned in the region of the asymmetric stretch of CO(2). Small complexes have resonances that are blueshifted from the asymmetric stretch of free CO(2), consistent with structures having linear Ni(+)-O=C=O configurations. Fragmentation of larger Ni(+)(CO(2))(n) clusters terminates at the size of n=4, and new vibrational bands assigned to external ligands are observed for n> or =5. These combined observations indicate that the coordination number for CO(2) molecules around Ni(+) is exactly four. Trends in the loss channels and spectra of Ni(+)(O(2))(CO(2))(n) clusters suggest that each oxygen atom occupies a different coordination site around a four-coordinate metal ion in these complexes. The spectra of larger Ni(+)(CO(2))(n) clusters provide evidence for an intracluster insertion reaction assisted by solvation, producing a metal oxide-carbonyl species as the reaction product.     

Structure and stability of Ne+He(n): experiment and diffusion quantum Monte Carlo theory with "on the fly" electronic structure

New data are reported for the mass-spectrometry fragmentation patterns of helium clusters, either pure or containing a Ne or an Ar atom. The patterns for He(n)+ and Ar+He(n) show clear evidence of structure, while those of Ne+He(n) do not. To better understand the surprising result for the Ne+He(n) fragments, diffusion quantum Monte Carlo (DMC) calculations of the energies and structural properties of these ions were performed using a diatomics-in-molecule (DIM) parametrization of the potential energy. Using DIM for electronic energy evaluation allows us to sample 10(9) configurations even for a cluster as large as Ne+He14. The results of the DMC calculation are very surprising. For n > 7, the DMC random walkers rarely venture within 100 cm(-1) of the minimum potential energy. Analysis of the resulting particle density distributions shows that the zero-point energy does more than spread the wave function around the potential-energy minima, resulting in very diffuse wave functions. For some of the clusters the quantum effects nearly exclude the region of the potential minimum from the overall wave function. An important result of this effect is that the incremental bonding energy of the nth helium atom varies quite smoothly with n, for n > 5. This eliminates the expected shell structure and explains the lack of magic-number-type features in the data.     

Noble‐Gas Complexes: Theoretical Investigation of Multicenter Polynuclear Species

Ab initio calculations at the MP2 level of theory disclose the conceivable existence of neutral complexes containing four or five distinct noble gases (Ng) each bound to a distinct Be‐atom. These multicenter polynuclear Ng molecules are formally obtained by replacing the H‐atoms of CH₄ and but‐2‐yne with ? NBeNg moieties, which behave as independent monovalent ‘functional groups’. Our investigated complexes include the five homotetranuclear [C(NBeNg)₄] complexes 1 – 5 (Ng=He? Xe), the five heterotetranuclear complexes [CN₄Be₄(He)(Ne)(Ar)(Kr)] ( 6 ), [CN₄Be₄(He)(Ne)(Ar)(Xe)] ( 7 ), [CN₄Be₄(He)(Ne)(Kr)(Xe)] ( 8 ), [CN₄Be₄(He)(Ar)(Kr)(Xe)] ( 9 ), and [CN₄Be₄(Ne)(Ar)(Kr)(Xe)] ( 10 ), and the heteropentanuclear complex [HC₄N₅Be₅(He)(Ne)(Ar)(Kr)(Xe)] ( 11 ). We also investigated the five model complexes [H₃CNBeNg] (Ng=He? Xe) containing a single ? NBeNg moiety. The geometries and vibrational frequencies of all these species, invariably characterized as minimum‐energy structures, were computed at the MP2(full)/6‐31G(d,p)/SDD level of theory, and their stability with respect to the loss of the various Ng‐atoms was evaluated by single‐point calculations at the MP2(full)/6‐311G(d)/SDD level of theory. The beryllium‐Ng binding energies range from ca. 17 (Ng=He) to ca. 63 (Ng=Xe) kJ/mol, and the results of natural‐bond‐orbital (NBO) and atoms‐in‐molecules (AIM) analysis reveal that the Be? Ng interaction is essentially electrostatic for helium, neon, argon, and krypton, and has probably a small covalent contribution for xenon.     

Stark broadening and regularities of ionized neon and argon spectral lines

Stark widths of five Ne III, five Ne IV, one Ar III and nine ArIV spectral lines have been measured in a linear-pinch discharge plasma. The results were compared with existing experimental and theoretical results, and used to establish several types of regularities. Electron densities determined with single-wavelength laser interferometry were 2.18·10²³ m^?3 and 2.80·10²³ m^?3 in neon and argon plasma, respectively. The electron temperatures determined from the Boltzmann slope of several Ne III spectral lines, and ratios of Ne III to Ne IV or Ar III to Ar IV spectral lines were 59 000 K and 42 000 K in neon and argon plasma, respectively. The investigated spectral lines originate predominantly, from 3s–3p and 3s′–3p′ Ne III and Ne IV, and from 4s–4p and 4s′–4p′ Ar III and Ar IV transition arrays. The emphasis is on the Stark width (θ) dependence on the upper level ionization potential (I), the emitter core net charge (z) and electron temperature (T) for a given electron density. This dependence was found to be of the form: θ=az ² T ^?1/2 I ^?b , wherea andb are constants within(i) several stages of ionization of neon or argon and(ii) within nitrogen like (NI, O II, F III and Ne IV) 3s–3p or phosphorus like (P I, S II, Cl III and Ar IV) 4s–4p transition arrays. The established overall trends were used to predict the Stark widths of univestigated spectral lines originating from the given transition arrays.     

Electronic spectroscopy of toluene-rare-gas clusters: the external heavy atom effect and vibrational predissociation

Toluene-X van der Waals clusters (where X = Ne, Ne2, Ar, Ar2, Kr, Xe) have been investigated by fluorescence excitation spectroscopy in the region of the S1-S0 transition. With the exception of Xe, for each rare-gas studied, we have assigned cluster transitions in the region of all the strong monomer vibrational bands up to 1000 cm(-1) above the origin band. We have further investigated the S1 relaxation dynamics for each vibrational level of each complex, via their fluorescence decay profiles. Clustering with neon has little appreciable effect on the vibrationless S1 lifetime. By contrast, the clusters with argon and krypton exhibit markedly shorter fluorescence lifetimes compared with the monomer. The effect is so severe in the case of toluene-Xe clusters that no fluorescence signals were observed. We interpret these results in terms of an external heavy atom effect in which the rate of intersystem crossing in toluene is influenced by the cluster partner. For clusters built upon excited S1 vibrational levels, the situation is potentially complicated by intramolecular vibrational redistribution and vibrational predissociation (VP). The majority of the fluorescence decay profiles were satisfactorily modeled using single exponential decays. The emission following pumping of the 37(1) level in the toluene-Kr cluster, however, is an exception. We have modeled the decay of this level with a simple kinetic scheme including VP and determined a predissociation rate of (1.04 +/- 0.54) x 10(7) s(-1).     

On the noble-gas-induced intersystem crossing for the CUO molecule: experimental and theoretical investigations of CUO(Ng)n (Ng = Ar, Kr, Xe; n = 1, 2, 3, 4) complexes in solid neon

Uranium atoms excited by laser ablation react with CO in excess neon to produce the novel CUO molecule, which forms distinct Ng complexes (Ng = Ar, Kr, Xe) when the heavier noble gases are added. The CUO(Ng) complexes are identified through CO isotopic and Ng substitution on the neon matrix infrared spectra and by comparison to DFT frequency calculations. The U-C and U-O stretching frequencies of CUO(Ng) complexes are slightly red-shifted from frequencies for the (1)Sigma(+) CUO ground state, which identifies singlet ground state CUO(Ng) complexes. In solid neon the CUO molecule is also a complex CUO(Ne)(n), and the CUO(Ne)(n-1)(Ng) complexes are likewise specified. The next singlet CUO(Ne)(x)(Ng)(2) complexes in excess neon follow in like manner. However, the higher CUO(Ne)(x)(Ng)(n) complex (n = 3, 4) stretching modes approach pure argon matrix CUO(Ar)(n) values and isotopic behavior, which are characterized as triplet ground state complexes by DFT frequency calculations. This work suggests that the singlet-triplet crossing occurs with 3 Ar, 3 Kr, or 4 Xe and a balance of Ne atoms coordinated to CUO in the neon matrix host.     

Excitation of singly-ionized argon species in helium-matrix Grimm glow discharge plasmas II – Comparison between argon and neon

A considerable intensity enhancement of several Ar II lines assigned to the 3p(4)4p-3p(4)4s transition in a helium-argon Grimm glow discharge plasma has been previously reported and attributed to argon ions excited by metastable helium atoms. In this paper the behavior of Ne II lines assigned to the 2p(4)3p-2p(4)3s transition in a helium-neon plasma was investigated to obtain detailed information on the excitation of plasma gases in the helium-matrix plasmas. No Ne II lines with enhanced emission intensities have been found; on the contrary, the intensities of the doublet Ne II lines decreased in the helium-matrix plasma.     

Intramolecular penning ionization in organic molecule-rare gas clusters

A supersonic beam of organic molecules (benzonitrile (Bn), toluene (Tol), benzene (Bz) and pyridine (Pyr)) seeded into Ne or Ar was ionized by VUV radiation from the Berlin electron storage ring (BESSY). Photoionization efficiency curves were measured for Bn, Bn·Ne, Bn·Ar, Tol, Tol·Ar, Tol·Ne, Bz, Pyr, Pyr-Ar, and Pyr-Ne. Resonance peaks in these spectra at the positions of the atomic rare gas resonance lines confirm our previous measurements on Bn seeded into Ar and Kr, showing that the excitation energy of the rare gas atom is transferred to the attached organic molecule within a heterogeneous cluster, leading to ionization of the molecule and fragmentation of the cluster.     

Structural properties and energetics of diffuse 87Rb clusters in three-dimension

A correlated two-body basis function is used to describe the three-dimensional bosonic clusters interacting via two-body van der Waals potential. We calculate the ground state and the zero orbital angular momentum excited states for Rb(N) clusters with up to N = 40. We solve the many-particle Schro?dinger equation by potential harmonics expansion method, which keeps all possible two-body correlations in the calculation and determines the lowest effective many-body potential. We study energetics and structural properties for such diffuse clusters both at dimer and tuned scattering length. The motivation of the present study is to investigate the possibility of formation of N-body clusters interacting through the van der Waals interaction. We also compare the system with the well studied He, Ne, and Ar clusters. We also calculate correlation properties and observe the generalised Tjon line for large cluster. We test the validity of the shape-independent potential in the calculation of the ground state energy of such diffuse cluster. These are the first such calculations reported for Rb clusters.     

A polynomial version of the generator coordinate Dirac-Fock method

A polynomial version of the Generator Coordinate Dirac-Fock (p-GCDF) method is introduced and applied to develop Adapted Gaussian Basis Sets (AGBS) for helium- and beryllium-like atomic species (He, Ne +8, Ar +16, Sn +48, Be, Ne +6, Ar +14, and Sn +46) and for Kr and Xe atoms. The Dirac-Fock-Coulomb and Dirac-Fock-Breit energies obtained with these basis sets are in excellent agreement with numerical finite-difference calculations. Moreover, the sizes of the AGBS generated here with the p-GCDF method are significantly smaller than the size of previous relativistic Gaussian basis sets.     

Selective adsorption, bound states, and potential parameters for He, Ne, and Ar interacting with a Cu(110) surface

Using nozzle beams of He, Ne, and Ar, we have measured diffractive selective adsorption resonances from a Cu(110) surface kept at 20 K. Bound state energies of the atom-surface potentials have been determined from plots of the measured resonance energies versus incident angle and their fits to calculated kinematical dispersion relations. For 3He and 4He we have found a unique level assignment that is compatible with a single gas-surface potential curve with a well depth of 6.05 meV of the He-Cu(110) potential. This value is about 10% larger than the prediction of 5.55 meV from the current physisorption theory. The Ne and Ar data reveal a large number of closely spaced levels with level separations and estimated van der Waals coefficients that are compatible with available theoretical data.