The structure, properties, and nature of HArF-HOX (X = F, Cl, Br) complex: an ab initio study and an unusual short hydrogen bond

The structure and properties (geometric, energetic, electronic, spectroscopic, and thermodynamic properties) of HArF‐HOX (X = F, Cl, Br) complex have been investigated at the MP2/aug‐cc‐pVTZ level. Three types of complexes are formed through a hydrogen bond or a halogen bond. The HArF‐HOX complex is the most stable, followed by the FArH‐OHX complex, and the HArF‐XOH complex is the most unstable. The binding distance in FArH‐OHX complex is very short (1.1–1.7 Å) and is smaller than that in HArF‐HOX complex. However, the interaction strength in the former is weaker than that in the latter. Thus, an unusual short hydrogen bond is present in FArH‐OHX complex. The associated H‐Ar bond exhibits a red shift, whereas the distant one gives a blue shift. A similar result is also found for the O? H and O? X bonds. The isotropic chemical shift is negative for the associated hydrogen atom but is positive for the associated halogen atom. However, a reverse result is found for the anisotropic chemical shift. The analyses of natural bond orbital and atoms in molecules have been performed for these complexes to understand the nature and properties of hydrogen and halogen bonds. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

An ab initio potential energy surface and predissociative resonances of HArF

A three-dimensional potential energy surface of the ground electronic state HArF is constructed from more than 2000 ab initio points at the multireference averaged quadratic coupled-cluster level employing an augmented large basis set. The calculations indicate that the linear HArF molecule is metastable with a barrier of 0.643 eV in the atomization (HArF --> H + Ar + F) channel and a barrier of 1.017 eV in the dissociation (HArF --> Ar + HF) channel. Variational calculations of low-lying predissociative resonances of both HArF and DArF are performed on the three-dimensional potential energy surface using a complex-symmetric Lanczos propagation method, which yields both positions and widths of the resonance states. The resonance lifetime generally decreases with energy, but strong mode selectivity exists. Reasonably good agreement with experiment confirms the accuracy of our potential. These calculations provide valuable information on the stability and dynamics of HArF/DArF in its ground electronic state.     

Complexes of HArF and AuX (X = F,Cl, Br,I). Comparison of H-bonds,halogen bonds,F-shared bonds and covalent bonds

The various sorts of complexes in which HArF and AuX (X = F, Cl, Br, I) can engage are probed by MP2/aug-cc-pVTZ calculations. The most weakly bound are those containing a halogen bond (XB) of the AuX⋯FArH sort, with binding energies less than 8 kcal/mol. H-bonded dimers FArH⋯XAu are a little stronger, held together by some 12 kcal/mol. Being the most strongly bound places the F atom of HArF roughly midway between Ar and Au in an F-shaped structure, bound by some 43–54 kcal/mol. The last sort of product involves atomic rearrangements wherein the H atom migrates from Ar to Au, followed by formation of a covalent Ar–Au bond. The resulting molecular unit is stabilized by 30–40 kcal/mol relative to the original HArF and AuX reactants. The H-bonded dimers are held together by an unusually large polarization component, surpassing electrostatic attraction, while dispersion predominates for the halogen bonds. Perturbations of the geometries and stretching frequencies offer a ready means of distinguishing the different types of complexes by spectroscopic techniques.     

After the electronic field: Structure,bonding, and the first hyperpolarizability of HArF

In this work, we add different strength of external electric field (E_ext) along molecule axis (Z‐axis) to investigate the electric field induced effect on HArF structure. The H‐Ar bond is the shortest at E_ext = ?189 × 10^?4 and the Ar‐F bond show shortest value at E_ext = 185 × 10^?4 au. Furthermore, the wiberg bond index analyses show that with the variation of HArF structure, the covalent bond H‐Ar shows downtrend (ranging from0.79 to 0.69) and ionic bond Ar‐F shows uptrend (ranging from 0.04 to 0.17). Interestingly, the natural bond orbital analyses show that the charges of F atom range from ?0.961 to ?0.771 and the charges of H atoms range from 0.402 to 0.246. Due to weakened charge transfer, the first hyperpolarizability (β_tot) can be modulated from 4078 to 1087 au. On the other hand, make our results more useful to experimentalists, the frequency‐dependent first hyperpolarizabilities were investigated by the coupled perturbed Hartree‐Fork method. We hope that this work may offer a new idea for application of noble‐gas hydrides. © 2013 Wiley Periodicals, Inc.     

Formation of HArF in solid Ar revisited: are mobile vacancies involved in the matrix-site conversion at 30 K?

The HArF molecule can occupy in solid Ar thermally unstable and stable configurations, and their microscopic structure is not understood at the moment. We present additional experimental results on the formation of two HArF configurations and analyze them with emphasis on possible reactions of the unstable configuration with matrix vacancies to form the stable configuration. We conclude that the existing computational scenarios do not describe fully the present experimental data. In order to explain qualitatively the experimental results, two tentative models are discussed. The first model is based on local mobility of matrix vacancies produced during photolysis and the second model considers isomerization of the HArF at Arn supermolecule. More importantly, the present results constitute the experimental basis for future theoretical studies.     

Potential-energy surface, van der Waals energy spectrum, and vibronic transitions in s-tetrazine-argon complex

The van der Waals vibrational states and the structure of the vibronic spectrum of s-tetrazine-argon complex have been studied by the ab initio methods. The potential-energy surface of the ground S(0) electronic state of the complex has been constructed by fitting the analytical many-body expansion to a large set of the interaction energy values computed using the second-order M?ller-Plesset perturbation theory combined with the standard aug-cc-pVDZ basis set. The equilibrium structure of the complex found is that with argon located above the tetrazine ring at a distance of 3.394 A. The calculated dissociation energy of 354 cm(-1) is compatible with the experiment. The van der Waals energy spectrum calculated from the potential-energy surface is explained analyzing a correlation with a simpler energy spectrum of benzene-argon. A new assignment of the S(0)-S(1) vibronic spectrum is proposed on the basis of the rigorous selection rules, vibrational energy levels in S(0) and S(1) states and vibronic transition intensities calculated from the electronic transition dipole moment surfaces.     

Gas hydrates of argon and methane synthesized at high pressures: composition, thermal expansion, and self-preservation

For the first time, the compositions of argon and methane high-pressure gas hydrates have been directly determined. The studied samples of the gas hydrates were prepared under high-pressure conditions and quenched at 77 K. The composition of the argon hydrate (structure H, stable at 460-770 MPa) was found to be Ar.(3.27 +/- 0.17)H(2)O. This result shows a good agreement with the refinement of the argon hydrate structure using neutron powder diffraction data and helps to rationalize the evolution of hydrate structures in the Ar-H(2)O system at high pressures. The quenched argon hydrate was found to dissociate in two steps. The first step (170-190 K) corresponds to a partial dissociation of the hydrate and the self-preservation of a residual part of the hydrate with an ice cover. Presumably, significant amounts of ice Ic form at this stage. The second step (210-230 K) corresponds to the dissociation of the residual part of the hydrate. The composition of the methane hydrate (cubic structure I, stable up to 620 MPa) was found to be CH(4).5.76H(2)O. Temperature dependence of the unit cell parameters for both hydrates has been also studied. Calculated from these results, the thermal expansivities for the structure H argon hydrate are alpha(a) = 76.6 K(-1) and alpha(c) = 77.4 K(-1) (in the 100-250 K temperature range) and for the cubic structure I methane hydrate are alpha(a) = 32.2 K(-1), alpha(a) = 53.0 K(-1), and alpha(a) = 73.5 K(-1) at 100, 150, and 200 K, respectively.     

Matrix isolation spectroscopy and molecular dynamics simulations for 2,7,12,17-tetra-tert-butylporphycene in argon and xenon

Electronic absorption spectra of 2,7,12,17-tetra-tert-butylporphycene (TTPC) have been recorded in low-temperature argon and xenon matrices for various deposition conditions. In the region of the S(0)-S(1) electronic transition, the spectra of TTPC in argon reveal a rich site structure, characterized by a series of more than 30 absorption peaks. Studies of the temperature dependence of the electronic spectra in solid argon demonstrated remarkable spectral changes, resulting in the broadening of all bands with increasing temperature. These temperature-induced spectral changes are, to a large degree, reversible, so lowering of temperature is accompanied by the recovery of the original fine-line spectrum. The absorption spectra in xenon reveal broad bands, on which a rich pattern of lines becomes superimposed at low temperatures. Trapping site distribution and the structure of the microenvironment around the TTPC chromophore, embedded in argon and xenon hosts, have been analyzed using molecular dynamics (MD) simulations. The MD results show that the trapping of TTPC in rare-gas solids is influenced by favorable embedding of the bulky tert-butyl groups inside the matrix cage. The crucial role of the tert-butyl groups for the thermodynamics and kinetics of matrix deposition is demonstrated by comparing the results with those obtained for the parent, unsubstituted porphycene.     

Towards an insight on the photoluminescence of disordered CaWO4 from a joint experimental and theoretical analysis

A joint experimental and theoretical study has been carried out to rationalize for the first time the photoluminescence (PL) properties of disordered CaWO₄ (CWO) thin films. From the experimental side, thin films of CWO have been synthesized following a soft chemical processing, their structure has been confirmed by X-ray diffraction data and corresponding PL properties have been measured using the 488 nm line of an argon ion laser. Although we observe PL at room temperature for the crystalline thin films, the structurally disordered samples present much more intense emission. From the theoretical side, first principles quantum mechanical calculations, based on density functional theory at B3LYP level, have been employed to study the electronic structure of a crystalline (CWO-c) and asymmetric (CWO-a) periodic model. Electronic properties are analyzed in the light of the experimental results and their relevance in relation to the PL behavior of CWO is discussed. The symmetry breaking process on going from CWO-c to CWO-a creates localized electronic levels above the valence band and a negative charge transfer process takes place from threefold, WO₃, to fourfold, WO₄, tungsten coordinations. The correlation of both effects seems to be responsible for the PL of amorphous CWO.     

The influence of nuclear volume and electronic structure on the rotational energy of platinum monoxide, PtO

The pure rotational spectra of seven isotopic species of platinum monoxide have been measured with a cavity pulsed jet Fourier-transform microwave spectrometer. The molecules were prepared by laser ablation of Pt foil in the presence of O2 and stabilized in a supersonic jet of argon. A multi-isotopomer Dunham-type analysis of the spectra produced values for Y01 and Y11, along with unusually large values for Born-Oppenheimer breakdown (BOB) parameters for both Pt and O atoms. The values of the BOB parameters have been rationalized in terms of the molecular electronic structure and finite nuclear size (field shift) effects. A large negative 195Pt effective nuclear spin-rotation constant has been rationalized in terms of the electron-nucleus dipole-dipole hyperfine constant. Precise internuclear separations have been evaluated.     

Infrared spectra and structures of the OSc(N2), OScNN, and OScNN+ complexes in solid argon

Scandium monoxide-dinitrogen complexes-OSc(N2), OScNN, and OScNN+-have been prepared by the reactions of laser-evaporated scandium monoxide with N2 or scandium atoms with N2O in solid argon. The ground-state scandium monoxide molecule reacted with N2 to form the side-bonded OSc(N2) complex spontaneously on annealing. This complex rearranged to the end-on bonded OScNN complex upon UV irradiation. Both the OSc(N2) and OScNN complexes in solid argon can be assigned to have 2A' ' electronic ground state with Cs symmetry arising from the 2Delta first excited-state ScO. The neutral complexes can also be photoionized to the OScNN+ cation complex upon UV irradiation.     

The effect of boron nitride nanotubes size on the HArF interaction by NBO and AIM analysis

Three molecules HArF@BNNT(5,0), HArF@BNNT(6,0), and HArF@BNNT(7,0) have been formed by HArF encapsulated in boron nitride nanotubes (BNNTs) with different sizes. Due to the interaction between the HArF and the BNNTs, the H? Ar bond lengths are in a decrease trend, while the Ar? F bond lengths are in an increase trend compared with those of HArF. To investigate the nature of the interaction between H and Ar and the interaction between Ar and F, the quantum theory of “atoms in molecules” was carried out. The Laplacian (?²ρ_b) values of H? Ar suggest that the covalent interaction plays a key role in the H‐Ar interaction. For Ar? F, the results indicate that the Ar‐F interaction has a dominant noncovalent character. Moreover, the results obtained from the ratio of the kinetic‐energy density (G_b) and the potential‐energy density (V_b) (?G_b/V_b) and the total energy density (H_b) are in good agreement with that of ?²ρ_b values. In addition, the results of natural bond orbital charge and electron density difference between the HArF and BNNTs show that less electrons transfer away from the HArF to BNNTs with the gradual increase in the diameters of the BNNTs. © 2014 Wiley Periodicals, Inc.     

Matrix isolation study of the interaction of excited argon atoms with methyl cyanide,vibrational and electronic spectra of ketenimine

When methyl cyanide mixed with an excess of argon is codeposited at 14 K with a beam of argon atoms that has been excited by a low power microwave discharge, infrared and ultraviolet absorptions of several previously unidentified products appear. The most prominent set of absorptions is assigned to ketenimine, previously tentatively identified as the product of the reaction of NH with C₂H₂ in an argon matrix. Using a molecular geometry resulting from a recent ab initio calculation and a valence force field with four interaction constants, it has been possible to obtain a satisfactory least-squares force constant fit to the infrared data for seven isotopic species of ketenimine. Two electronic band systems are also reported for ketenimine, which is photodissociated by 2537-A radiation. The mechanism by which ketenimine is formed may involve an initial electron transfer from excited argon to methyl cyanide. Spectrospic data are also considered for the other products, one of them tentatively identified as CH₂CH, which differ in their behavior on mercury-are photolysis of the sample.     

Reactivity of atomic cobalt with molecular oxygen: a combined IR matrix isolation and theoretical study of the formation and structure of CoO2

The reactivity of atomic cobalt toward molecular oxygen in rare gas matrices has been reinvestigated. Experiments confirm that Co atoms in their a(4)F ground state are inert toward O(2) in solid argon and neon but reactive in the b(4)F first excited state, in agreement with the previous gas-phase study of Honma and co-workers. The formation of CoO(2) starting from effusive beams of Co and O(2) has been followed by IR absorption spectroscopy, both in neon and argon matrices. Our observations show that only the dioxo form, OCoO, is stabilized in the matrix and that IR absorptions previously assigned to the peroxo and superoxo forms are due to other, larger species. The present data strongly support the linear geometry in rare gas matrices proposed by Weltner and co-workers. We report on measurements on all IR-active fundamental modes for (16)OCo(16)O, (18)OCo(18)O, and (16)OCo(18)O with additional combination transitions supplying anharmonicity correction. This allows for a 5.93 +/- 0.02 mdyne/A CoO harmonic bond force constant in solid neon. Using the empirical relationship previously optimized for the CoO diatomics, an approximate value for the CoO internuclear bond distance is proposed (1.615 +/- 0.01A). In light of recent theoretical studies predicting (2)A(1) or (6)A(1) electronic ground states, the geometry and electronic structure of the OCoO molecule has also been reconsidered. Calculations carried out at the CCSD(T)/6-311G(3df) level indicate a linear structure with an r(e) = 1.62 A bond distance, consistent with the experimental estimate. For later studies of larger systems, where CCSD(T) calculations become too time-consuming, an effective DFT-based method is proposed which reproduces the basic electronic and geometrical properties of cobalt dioxide. Quantitative results are compared to the experimental data and high-level results regarding bond length and frequencies. This DFT method is used to propose a reaction pathway.     

Structure and barrier to methyl group internal rotation for (CF3)2CFCF2OCH3 and its isomer n-C4F9OCH3 (HFE-7100)

The hydrofluoroether C(4)F(9)OCH(3) (methoxynonafluorobutane, HFE-7100) has been studied by chirped pulse Fourier transform microwave spectroscopy as vapor from the liquid participates in a supersonic expansion of argon. Two isomers are present, (CF(3))(2)CFCF(2)OCH(3) and n-C(4)F(9)OCH(3), and in each case the rotational spectra of only one, dominating, conformer has been assigned. Rotational constants, centrifugal distortion constants, and barriers to methyl group internal rotation for the observed species have been experimentally determined for the first time. We note that Ray's asymmetry parameter for the (CF(3))(2)CFCF(2)OCH(3) isomer is 0.007?083(1), indicating almost "perfect" asymmetry. Also, electronic structure calculations show an extremely short C(frame)-O ether bond length of 1.337 ?.     

Approximate SCF CI calculation of excited state geometries of phenol,aniline, para-fluorophenol and para-fluoroaniline

The CNDO/s method has been used to study the electronic structure, spectra, geometry and rotational constants in the ground and the first excited singlet states of phenol, aniline, para-fluorophenol and para-fluoroaniline. The ground state geometry has also been studied using CNDO/2 and INDO methods. Calculated bond length changes following the electronic excitation have been compared with experimental results and ambiguities present in the latter have been resolved.     

Absorption spectra of ground-state and low-lying electronic States of copper nitrosyl: a rare gas matrix isolation study

The reaction of ground-state Cu atoms with NO during condensation in solid argon, neon, and binary argon/neon mixtures has been reinvestigated. In addition to the ground-state already characterized in rare gas matrixes by its nu1 mode in reactions of laser-ablated Cu with nitric oxide, another very low lying electronic state is observed for CuNO in solid argon. Photoconversion and equilibrium processes are observed between the two lowest lying electronic states following photoexcitations to second and third excited states in the visible and near-infrared. The electronic spectrum of the CuNO complex was also recorded to understand the photoconversion processes. In solid neon, only the ground state (probably 1A') and the second and third excited states are observed. This suggests that interaction with the argon cage stabilizes the triplet state to make 1A' and 3A' ' states almost isoenergetic in solid argon. On the basis of previous predictions founded on DFT calculations on the very low lying 1A' and 3A' ', a mechanism is proposed, involving the singlet-triplet state manifolds. For these two lower and one higher electronic states, 14N/15N, 16O/18O, and 63Cu/65Cu isotopic data on nu1, nu2, and nu3 have been measured. On the basis of harmonic force-field calculations and relative intensities in the vibronic progressions, some structural parameters are estimated. The molecule is bent in all electronic states, with Cu-N-O bond angles varying slightly around 130 +/- 10 degrees , but the Cu-N bond force constants are substantially different, denoting larger differences in bond lengths.     

Vibrational spectrum and structure of CoO6: a model compound for molecular oxygen reversible binding on cobalt oxides and salts; a combined IR matrix isolation and theoretical study

The formation and structure of a novel species, a disuperoxo-cobalt dioxide complex (CoO(6)), has been investigated using matrix isolation in solid neon and argon, coupled to infrared spectroscopy and by quantum chemical methods. It is found that CoO(6) can be formed by successive complexation of cobalt dioxide by molecular oxygen without activation energy by diffusion of ground state O(2) molecules at 9K in the dark. The IR data on one combination and seven fundamentals, isotopic effects, and quantum chemical calculations are both consistent with an asymmetrical structure with two slightly nonequivalent oxygen ligands complexing a cobalt dioxide subunit. Evidence for other, metastable states is also presented, but the data are not complete. The electronic structure and formation pathway of this unique, formally +VI oxidation state, complex has been investigated using several functionals of current DFT within the broken-symmetry unrestricted formalism. It has been shown that the M06L pure local functional well reproduce the experimental observations. The ground electronic state is predicted to be an open shell (2)A' doublet with the quartet states above by more than 9 kcal/mol and the sextet lying even higher in energy. The ground state has a strong and complex multireference character that hinders the use of more precise multireference approaches and requires caution in the methodology to be used. The geometrical, energetic, and vibrational properties have been computed.     

Effective chromophore potential, dissipative trajectories, and vibrational energy relaxation: Br2 in Ar matrix

The intramolecular wave packet dynamics on the electronic B (3pi0) potential of Br2 in solid argon is induced and interrogated by femtosecond pump-probe spectroscopy. An effective potential of the chromophore in the solid is derived from the wave packet period for different excitation photon energies. Deep in the potential well, it is consistent with vibrational energies from wavelength-resolved spectra. It extends to higher energies, where the vibrational bands merge to a continuum, and even beyond the dissociation limit, thus quantifying the cage effect of the argon matrix. This advantage of pump-probe spectroscopy is related to a reduced contribution of homogeneous and inhomogeneous line broadenings. The vibrational energy relaxation rates are determined by a variation of the probe window spatial position via the probe quantum energy. A very large energy loss in the first excursion of the wave packet is observed near the dissociation limit. This strong interaction with the argon matrix is directly displayed in an experimental trajectory.     

Intermolecular complexes of HArF and HKrF with CO

Stable linear weakly bound hydrogen-bonded complexes of HArF and HKrF with the CO molecule have been predicted by ab initio computations at the MP2/6- 311+ +G(2d,2p) level of theory. The complexes, having stabilities in the order, FArH...CO>FKrH...CO>FArH...OC>FKrH...OC are compared. They exhibit unusual blueshifts of the Ar-H (Kr-H) stretching frequency, as well as contraction of the Ar-H (Kr-H) bond, and these effects are rationalized mainly in terms of shifts in the electron density of HArF (HKrF) on complexation, caused mainly by a combination of the intermolecular electrostatic interaction, electron-electron (Pauli) and nuclear-nuclear repulsion and charge density transferred from the CO molecule to the rare-gas-containing molecule.