How van der Waals bonds orient molecules in zeolites

We show that weak bonds are responsible for the way a molecule is held in a zeolite, and for its reactivity.     

Model for vibrational predissociation of van der Waals molecules

We advance a theoretical model for vibrational predissociation (VP) of a linear triatomic molecular complex consisting of a rare-gas atom bound to diatomic, which rests on the decay of a bound state into a manifold of coupled translational continua. We explored the dependence of the VP rate on the molecular parameters of the complex, establishing an energy gap law for VP. The effects of intercontinuum coupling on the dynamics of VP were investigated.     

Calculation of the van der Waals volumes of organic molecules

A new and more precise method is proposed for calculating van der Waals atomic and molecular volumes of organic compounds. The method provides for intersections of three or more spheres at one point of space. Such a possibility is essential for calculating the volumes of sterically overcrowded molecules and of molecules with intramolecular hydrogen bonds. A computer program for IBM PC/AT(XT) is developed. Depending on the atomic environment in the molecule, the average values of the volume increments for atoms C, N, O, H, F, Cl, and S are obtained using the data from the Cambridge Structural Database.N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 117071. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 922–931, April, 1992.     

Reactions of O with CO van der Waals molecules and clusters

The reaction of O(³ P) with COR _m clusters to produce electronically excited CO₂ was studied under molecular beam conditions. It was found that the spectrum of the chemiluminescence produced extended from the blue all the way to the near infrared. The dependence of the total emission intensity on stagnation pressure was investigated for (CO) _m as well as for COR _m , R=He, Ne, Ar, N₂, CO₂ and SO₂. The low pressure data indicate that small (CO) _m polymers are more efficient than clusters of CO with other species in inducing the chemiluminescent reaction. The larger CO-rare gas clusters, however, exhibited larger reaction cross-sections than those of the CO polymers. Rare gas clusters ofm≧5, on the other hand have successively smaller cross sections for reaction. The reactivity of the CO₂ and SO₂ clusters seems to peak at aboutm=1 and then decreases for larger species. An equilibrium model for cluster formation was proposed and it was found capable of explaining and simulating the experimental observations. Contrary to what was reported from afterglow experiments, no barrier for the reaction was detected.     

The role of van der Waals molecules in vibrational relaxation kinetics

The relaxation kinetics of N₂O and CO₂ vibrationally excited molecules (VEM) in two-phase gas-cluster systems was investigated under conditions of supersonic expansion with condensation. The catalytic effect of clusters on the vibrational relaxation rate was revealed. The relaxation rate of clustered VEM, R_c, and the probability of relaxation of VEM per collision with a cluster, $\text{P}$, as functions of the average number of molecules in a cluster, $\text{N}$, were obtained. Values of R_c and $\text{P}$ increase rapidly with increasing $\text{N}$, and at $\text{N}$ = constant they decrease with decreasing cluster temperature.     

Resolved high Rydberg spectroscopy of polyatomic molecules and van der Waals clusters

Using sub-Doppler double resonance excitation with Fourier-transform limited laser pulses and pulsed field ionization techniques we were able to resolve individual high n Rydberg states (45 < n < 110) below and above the lowest ionization energy of van der Waals clusters of benzene with the noble gases neon and argon. By choosing various selected J'K' intermediate rotational states we detected and assigned several Rydberg series with nearly vanishing quantum defect. They converge to different limits representing the rotational states in the vibrational states of the cluster cation. Even far above the ionization threshold sharp high-n Rydberg states with a width of 750 MHz are observed converging to intramolecular vibrational states located up to 800 cm-1 above the dissociation threshold of the cluster ion. This points to a slow dissociation rate of the cluster ion in the range of 3 x 10(5) s-1 < k < 5 x 10(8) s-1. In further studies single high Rydberg states of benzonitrile, a polyatomic molecule with an high dipole moment of 4.18 D, were detected in the range from n = 50 to 100. We plan to investigate the influence of the strong anisotropic dipole field of this molecule on the coupling between the high Rydberg electron and the molecular core.     

Heterogeneous dynamics, ageing, and rejuvenating in van der Waals liquids

It has been shown over the past ten years that the dynamics close to the glass transition is strongly heterogeneous: fast domains coexist with domains three or four decades slower, the size of these regions being about 3 nm at T(g). The authors extend here a model that has been proposed recently for the glass transition in van der Waals liquids. The authors describe in more details the mechanisms of the alpha relaxation in such liquids. It allows then to interpret physical ageing in van der Waals liquids as the evolution of the density fluctuation distribution towards the equilibrium one. The authors derive the expression of macroscopic quantities (volume, compliance, etc.). Numerical results are compared with experimental data (shape, times to reach equilibrium) for simple thermal histories (quenches, annealings). The authors explain the existence of a "Kovacs memory effect" and the temporal asymmetry between down jump and up jump temperatures experiments, even for systems for which there is no energy barriers. Their model allows also for calculating the evolution of small probe diffusion coefficients during ageing.     

The van der Waals interaction between protein molecules in an electrolyte solution

In this report we present a general formulation to calculate the van der Waals interaction between two protein molecules in an electrolyte solution using boundary element method of solving linearized Poisson-Boltzmann equation. Our formulation is based upon an inhomogeneous dielectric model of proteins at the residue level. Our results for bovine pancreatic trypsin inhibitor at various relative orientations indicate that the anisotropy of the interaction can be tens of kBT.     

Body-fixed complex-coordinate coupled-channel formalism for rotational predissociation of van der Waals molecules

The method of complex-coordinate coupled-channel (CCCC) formalism previously developed in the space-fixed (SF) frame is reformulated in the body-fixed (BF) frame, more appropriate for strong-coupling van der Waals complexes. The utility of the method is demonstrated through a study of the level widths and energies of rotationally predissociating atom-diatom model systems. The possible usefulness of incorporating the centrifugal decoupling approximation in the BF CCCC theory is pointed out.     

Characteristics and relaxation dynamics of van der Waals complexes between p-difluorobenzene and Ne

Characteristics of the single and double Ne van der Waals complexes of p-difluorobenzene (pDFB) have been explored with ultraviolet fluorescence excitation and dispersed fluorescence spectroscopy. Eight S(1)-S(0) fluorescence excitation bands involving six ring modes of pDFB-Ne and two bands of pDFB-Ne(2) have been identified. Band assignments are confirmed by dispersed fluorescence from the pumped band. Shifts of the complex bands from the analogous monomer bands are generally 4 cm(-1) to the red for pDFB-Ne and 8 cm(-1) for pDFB-Ne(2). None of the observed ring modes is significantly perturbed by complexation in either the S(1) or S(0) states. The pDFB-Ne S(1) van der Waals binding energy D(0')相似文献   

Augmented van der Waals equations of state: SAFT-VR versus Yukawa based van der Waals equation

Performance of the SAFT-VR equation of state developed for the hard sphere based simple fluids, namely the square-well, Sutherland and Yukawa fluids, is examined by comparing its results with simulation data and an augmented van der Waals (vdW) equation based on a Yukawa (Y) reference. Its shown that both for the equilibrium vapor-liquid data and data along selected isotherms in the liquid and supercritical fluid phases the vdW(Y) equation provides better results, particularly when going to lower temperatures.     

On the angular shape of van der Waals dimers of small polar molecules

Ab initio calculations on twenty van der Waals dimers of small polar molecules at the experimentally observed intermolecular separation R, using Hartree-Fock molecular moments, show that the minima in the electrostatic interaction expanded up to R⁻⁶ converges to angular structures which are close to those observed experimentally for such complexes.     

Resonances of triatomic van der Waals molecules by the complex discrete variable representation

Summary The results of Light and co-workers [J. Chem. Phys. 85:4594 (1986); 86:3065 (1987); 92:2129 (1990)] for the Hamiltonian matrix of a triatomic van der Waals molecule in the discrete variable representation, DVR, is extended to complex-scaled Hamiltonians. As an illustrative numerical example theJ=1 resonances positions and widths of a van der Waals model system were obtained by the calculation of the complex-scaled Hamiltonian matrix in the DVR formalism.Supported in part by the Albert Einstein Research Fund, and the Fund for the Promotion of Research at the Technion     

Spectroscopy and dynamics of 9,10-dichloroanthracene-Arn van der Waals complexes

In this paper we report on the measurements of the absorption spectra of large van der Waals complexes in planar supersonic jets. The absorption spectra and the fluorescence excitation spectra of the complexes of 9,10-dichloroanthracene (DCA) with Ar atoms are reported for the S₀ → S₁(0) vibrationless transition of DCA·Ar_n (n = 1?6), and from the S₀ → S₁ (1390 cm^?1) transition of DCA·Ar_n (n = 1?4). Information on the structure of these complexes was inferred from the additivity of the spectral shifts per added rare-gas atom (ASSRA) for DCA·AR_n (n = 1.2) and from deviations from the ASSRA for CDA-Ar_n (n = 3?6). The vibrational predissociation (VP) dynamics of DCA-Ar_n (n = 1?3) complexes was interrogated by fluorescence quantum yield, Y, measurements. The value of the S₁ (1390 cm^?1) state of DCA·Ar_n (n = 1?3) exhibits a dramatic enhancement relative to that of DCA. Utilizing the dependence of Y on the excess vibrational energy of bare DCA, we were able to estimate the internal energy of the fragments resulting from VP of DCA·Ar_n of DCA·Ar_n (n = 1?3). An upper limit of ? 100 ps was estimated for the VP (and/or vibrational energy redistribution) lifetime from the S₁ (1390 cm^?1) state of DCA·Ar₃.     

Prediction of physicochemical properties of organic molecules using van der Waals surface electrostatic potentials

The generalized interaction properties function (GIPF) methodology developed by Politzer and coworkers, which calculated molecular surface electrostatic potential (MSESP) on a density envelope surface, was modified by calculating the MSESP on a much simpler van der Waals (vdW) surface of a molecule. In this work, vdW molecular surfaces were obtained from the fully optimized structures confirmed by frequency calculations at B3LYP/6-31G(d) level of theory. Multiple linear regressions for normal boiling point, heats of vaporization, heats of sublimation, heats of fusion, liquid density, and solid density were performed using GIPF variables from vdW model surface. Results from our model are compared with those from Politzer and coworkers. The surface-dependent beta (and gamma) values are dependent on the surface models but the surface-independent alpha and regression coefficients (r) are constant when vdW surface and density surface with 0.001 a.u. contour value are compared. This interesting phenomenon is explained by linear dependencies of GIPF variables.     

Phototransformation of stilbene in van der Waals nanocapsules

We have utilized para-hexanoylcalix[4]arene nanocapsules as hosts to carry out phototransformations of cis- and trans-stilbene. Single-crystal X-ray diffraction studies were performed to define precisely the location of encapsulated stilbenes inside the capsule and to analyze possible pathways of phototransformation. cis-Stilbene stacks as a pi-pi dimer located at the center of the capsule, whereas trans-stilbene does not form such a dimer. Irradiation of the crystalline inclusion complexes of each isomer of stilbene in the solid state leads to the appearance of the second isomer, and after prolonged photolysis, photodimerization also occurs. syn-Tetraphenylcyclobutane is formed as the major product of dimerization and its yield depends on the time and intensity of irradiation. In most cases, the single crystals of the complexes remain intact during irradiation; hence, the nanocapsules have the potential to serve as robust nanoreactors in the solid state. The confinement in the nanocapsules is sufficient to keep the reacting molecules together, although this is less restrictive than for trans-stilbene crystals, in which the molecules cannot achieve a favorable orientation for dimerization.     

van der Waals interactions across stratified media

Working at the Lifshitz level, we investigate the van der Waals interactions across a series of layers with a periodic motif. We derive the complete form of the van der Waals interaction as an explicit function of the number of periodic layers. We then compare our result with an approximation based on an anisotropic-continuum representation of the stratified medium. Satisfactory agreement between discrete-layer and continuum models is reached only for thicknesses of ten or more layers.