Experimental Vibrational Spectroscopy Research Articles

Signatures of coherent vibrational dynamics in ethylene carbonate.

Despite having practical applications in battery technology and serving as a model system for Fermi resonance coupling, ethylene carbonate (EC) receives little direct attention as a vibrational probe in nonlinear vibrational spectroscopy experiments. EC contains a Fermi resonance that is well-characterized in the linear spectrum, and the environmental sensitivity of its Fermi resonance peaks could make it a good molecular probe for two-dimensional infrared spectroscopy (2DIR) experiments. As a model system, we investigate the linear and 2DIR vibrational spectrum of the carbonyl stretching region of ethylene carbonate in tetrahydrofuran. The 2DIR spectrum reveals peak dynamics that evolve coherently. We characterize these dynamics in the context of Redfield theory and find evidence that EC dynamics proceed through coherent pathways, including singular coherence transfer pathways that have not been widely observed in other studies. We find that coherent contributions play a significant role in the observed dynamics of cross-peaks in the 2DIR spectrum, which must be accounted for to extract accurate measurements of early waiting time dynamics.

Neural-network-based molecular dynamics simulations reveal that proton transport in water is doubly gated by sequential hydrogen-bond exchange.

The transport of excess protons in water is central to acid-base chemistry, biochemistry and energy production. However, elucidating its mechanism has been challenging. Recent nonlinear vibrational spectroscopy experiments could not be explained by existing models. Here we use both vibrational spectroscopy calculations and neural-network-based molecular dynamics simulations that account for nuclear quantum effects for all atoms to determine the proton transport mechanism. Our simulations reveal an equilibrium between two stable proton-localized structures with distinct Eigen-like and Zundel-like hydrogen-bond motifs. Proton transport follows a three-step mechanism gated by two successive hydrogen-bond exchanges: the first reduces the proton-acceptor water coordination, leading to proton transfer, and the second, the rate-limiting step, prevents rapid back-transfer by increasing the proton-donor coordination. This sequential mechanism is consistent with experimental characterizations of proton diffusion, explaining the low activation energy and the prolonged intermediate lifetimes in vibrational spectroscopy. These results are crucial for understanding proton dynamics in biochemical and technological systems.

Harmonic and anharmonic vibrational computations for biomolecular building blocks: Benchmarking DFT and basis sets by theoretical and experimental IR spectrum of glycine conformers.

Advanced vibrational spectroscopic experiments have reached a level of sophistication that can only be matched by numerical simulations in order to provide an unequivocal analysis, a crucial step to understand the structure-function relationship of biomolecules. While density functional theory (DFT) has become the standard method when targeting medium-size or larger systems, the problem of its reliability and accuracy are well-known and have been abundantly documented. To establish a reliable computational protocol, especially when accuracy is critical, a tailored benchmark is usually required. This is generally done over a short list of known candidates, with the basis set often fixed a priori. In this work, we present a systematic study of the performance of DFT-based hybrid and double-hybrid functionals in the prediction of vibrational energies and infrared intensities at the harmonic level and beyond, considering anharmonic effects through vibrational perturbation theory at the second order. The study is performed for the six-lowest energy glycine conformers, utilizing available "state-of-the-art" accurate theoretical and experimental data as reference. Focusing on the most intense fundamental vibrations in the mid-infrared range of glycine conformers, the role of the basis sets is also investigated considering the balance between computational cost and accuracy. Targeting larger systems, a broad range of hybrid schemes with different computational costs is also tested.

Vibrational properties of a mononuclear dysprosium containing singlemolecule magnet

Dysprosium(III)-containing single-molecule magnets (SMMs) show blocking of the molecular magnetization and hysteresis effects in one molecule. They belong to the class of the best performing SMMs at present. Here, we present first results of 161Dy-Nuclear Resonance Vibrational Spectroscopy (NRVS) experiments on the dysprosium(III) complex [Dy(H2dapp)(NO3)2](NO3) with H2dapp being 2,6-bis((E)-1-(2-(pyridine-2-yl)-hydrazineylidene)ethyl)pyridine. For the 161Dy-NRVS experiments a compact novel He flow cryostat was used at the Advanced Photon Source, Argonne National Laboratories, which enables low temperature NRVS experiments in helium vapour circumventing the often-observed difference between sensor read and “real” sample temperature in mostly used LHe and/or closed cycle cryostats with the NRVS sample being in vacuum. To explore the vibrational modes of the molecule simulations based on first density functional theory (DFT) calculations are presented.

On the solvation structures formed in conditioning-free MMAC-based electrolytes: A theoretical–experimental spectroscopic insight of interest to Mg battery area

The 2.39:1 Mg:MgCl2:AlCl3 (MMAC)-tetrahydrofuran (THF) and 1:1.22 MMAC-diethylene glycol dimethyl ether (G2) electrolytes, which have been already investigated by electrochemical measurements, are studied in the current work by using experimental vibrational spectroscopy allied to ab initio molecular dynamics (AIMD) simulations of spectra. Raman data are practically identical to the 2:1 MgCl2:AlCl3 (MACC)-THF and 3:5 MACC-G2 binary systems, except for a 330 cm−1 band, commonly assigned to [AlCl3(THF)1-2] and/or [AlCl2]+, which is absent for the THF-based ternary system. Subtle changes are also seen in the far-IR spectra, where a band at around 315 cm−1 shows strong dependence on the MgCl2 content and so may be associated to the [Mg2(μ-Cl)3]+ dimer. The monomeric species, [MgCl]+, is also observed in both electrolytes by means of IR bands at 270–285, 300 and 325–330 cm−1. The varied amounts of monomer and dimer seem to be related to the electrochemical activities determined for these ternary systems.

Insights into structural and vibrational characteristics of 1-methoxy-4-[2-(phenylsulfonyl)vinyl]benzene: An application of experimental vibrational spectroscopy and density functional theory

Fourier transform infrared and Raman spectra, in the spectral range 4000- 400 and 4000–50 cm−1, respectively, were measured for 1‑methoxy-4-[2-(phenylsulfonyl)vinyl]benzene (MPB). Initial values of torsion angles around five flexible bonds C1-S, S-C15, C17-C19, C22-O and OC30 (see Fig. 1 for numbering), essential for starting geometry optimization, were determined using "bond-pairing method" proposed earlier by us. Optimized structure parameters, harmonic general valence force field, vibrational fundamentals, potential energy distribution and infrared and Raman band intensities were determined using density functional theory, employing B3LYP/ 6–311++G(d,p) formalism. Good agreement was found, between measured and computed quantities investigated here. The r.m.s error between experimental and theoretical vibrational wavenumbers was 8.6 cm−1, for MPB. With the help of PED and eigenvectors, all vibrational fundamentals of the molecule were assigned unambiguously for the first time.

Behavior of Hydrogarnet‐Type Defects in Hydrous Stishovite at Various Temperatures and Pressures

AbstractDense polymorphs of silica have been demonstrated experimentally to incorporate from 1.5 wt% to as much as 11.6 wt% H2O as OH groups, with implications for the hydrogen budgets of Earth and other planets. This OH is thought to enter the SiO2 structure via a charge‐balanced substitution in which silicon vacancies (VSi) are compensated by protonating four of the surrounding six oxygen atoms, often referred to as a hydrogarnet‐type defect. There are many possible configurations for this defect structure in dense silica, but the nature of these configurations and whether they can be distinguished experimentally is unknown. We present here density functional theory calculations that systematically assess the possible configurations of a hydrogarnet‐type defect in stishovite (rutile‐type SiO2), with direct comparisons to experimental vibrational spectroscopy data. We predict that stishovite synthesized at 450 K and 10 GPa quenched to room temperature is dominated by a single defect type with tetrahedral geometry. This leads to OH stretching modes (2,500–3,000 cm−1) and SiOH bending modes (∼1,400–1,450 cm−1) largely consistent with experimentally observed modes. One remaining issue is that our calculations produce results compatible with experimental data on H to D exchange, but do not explain why a considerable fraction of the 1,420 cm−1 mode shifts by only 40 cm−1 in deuterated samples. At elevated pressures and temperatures, we find that a second square planar defect configuration also becomes favorable, leading to modes that should allow differentiation from the tetrahedral configuration.

Substrate-Gated Transformation of a Pre-Catalyst into an Iron-Hydride Intermediate [(NO)2(CO)Fe(μ-H)Fe(CO)(NO)2]- for Catalytic Dehydrogenation of Dimethylamine Borane.

Continued efforts are made on the development of earth-abundant metal catalysts for dehydrogenation/hydrolysis of amine boranes. In this study, complex [K-18-crown-6-ether][(NO)2Fe(μ-MePyr)(μ-CO)Fe(NO)2] (3-K-crown, MePyr = 3-methylpyrazolate) was explored as a pre-catalyst for the dehydrogenation of dimethylamine borane (DMAB). Upon evolution of H2(g) from DMAB triggered by 3-K-crown, parallel conversion of 3-K-crown into [(NO)2Fe(N,N'-MePyrBH2NMe2)]- (5) and an iron-hydride intermediate [(NO)2(CO)Fe(μ-H)Fe(CO)(NO)2]- (A) was evidenced by X-ray diffraction/nuclear magnetic resonance/infrared/nuclear resonance vibrational spectroscopy experiments and supported by density functional theory calculations. Subsequent transformation of A into complex [(NO)2Fe(μ-CO)2Fe(NO)2]- (6) is synchronized with the deactivated generation of H2(g). Through reaction of complex [Na-18-crown-6-ether][(NO)2Fe(η2-BH4)] (4-Na-crown) with CO(g) as an alternative synthetic route, isolated intermediate [Na-18-crown-6-ether][(NO)2(CO)Fe(μ-H)Fe(CO)(NO)2] (A-Na-crown) featuring catalytic reactivity toward dehydrogenation of DMAB supports a substrate-gated transformation of a pre-catalyst [(NO)2Fe(μ-MePyr)(μ-CO)Fe(NO)2]- (3) into the iron-hydride species A as an intermediate during the generation of H2(g).

Assignment of Vibrational Bands of Critical Surface Species Containing Nitrogen in the Selective Catalytic Reduction of NO by NH3.

The selective catalytic reduction (SCR) of NO by NH3 on metal oxides plays a key role in minimizing NOx emissions. Electronic structure calculations at the density functional theory level have been performed to predict the vibrational modes of NH3/NH4+ bound to validated cluster models of vanadium oxide bound to a TiO2 surface. Excellent agreement of the scaled calculated values with the observed bands attributed to surface-bound species is found. The presence of NH3 bound to Lewis acid sites and NH4+ bound to Brønsted acid sites when VOH groups are present is supported by our predictions. NH4+ is expected to dominate the spectra even at low concentrations, with predicted intensities 5 to 30 times greater than those predicted for surface-bound NH3. This is particularly evident in the lowest-energy N-H stretches of surface NH4+ due to partial proton transfer interactions with the vanadium oxide surface model. The current work is consistent with experimental vibrational spectroscopy results and does not support the presence of a significant amount of NH2 on the catalyst surface for the SCR reaction on VOx/TiO2. The combined experimental and computational results support the presence of both NH3- and NH4+-type species bound to the surface.

Local mode analysis of characteristic vibrational coupling in nucleobases and Watson–Crick base pairs of DNA

Two-dimensional infrared spectroscopy has reported highly delocalized in-plane base vibrations in the fingerprint region of nucleotide monophosphates, suggesting the involvement of base pair C=O and C=C ring bonds and considerable interaction between C=O bond stretches. The high delocalization results in congested vibrational spectra, which complicates the assignment of the peaks. This congestion also extends to Watson–Crick base pairs. We applied in this work the characterization of normal mode procedure, a special feature of our local mode analysis, and could for the first time identify the C=O and C=C bonds being engaged in base pair coupling and quantify their contribution to each of the delocalized fingerprint vibration. In addition, a detailed and quantitative description of the hydrogen bonds involved in the Watson–Crick base pairs was provided. Based on the results of this study, we developed a new protocol to elucidate on the assignment of bands in the vibrational spectra of nucleic acids by probing the vibrational space for specific interactions between functional groups prior to and upon base pairing. This protocol will aid to fill the gap between deoxyribonucleic acid structural information and vibrational spectroscopy experiments by facilitating the interpretation of spectra on a quantitative basis.

Complex investigation of H-bond in Water-N-methylacetamide system: Volumetric properties, DFT, IR, MD analysis

• Behavior of the volumetric properties of the binary water-NMA mixture was studied over wide pressure ranges. • Hydrogen bonds in NMA–water mixtures were analyzed using computer chemistry and vibrational spectroscopy. • The analysis of the strength of the hydrogen bond between amides and surrounding water molecules is carried out. • The hydrogen atoms of water and amide compete as hydrogen bond donors. A combined approach of computational chemistry, vibrational spectroscopy experiments, and density measurements was used to study the structural properties of water-N-methylacetamide mixtures over the entire concentration range. The structure of N-methylacetamide dimers and hydrogen-bonded complexes of N-methylacetamide with water molecules was investigated by the quantum chemical method on the basis of the density functional theory. The vibrational spectra of aqueous solutions of N-methylacetamide were recorded. Based on quantum chemical calculations, the bands of the vibrational spectrum were identified, which made it possible to trace the change in hydrogen bonding in the system. At increased N-methylacetamide concentration, the hydrogen bond network rearranges. The number of hydrogen bonds between water molecules decreases, water molecules bind to N-methylacetamide molecules, changing the nature of its environment. Aqueous mixture containing N-methylacetamide shows strong deviations of volumetric properties from ideality. For the further analysis of the data obtained, molecular dynamics simulation of this system was conducted at various temperatures and pressures. It was shown that the resulting hydrogen bonds are of medium strength, but their strength depends on the water molecule environment, which is proved by NBO and QTAIM data. A network of hydrogen bonds is formed in N-methylacetamide aqueous solution, which is noticeably destroyed with an increase in temperature and slightly changes with an increase in pressure.

Carbon Nanoparticle-Induced Changes to Lipid Monolayer Structure at Water-Air Interfaces.

Surface specific vibrational spectroscopy experiments together with surface tension measurements and spectroscopic ellipsometry data were used to characterize the effects of soluble carbon particulates on compressed and partially compressed lipid monolayers adsorbed to the water-air interface. The lipid monolayers consisted of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DPPC), and measurements were made for both tightly packed monolayers (40 Å2/molecule) and monolayers in their liquid condensed state (55 Å2/molecule). Langmuir trough data show that very small amounts of PHF (0.0075 mg/mL or 6.4 × 10-6 M) decrease lipid film compressibility. This finding supports a cooperative adsorption mechanism whereby the soluble PHFs are drawn to the surface and associate with the insoluble DPPC monolayer. Excess free energies (ΔGmixE) were positive, consistent with the cooperative adsorption mechanism, and although the excess free energies are small (≤1 kJ/mol), adsorbed PHF has measurable effects on monolayer structure. Further support for the cooperative adsorption mechanism at the water-air interface comes from vibrational sum frequency generation (VSFG) experiments. Low PHF concentrations (≤0.06 mg/mL) increase DPPC acyl chain ordering in liquid condensed lipid films and decrease DPPC acyl chain ordering and film thickness in tightly packed lipid films.

Revisiting OD-stretching dynamics of methanol‑d4, ethanol-d6 and dilute HOD/H2O mixture with predefined potentials and wavelet transform spectra

• The stretching profiles of OD probes were obtained from classical trajectories. • The normalized frequency distribution and rotational anisotropy are reported. • An accurate and efficient method was reported for the spectral profiles. • The reported results are in an excellent agreement with that of the experiment. Classical molecular dynamics simulations were performed to explore the stretching profiles of hydrogen-bonded liquids using the wavelet transform of classical trajectories to calculate the time-resolved vibrational stretching frequencies of the probes. This method considers the instantaneous distance fluctuations of the unit vector and the momentum along the corresponding bond to calculate the instantaneous stretching frequencies and equilibrium distribution. In this work, we calculated the vibrational spectral properties of the O-D stretch modes in hydrogen-bonding liquids, water, methanol, and ethanol. The time-varying vibrational stretching frequencies of the probes were obtained from the simulated trajectory accurately as compared to other methods. The normalized frequency distribution, time-dependent decay of frequency fluctuations, rotational anisotropy calculations are reported, and relative comparison is made with the existing results. The results of the isotopically diluted HOD mixture and deuterated methanol molecules are in excellent agreement with the experiment, and the ethanol results are satisfactory. This computational method of determining the stretching frequency distribution comparable to the reported vibrational spectrum is one of the complementary accurate theoretical models for the ultrafast vibrational echo spectroscopy experiments. Further, the method can also be adapted to calculate the instantaneous stretching frequency of any probe of interest in a complicated molecular environment.

Ionic liquid-air interface probed by sum frequency generation spectroscopy and molecular dynamics simulation: influence of alkyl chain length and anion volume

ABSTRACT Understand the structure of the ILs/air interface on a molecular level is significant. In this work, the liquid-air interface of a class of ILs containing 1-alkyl-3-methylimidazolium cations ([Cnmim]+, n = 4, 6 and 8) was investigated by a sum-frequency generation vibrational spectroscopy experiment. The length of the alkyl chain of cations and anion type (tetrafluoroborate ([BF4]−), thiocyanate ([SCN]−), dicyanamide ([DCA]−), hexafluorophosphate ([PF6]−)) were varied to determine their intrinsic effects to the micro-structure on the interface. Meanwhile, combining with the experiment, the orientation angle and surface density for cations and anions of ILs at the air interface was analyzed by molecular dynamics simulation. It is found that the butyl side chain of cations protrudes out into the air as well as the orientation angle between the side chain and interface is 30°–50°. Meanwhile, the anion volume of ILs has almost no influence on the butyl side chain and the methyl on the side chains tend almost planar to the interface with the increased chain length. This research is highly significant for the theoretical and quantitative understanding of the interface chemistry of imidazole-based ILs.

A New Solid-State Proton Conductor: The Salt Hydrate Based on Imidazolium and 12-Tungstophosphate.

We report the structure and charge transport properties of a novel solid-state proton conductor obtained by acid–base chemistry via proton transfer from 12-tungstophosphoric acid to imidazole. The resulting material (henceforth named Imid3WP) is a solid salt hydrate that, at room temperature, includes four water molecules per structural unit. To our knowledge, this is the first attempt to tune the properties of a heteropolyacid-based solid-state proton conductor by means of a mixture of water and imidazole, interpolating between water-based and ionic liquid-based proton conductors of high thermal and electrochemical stability. The proton conductivity of Imid3WP·4H2O measured at truly anhydrous conditions reads 0.8 × 10–6 S cm–1 at 322 K, which is higher than the conductivity reported for any other related salt hydrate, despite the lower hydration. In the pseudoanhydrous state, that is, for Imid3WP·2H2O, the proton conductivity is still remarkable and, judging from the low activation energy (Ea = 0.26 eV), attributed to structural diffusion of protons. From complementary X-ray diffraction data, vibrational spectroscopy, and solid-state NMR experiments, the local structure of this salt hydrate was resolved, with imidazolium cations preferably orienting flat on the surface of the tungstophosphate anions, thus achieving a densely packed solid material, and water molecules of hydration that establish extremely strong hydrogen bonds. Computational results confirm these structural details and also evidence that the path of lowest energy for the proton transfer involves primarily imidazole and water molecules, while the proximate Keggin anion contributes with reducing the energy barrier for this particular pathway.

Structural Features of Y2O2SO4 via DFT Calculations of Electronic and Vibrational Properties

The traditional way for determination of molecular groups structure in crystals is the X-Ray diffraction analysis and it is based on an estimation of the interatomic distances. Here, we report the analysis of structural units in Y2O2SO4 using density functional theory calculations of electronic properties, lattice dynamics and experimental vibrational spectroscopy. The Y2O2SO4 powder was successfully synthesized by decomposition of Y2(SO4)3 at high temperature. According to the electronic band structure calculations, yttrium oxysulfate is a dielectric material. The difference between the oxygen–sulfur and oxygen–yttrium bond nature in Y2O2OS4 was shown based on partial density of states calculations. Vibrational modes of sulfur ions and [Y2O22+] chains were obtained theoretically and corresponding spectral lines observed in experimental Infrared and Raman spectra.

Study of the interactions of gold nanoparticles functionalized with aminolevulinic acid in membrane models

Gold nanoparticles have been intensively studied in cancer therapy to improve drug release, increasing therapeutic action and reducing adverse effects. The interaction between gold nanoparticles and cell membranes can give information about the cell internalization. In this study, gold nanoparticles with aminolevulinic acid (5-ALA) were synthesized using the photoreduction method (5-ALA: AuNPs). The prodrug 5-ALA is responsible for protoporphyrin IX synthesis inside the cell and allows the use of therapies as photodynamic and sonodynamic therapies. The cytotoxicity test was performed on a breast cancer tumor line (MCF-7), and high Content Screening assay was applied to evaluate the entry of nanoparticles into cells. DPPS Langmuir monolayers were assembled at the air/water interface and employed as a simplified membrane model for half of a tumorigenic cell membrane. We assessed the molecular interactions between 5-ALA: AuNPs and phospholipids using tensiometry (π-A isotherms) and vibrational spectroscopy (PM-IRRAS) experiments. We found that the functionalized gold nanoparticles strongly interact with DPPS polar head groups (especially phosphate and carbonyl), changing the phospholipid hydration and leading to a general decrease in the monolayer conformational order. This work then probes that specific interaction between 5-ALA: AuNPs and the negatively charged phospholipid can be assessed using Langmuir monolayers as simplified biomembrane models.

Synthesis, vibrational and thermal properties of new functionalized 1- (2-hydroxyethyl) -3-methylimidazolium dihydrogenophosphate ionic liquid

Very recently, the hydroxyl-functionalized ionic liquids have gained immense interest and were developed for a number of interesting applications. In this work and for the first time new hydroxyl-functionalized namely; 1-(hydroxyethyl)-3-methylimidazolium dihydrogenophosphate ionic liquid [EtOHMIM+][H2PO4−] was synthesized in our laboratory. The synthesis is based on an alkylation reaction of 1-methylimidazole followed by anion exchange. The obtained IL is characterized by 1H-NMR, 13C-NMR spectroscopy. Their experimental vibrational spectroscopy have been investigated using Infrared and Raman spectroscopy, based on the infrared (IR) and Raman spectroscopies results, complete vibrational assignments have been performed. Besides, thermal properties of this hydroxyl-functionalized IL were investigated by using following techniques, (i) Thermogravimetric Analysis (TGA) and Derivative Thermogravimetry (DTG) in the temperature range from 20 to 600 C°, (ii) differential scanning calorimetry (DSC) from-100 °C to 200 °C. The thermogravimetry analysis was coupled with mass spectrometry in order to assess the influence of anion on the measured property.

Fingerprint region of the formic acid dimer: variational vibrational computations in curvilinear coordinates.

Curvilinear kinetic energy models are developed for variational nuclear motion computations including the inter- and the low-frequency intra-molecular degrees of freedom of the formic acid dimer. The coupling of the inter- and intra-molecular modes is studied by solving the vibrational Schrödinger equation for a series of vibrational models, from two up to ten active vibrational degrees of freedom by selecting various combinations of active modes and constrained coordinate values. Vibrational states, nodal assignment, and infrared vibrational intensity information is computed using the full-dimensional potential energy surface (PES) and electric dipole moment surface developed by Qu and Bowman [Phys. Chem. Chem. Phys., 2016, 18, 24835; J. Chem. Phys., 2018, 148, 241713]. Good results are obtained for several fundamental and combination bands in comparison with jet-cooled vibrational spectroscopy experiments, but the description of the ν8 and ν9 fundamental vibrations, which are close in energy and have the same symmetry, appears to be problematic. For further progress in comparison with experiment, the potential energy surface, and in particular, its multi-dimensional couplings representation, requires further improvement.

The Effect of Conformation Order on Gas Separation Properties of Polyetherimide Ultem Films.

Changes of the spectral characteristics of absorption bands depending on the films’ treatment method were registered for polyetherimide Ultem films. The possibility of selection of structural criteria (the ratio of the functional groups absorption bands intensities) showing all conformational changes in elementary unit with metrological processing of the results is shown. It is demonstrated that film formation from chloroform solution leads to elementary unit fragments, Ph–O–Ph′, which have an effect on macromolecule conformation and result in increasing of space between fragments of macromolecules (local polymer matrix packing loosening). Desorption of residual chloroform from films by ethanol or supercritical CO2 leads to a change of conformers set in Im–Ph–Im′ units. Quantum chemical modeling showed the possibility of convergence of these fragments in neighboring macromolecules, and consequently of interchain π–π interaction (local densification of chain packing of the polymer matrix). After annealing at a temperature higher than glass transition temperature, the polyetherimide film exhibits the most disordered (amorphous) state at all of the fragments. It is demonstrated that the results, obtained by the combination of theoretical and experimental vibrational spectroscopy methods, are in good agreement with data of chain packing ordering found by analysis of gas separation parameters.