Antisymmetric Stretch Research Articles

Infrared Matrix-Isolation and Theoretical Studies of the Reactions of Bis(benzene)chromium with Ozone.

Reactions of bis(benzene)chromium (Bz2Cr) and ozone (O3) were studied using low-temperature argon matrix-isolation infrared spectroscopy with supporting DFT calculations. When Bz2Cr and O3 were co-deposited, they reacted upon matrix deposition to produce two new prominent peaks in the infrared spectrum at 431 cm-1 and 792 cm-1. These peaks increased upon annealing the matrix to 35 K and decreased upon UV irradiation at λ = 254 nm. The oxygen-18 and mixed oxygen-16,18 isotopic shift pattern of the peak at 792 cm-1 is consistent with the antisymmetric stretch of a symmetric ozonide species. DFT calculations of many possible ozonide products of this reaction were made. The formation of a hydrogen ozonide (H2O3) best fits the original peaks and the oxygen-18 isotope shift pattern. Energy considerations lead to the conclusion that the chromium-containing product of this reaction is the coupled product benzene-chromium-biphenyl-chromium-benzene (BzCrBPCrBz). 2Bz2Cr+O3→H2O3+BzCrBPCrBz, ∆Ecalc=-52.13kcal/mol.

Generation of High-Lying Vibrational States in Carbon Dioxide through Coherent Ladder Climbing.

Mid-infrared laser excitation of molecules into high-lying vibrational states offers a novel route to realize controlled ground-state chemistry. Here we successfully demonstrate vibrational ladder climbing in the antisymmetric stretch of CO2 in the condensed phase by using intense down-chirped mid-infrared pulses. Spectrally resolved pump-probe measurements directly observe excited-state absorptions attributed to vibrational populations up to the v = 9 state, whose corresponding energy of 2.5 eV is 46% of the dissociation energy. By the use of global fitting analysis, important spectroscopic parameters in the high-lying vibrational states, such as transition frequencies and relaxation times, are quantitatively characterized. Remarkably, our analysis shows that 40% of the molecules are excited above the typical activation barriers in the metal-catalyzed CO2 conversions. These results not only demonstrate the promising ability of infrared excitation to produce elevated vibrational states but also represent a significant step toward accelerating CO2 conversions and other chemical processes via mode-specific vibrational excitation.

How the nature and charge of metal cations affect vibrations in acetone solvent molecules.

Vibrational spectra of a series of gas-phase metal 1+ and 2+ ions solvated by acetone molecules are collected to investigate how the metal charge, number of solvent molecules and nature of the metal affect the acetone. The spectra of Cu+(Ace)(N2)2, Cu+(Ace)4, and M2+(Ace)4, where M = Co, Ni, Cu, and Zn are measured via photodissociation by monitoring fragment ion signal as a function of IR wavenumber. The spectra show a red shift of the CO stretch and a blue shift of the C-C antisymmetric stretch. DFT calculations are carried out to provide the simulated spectra of possible isomers to be compared with the observed vibrational spectra, and specific structures are proposed. The red shift of the CO stretch increases as the number of acetone molecules decreases. Higher charge on the metal leads to a larger red shift in the CO stretch. Although all of the M2+ complexes have very similar red shifts, they are predicted to have different geometries due to their different electron configurations. Unexpectedly, we find that the calculated red shift in the CO stretch in M+/2+(Ace) is highly linearly correlated with the ionization energy of the metal for a wide range of metal cations and dications.

On the detectability of interstellar diaminomethane ((NH2)2CH2)

ABSTRACT The recent synthesis of diaminomethane ((NH2)2CH2) under simulated interstellar conditions implies that this molecule is likely present in the interstellar medium (ISM), and this work provides the highly accurate quantum chemically computed rotational constants and IR frequencies for comparison to experiment that may aid in its potential future detection. This simplest geminal diamine of prebiotic note has a transition for its ν18 fundamental frequency at 702.5 cm−1 (14.23 μm) with an intensity on level with that of the antisymmetric stretch in carbon dioxide. Additionally, its 1.72 D dipole moment for the most stable C2v conformer should make it detectable with radiotelescopes as well. The C2 conformer may also be detectable in similar regions where the C2v form is present, but only warmer or higher-energy regions will allow for possible observation of the C1 conformer. In any case, rotational constants for these other two conformers are also provided in addition to the full set of fundamental vibrational frequencies for the C2v conformer. These data will assist with further laboratory classification and possible interstellar detection of this prebiotic molecule.

Supercapacitor electrode properties of NiWO4 nanocrystals processed by thermal plasma and deposited on the FTO substrate

In this communication, nickel tungstate (NiWO4) nanocrystals were prepared using the coprecipitation method at 90 °C for 6 h and processed by thermal plasma (TP) at 600 °C for 1 h. X-ray diffraction (XRD), Rietveld refinement data, micro-Raman, and Fourier transform infrared (FT-IR) spectroscopies were employed to analyze their structure and optical data. The morphology was observed through field emission scanning electron microscopy (FE-SEM) images. Moreover, their supercapacitor electrode properties were investigated in detail. XRD patterns, Rietveld refinement, micro-Raman/FTIR spectra, and FE-SEM images confirm pristine NiWO4 nanocrystals with a monoclinic structure, symmetric and antisymmetric stretch vibrations of ONiO and OWO bonds, which are related to IR- and Raman-active vibrational modes, spherical shape with average crystal sized ~29.2 nm. These NiWO4 nanocrystals present a high specific capacitance of 351.26 F g−1 at 40 mV s−1, in comparison with NiWO4 nanocrystals processed in heat treatment conventional (120 F g−1 at 40 mV s−1), which can be applied as a stable cathodic electrode. These results suggest that NiWO4 nanocrystals processed by TP and deposited on FTO substrate are good candidates for use as electrodes for energy storage devices in the next generation of batteries.

Structure, optical, colorimetric, and supercapacitor properties of anode α-CuWO4 crystals

In this work, alpha-copper tungstate (α-CuWO4) crystals were prepared by polymeric precursor method. The structural and optical data were performed by X-ray diffraction (XRD), Rietveld refinement, Fourier-transform infrared (FTIR), and ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopies. Moreover, their colorimetric and supercapacitor properties were investigated. Pristine α-CuWO4 crystals present a triclinic structure, symmetric and antisymmetric stretch vibrations in the O–Cu–O and O–W–O bonds corresponding to IR-active modes and an optical bandgap value of 2.24 eV. Colorimetric results showed that the α-CuWO4 crystals exhibit a brown color to be employed in pigments coating floors. The α-CuWO4 crystals present a specific capacitance of 275.68F/g at 5 mV/s to be applied as a stable anodic electrode. These results suggest that α-CuWO4 is an excellent candidate as an electrode for energy storage devices in the next generation of batteries.

State-resolved studies of CO2 sticking to CO2 ice.

Internal vibrations may affect the adsorption, scattering, and reactions of molecules impinging onto a surface. The energy of the ν 3 antisymmetric stretch vibration of CO2 slightly exceeds the desorption energy of CO2 bound to CO2 ice. We use supersonic molecular beam techniques and rovibrationally state-resolved excitation to determine whether this vibration affects condensation of gas phase CO2 to its ice. We detect sticking and CO2 ice formation using RAIRS and quantify the sticking probability using the King and Wells method with modulation of the vibrational excitation and Fourier transform based detection. We find that the influence of this vibration on the structure of the formed ice and on the sticking probability is negligible under our conditions. Based on our detection limit, we quantify the weighted average sticking probability at approximately 0.9 and the difference between the state-resolved and weighted average sticking probability as below 0.03%.

Temperature Dependences of IR Spectral Bands of Humic Substances of Silicate-Based Soils

Temperature-dependent IR spectroscopy capable of revealing specific changes in the band intensities, positions, and shape was used to increase the information on humic substances (HS) from soils. Temperature dependences of IR spectra of HS isolated from silicate-based soils differing in the contents and nature of organic matter, chernozem and soddy podzolic soil, were investigated by attenuated total internal reflection FTIR in the mid-IR region (4000–400 cm−1) in the air within the moderate temperature range of 25–215 °C (298–488 K) with a step of 2.5 °C. The dependences of shifts in frequency (wavenumber) corresponding to band maxima and integrated band intensities were built for all major bands. Observed reversible frequency shifts upon heating and cooling can be interpreted as forming structures in the dry state. The behavior of integrated intensities of bands assigned to C–H and C–C vibrations, characteristic vibrations of polyaromatic compounds, carboxylic acids, and carboxylates were shown, and similar behavior for the same group (symmetric and antisymmetric stretches) were revealed. Differences in the temperature trends in chernozem and soddy podzolic soils due to different structures (aliphatic and aromatic) and functional groups (carboxylic and carboxylate) are shown. The different behavior of the bands corresponding to carboxylic groups and skeletal vibrations differentiates soil types with different organic matter. The temperature trends of band maximum and intensity shifts are less prone to measurement conditions and may serve as qualitative parameters characterizing the composition of soil humic substances.

Systematic investigation of coupling between symmetric and antisymmetric stretches of D2O in CHCl3 by 2D IR.

The coupling between the symmetric (νs) and antisymmetric (νa) OD stretch modes of monomeric D2O in CHCl3 is investigated using polarization-dependent two-dimensional infrared (2D IR) spectroscopy supported by numerical 2D IR simulations based on the exciton-band theory. The relationship between the local modes' and the exciton states' parameters is systematically studied, including center frequencies, diagonal anharmonicities, coupling, and off-diagonal anharmonicity. The mean coupling between νs and νa is accurately evaluated to be -49.96 ± 0.14cm-1. The degree of relaxation in the harmonic approximation is quantified, and the angle between the exciton-state dipoles is accurately evaluated to be 101.4° ± 3.6°. In addition, the effect of the local-mode frequency correlation on the resulting exciton-state frequency correlation and the spectral shape of the linear and 2D IR spectra are also investigated.

Direct Probing of Vibrational Interactions in UiO-66 Polycrystalline Membranes with Femtosecond Two-Dimensional Infrared Spectroscopy

UiO-66 is a benchmark metal-organic framework that holds great promise for the design of new functional materials. In this work, we perform two-dimensional infrared measurements on polycrystalline membranes of UiO-66 grown on c-sapphire substrates. We study the symmetric and antisymmetric stretch vibrations of the carboxylate groups of the terephthalate linker ions and find that these vibrations show a rapid energy exchange and a collective vibrational relaxation with a time constant of 1.3 ps. We also find that the symmetric vibration of the carboxylate group is strongly coupled to a vibration of the aromatic ring of the terephthalate ion. We observe that the antisymmetric carboxylate vibrations of different terephthalate linkers show rapid resonant (Förster) energy transfer with a time constant of ∼1 ps.

Ultraprecise relative energies in the (2 0 0) vibrational band of H2 16O

The technique of Noise-Immune Cavity Enhanced Optical Heterodyne Molecular Spectroscopy (NICE-OHMS) is employed to detect rovibrational transitions of at wavelengths of 1.4 m. This intracavity-saturation approach narrows down the typical Doppler-broadened linewidths of about 600 MHz to the sub-MHz domain. The locking of the spectroscopy laser to a frequency-comb laser and the assessment of collisional and further line broadening effects result in transition frequencies with an absolute uncertainty below 10 kHz. The lines targeted for measurement are selected by the spectroscopic-network-assisted precision spectroscopy (SNAPS) approach. The principal aim is to derive precise and accurate relative energies from a limited set of Doppler-free transitions. The 71 newly observed lines, combined with further highly accurate literature transitions, allow the determination of the relative energies for all of the 59 rovibrational states up to J = 6 within the vibrational parent of , where J is the overall rotational quantum number and , , and are quantum numbers associated with the symmetric stretch, bend, and antisymmetric stretch normal modes, respectively. An experimental curiosity of this study is that for strong transitions an apparent signal inversion in the Lamb-dip spectra is observed; a novelty reserved to the NICE-OHMS technique.

Ultrafast vibrational dynamics of aqueous acetate and terephthalate

We study the vibrational population relaxation and mutual interaction of the symmetric stretch (νs) and antisymmetric stretch (νas) vibrations of the carboxylate anion groups of acetate and terephthalate ions in aqueous solution by femtosecond two-dimensional infrared spectroscopy. By selectively exciting and probing the νs and νas vibrations, we find that the interaction of the two vibrations involves both the anharmonic coupling of the vibrations and energy exchange between the excited states of the vibrations. We find that both the vibrational population relaxation and the energy exchange are faster for terephthalate than for acetate.

Machine Learning Approach for Describing Water OH Stretch Vibrations.

A machine learning approach employing neural networks is developed to calculate the vibrational frequency shifts and transition dipole moments of the symmetric and antisymmetric OH stretch vibrations of a water molecule surrounded by water molecules. We employed the atom-centered symmetry functions (ACSFs), polynomial functions, and Gaussian-type orbital-based density vectors as descriptor functions and compared their performances in predicting vibrational frequency shifts using the trained neural networks. The ACSFs perform best in modeling the frequency shifts of the OH stretch vibration of water among the types of descriptor functions considered in this paper. However, the differences in performance among these three descriptors are not significant. We also tried a feature selection method called CUR matrix decomposition to assess the importance and leverage of the individual functions in the set of selected descriptor functions. We found that a significant number of those functions included in the set of descriptor functions give redundant information in describing the configuration of the water system. We here show that the predicted vibrational frequency shifts by trained neural networks successfully describe the solvent-solute interaction-induced fluctuations of OH stretch frequencies.

Infrared spectra of complex organic molecules in astronomically relevant ice mixtures

Context. In the near future, high spatial and spectral infrared (IR) data of star-forming regions obtained by the James Webb Space Telescope may reveal new solid-state features of various species, including more intriguing classes of chemical compounds. The identification of complex organic molecules (COMs) in the upcoming data will only be possible when laboratory IR ice spectra of these species under astronomically relevant conditions are available for comparison. For this purpose, systematic series of laboratory measurements are performed, providing high-resolution IR spectra of COMs. Here, spectra of pure methylamine (CH3NH2) and methylamine-containing ices are discussed. Aims. The work is aimed at characterizing the mid-IR (500–4000 cm−1, 20–2.5 μm) spectra of methylamine in pure and mixed ices to provide accurate spectroscopic data of vibrational bands that are most suited to trace this species in interstellar ices. Methods. Fourier transform infrared spectroscopy is used to record spectra of CH3NH2 in the pure form and mixed with H2O, CH4, and NH3, for temperatures ranging from 15 to 160 K. The IR spectra in combination with HeNe laser (632.8 nm) interference data of pure CH3NH2 ice was used to derive the IR band strengths of methylamine in pure and mixed ices. Results. The refractive index of amorphous methylamine ice at 15 K was determined as being 1.30 ± 0.01. Accurate spectroscopic information and band strength values are systematically presented for a large set of methylamine-containing ices and different temperatures. Selected bands are characterized and their use as methylamine tracers is discussed. The selected bands include the following: the CH3 antisymmetric stretch band at 2881.3 cm−1 (3.471 μm), the CH3 symmetric stretch band at 2791.9 cm−1 (3.582 μm), the CH3 antisymmetric deformation bands, at 1455.0 and 1478.6 cm−1 (6.873 and 6.761 μm), the CH3 symmetric deformation band at 1420.3 cm−1 (7.042 μm), and the CH3 rock at 1159.2 cm−1 (8.621 μm). Using the laboratory data recorded in this work and ground-based spectra of ices toward YSOs (Young Stellar Objects), upper-limits for the methylamine ice abundances are derived. In some of these YSOs, the methylamine abundance is less than 4% relative to H2O.

Cuticular Lipid Topology on Insect Body Surfaces Studied by Synchrotron Radiation FTIR ATR Microspectroscopy.

The cuticular lipid covering the integument of insects is exposed to the environment and involved in a variety of functions offered by insect body surfaces, ranging from protection against the environment, such as the control of water transpiration, the reduction of abrasive damage, and the prevention of pathogen intrusion, to the communication between insects from intraspecific to interspecific interactions. In comparison with the importance of their physiological functions, there is remarkably little information on the structure and physical property of cuticular lipids on insect body surfaces. The lipid layer on the outer exoskeleton is very thin, estimated on the order of 0.01-1 μm or less, and this has led to a lack of practical methodologies for detailed structural analyses. To fill this devoid, we have exploited the characteristics of Fourier transform infrared (FTIR) attenuated total reflection (ATR) spectroscopy, which allows us to conduct a chemical analysis on insect body surfaces and also to investigate depth-dependent structural changes. We have applied a combination of FTIR ATR microspectroscopy with IR radiation provided by a synchrotron facility to obtain in situ two-dimensional (2D) information of the cuticular lipid layer on the surface of the integument. The 2D FTIR spectra measured on the two-spotted cricket and the American cockroach show that the IR bands due to the cuticular lipid, such as CH2 symmetric and antisymmetric stretch, νa(CH2) and νs(CH2), change in intensity significantly, depending on the location of measurements. As if to keep pace with this, the bands of the amide group for the underlying cuticular layer also change in intensity significantly, although the changes are in the opposite direction; as the lipid bands increase in intensity, the amide band decreases, and vice versa. The ATR spectral analysis, which takes into account the characteristics of the evanescent wave, points out that the lipid layer would vary tens of times in the range of 0.01-1 μm significantly. The νa(CH2) and νs(CH2) bands show frequency shifts, which correlate to some extent with their intensity changes, suggesting that the drastic uneven distribution of the cuticular lipid would be related to the solid-liquid phase separation and also the coarsening of the solid phase domains. The formation of such topological features, significant heterogeneity in the lipid layer thickness, and solid-liquid phase ratios would be accompanied by the partitioning of lipid components according to molecular structures and physicochemical properties. Considering that each lipid component in insect body surface lipids is involved in various physiological roles, the segregation of lipid components during the formation of such heterogeneous structures is thought to have a significant impact on the functionality of the insect body surface.

Structures of M+(CH4)n (M = Ti, V) Based on Vibrational Spectroscopy and Density Functional Theory.

Photofragment spectroscopy is used to measure the vibrational spectra of M+(CH4)(Ar) and M+(CH4)n (M = Ti, V; n = 1-4) in the C-H stretching region (2550-3100 cm-1). Spectra were measured by monitoring the loss of Ar from M+(CH4)(Ar) and loss of CH4 from the larger clusters. The experimental spectra are then compared to simulations done at the B3LYP/6-311++G(3df,3pd) level of theory to identify the structures of the ions. The spectra all have a peak near 2800 cm-1 due to the symmetric C-H stretch of the hydrogens adjacent to the metal. Some complexes also have a smaller peak due to the corresponding antisymmetric stretch. Most complexes also have a peak near 3000 cm-1 due to the C-H stretch of hydrogens pointing away from the metal. The symmetric proximate C-H stretches of M+(CH4)(Ar) to M+(CH4)4 are red-shifted from the symmetric stretch in bare CH4 by 149, 152, 128, and 107 cm-1 for the titanium complexes and 164, 175, 158, and 146 cm-1, respectively, for the vanadium complexes. In M+(CH4)(Ar) (M = Ti, V), the heavy atoms are collinear. Ti+(CH4)(Ar) has η3 methane hydrogen coordination (∠M-C-H = 180°), while V+(CH4)(Ar) has η2 (∠M-C-H = 124°). The n = 2 complexes have C-M-C linear. Ti+(CH4)2 has C2h symmetry with η3 CH4 while V+(CH4)2 has methane coordination intermediate between η2 and η3 (∠M-C-H = 156°). Both the M+(CH4)3 (M = Ti, V) complexes have C2v symmetry with one methane farther away from the metal in an η2 binding orientation and two methanes close to the metal with a nearly η2 methane for vanadium and coordination between η2 and η3 CH4 for titanium (∠M-C-H = 150°). In Ti+(CH4)4 and V+(CH4)4 all of the methanes have η2 coordination. The titanium complex has a distorted square planar geometry with two different Ti-C bond lengths and the vanadium complex is square planar.

IR multiple photon dissociation spectroscopy of MO2 + (M = V, Nb, Ta).

A laser vaporization cluster source is coupled to the Fourier-transform ion cyclotron resonance mass spectrometer beamline of the free-electron laser for intracavity experiments. Gas phase metal ions and their oxides (VO2 +, NbO2 +, and TaO2 +) are formed and spectroscopically characterized using IR multiple-photon dissociation spectroscopy via loss of atomic oxygen and overcoming fragmentation energies of 3 eV-6 eV. The signal is observed for all MO2 + fundamental modes: the symmetric and anti-symmetric ν1 and ν3 stretch modes in the 900 cm-1-1000 cm-1 range and the ν2 bending mode in the 300 cm-1-450 cm-1 range. A remarkable substructure is observed for the bending vibration, which is at least partly due to the rovibrational substructure.

Infrared spectroscopy and anharmonic theory of H3 +Ar2,3 complexes: The role of symmetry in solvation.

The vibrational spectra of H3 +Ar2,3 and D3 +Ar2,3 are investigated in the 2000 cm-1 to 4500 cm-1 region through a combination of mass-selected infrared laser photodissociation spectroscopy and computational work including the effects of anharmonicity. In the reduced symmetry of the di-argon complex, vibrational activity is detected in the regions of both the symmetric and antisymmetric hydrogen stretching modes of H3 +. The tri-argon complex restores the D3h symmetry of the H3 + ion, with a concomitant reduction in the vibrational activity that is limited to the region of the antisymmetric stretch. Throughout these spectra, additional bands are detected beyond those predicted with harmonic vibrational theory. Anharmonic theory is able to reproduce some of the additional bands, with varying degrees of success.

Intramolecular Vibrational Energy Relaxation of CO2 in Cross-Linked Poly(ethylene glycol) Diacrylate-Based Ion Gels.

Ultrafast two-dimensional infrared spectroscopy (2D-IR) and Fourier transform infrared spectroscopy (FTIR) were used to measure carbon dioxide (CO2) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]), cross-linked low-molecular-weight poly(ethylene glycol) diacrylate (PEGDA), and an ion gel composed of a 50 vol % blend of the two. The center frequency of the antisymmetric stretch, ν3, of CO2 shifts monotonically to lower wavenumbers with increasing polymer content, with the largest line width in the ion gel (6 cm-1). Increasing polymer content slows both spectral diffusion and vibrational energy relaxation (VER) rates. An unexpected excited-state absorbance peak appears in the 2D-IR of cross-linked PEGDA due to VER from the antisymmetric stretch into the bending mode, ν2. Thirty-two response functions are necessary to describe the observed features in the 2D-IR spectra. Nonlinear least-squares fitting extracts both spectral diffusion and VER rates. In the ion gel, CO2 exhibits spectral diffusion dynamics that lie between that of the pure compounds. The kinetics of VER reflect both fast excitation and de-excitation of the bending mode, similar to the ionic liquid (IL), and slow overall vibrational population relaxation, similar to the cross-linked polymer. The IL-like and polymer-like dynamics suggest that the CO2 resides at the interface of the two components in the ion gel.

Insight into the Chemistry of PETN Under Shock Compression Through Ultrafast Broadband Mid-Infrared Absorption Spectroscopy.

Thin films of pentaerythritol tetranitrate (PETN) were shock compressed using the laser driven shock apparatus at Los Alamos National Laboratory (LANL). Two spectroscopic probes were available to this apparatus: visible white light transient absorption spectroscopy (VIS) from 400 to 700 nm and mid-infrared transient absorption spectroscopy (MIR) from 1150 to 3800 cm-1. Important PETN vibrational modes are the symmetric and antisymmetric NO2 stretches at 1280 and 1650 cm-1, respectively, as well as CH stretches at ∼2900 cm-1. Shock strength was varied from approximately 3 to 55 GPa to span from the chemically unreactive regime to the regime in which fast chemical reaction took place on the 250 ps time scale of the measurements. VIS and MIR results suggest irreversible chemistry was induced in PETN at pressures above 30 GPa. At lower shock pressures, the spectroscopy showed minimal changes attributable to pressure induced effects. Under the higher-pressure reactive conditions, the frequency region at the antisymmetric NO2 stretch mode had a significantly increased absorption while the region around the symmetric NO2 stretch did not. No observable increased absorption occurred in the higher frequency regions where CH-, NH-, and OH- bond absorptions would be observed. A broad absorption appeared on the shoulder at the red-edge of the CO2 vibrational band around 2200 cm-1. In addition to the experiments, reactive molecular dynamics were carried out under equivalent shock conditions to correlate the evolution of the infrared spectrum to molecular processes. The simulations show results consistent to experiments up to 30 GPa but suggest that NO and NO2 related features provided the strongest contributions to the shocked infrared changes. Proposed mechanisms for shocked PETN chemistry are analyzed as consistent or inconsistent with the data presented here. Our experimental data suggests C≡O or N2O bond formation, nitrite formation, and absence of significant hydroxyl or amine concentrations in the initial chemistry steps in PETN shocked above 30 GPa.