Martin Losada

Water hexamer clusters: Structures, energies, and predicted mid-infrared spectra

We present an ab initio theoretical study of five low-energy isomers of the water hexamer {Chair, Cage(du)[1], Book, Prism, and Boat}, their intramolecular vibrations, binding energies De and dissociation energies D0. Moller–Plesset second order perturbation calculations using the aug-cc-pVTZ basis set at aug-cc-pVDZ optimized geometries including vibrational zero point energy corrections predict Chair to be the most stable isomer, followed closely by Cage(du)[1] (+0.02 kcal/mol) and Book (+0.05 kcal/mol), while Prism is 0.15 kcal/mol higher. The Boat conformer is least stable at both the De and D0 levels. The main focus is on the intramolecular normal modes of the five isomers. The calculated O–H stretching frequencies and intensities are compared to recent infrared spectra of water hexamer in supersonic jets, liquid-helium droplets and solid para-hydrogen matrices. The IR spectra indicate that Book and Chair are major species in the latter two environments and may also exist in supersonic jets. The (H2O...

Solvation of Propylene Oxide in Water: Vibrational Circular Dichroism, Optical Rotation, and Computer Simulation Studies

The solvation of propylene oxide (PO) in water has been studied using vibrational circular dichroism (VCD) spectroscopy, optical rotation dispersion (ORD) spectroscopy, molecular dynamics simulations, and ab initio calculations. VCD and ORD measurements were carried out for PO as neat liquid, in CCl4, and in water solutions. The classical molecular dynamics simulations were carried out for the PO + water binary mixtures at different concentrations, and the solvation information was derived from the radial distribution functions obtained in the simulations. The total number of water molecules within the closest vicinity of PO was predicted to be about 3. The geometry optimizations, vibrational frequencies, and VCD intensities were evaluated for the PO monomer and the PO-(H2O)n clusters with n = 1-3 , using density functional theory calculations at the B3LYP/aug-cc-pVTZ level of theory. The chirality transfer VCD feature, which is a direct result of the explicit H-bonding between water and the chiral PO solute, was detected experimentally at the water bending band region. This feature exhibits high sensitivity to the solvation structure around PO. Comparison of the calculated and experimental chirality transfer features leads to the conclusion that the PO-water binary complex is the dominating species in aqueous solution at room temperature and the anti conformation, where water is on the opposite side of the oxirane ring of the PO methyl group, is preferred over the syn one. This conclusion is also supported by the complementary ORD studies. Possible contributions from the ternary and quaternary PO-water complexes are also discussed.

Theoretical study of elementary steps in the reactions between aluminum and teflon fragments under combustive environments.

Gas-phase reactions between aluminum particles and Teflon fragments were studied to develop a fundamental understanding of the decomposition reactions and combustion processes of the Al-Teflon composites. The reactions were investigated theoretically using ab initio calculations at the MP2/aug-cc-pVDZ level, with the final thermokinetic data obtained with coupled cluster theory (CCSD(T)/aug-cc-pVTZ). Among reactions under oxygen-lean conditions, CF(3) + Al --> CF(2) + AlF channel is the fastest, followed by the CF(2) + Al --> CF + AlF and CF + Al --> C + AlF channels. Under oxygen-rich conditions, reactions of COF with aluminum are probed to be faster than those involving COF(2) species. Reaction path multiplicity has been considered. Our results show that multiplicity plays a very important role in determining the reaction order, that is first order or addition-elimination reactions of Al with CF(3) are predicted to be faster than those proceeding through direct abstraction or second order. In addition, the present kinetic model suggests that CF(3) + Al --> CF(2) + AlF with m = 1 and COF + Al --> CO + AlF channels are very competitive under the same thermal conditions. The computed enthalpies of reaction are systematically compared with the available literature. The predicted kinetic model and its time constants (tau) are in good qualitative agreement with experimental observations of the reactions between Al nanoparticles and Teflon for the 500-1200 K temperature range.

Finite size effects on aluminum/Teflon reaction channels under combustive environment: A Rice–Ramsperger–Kassel–Marcus and transition state theory study of fluorination

The effect of particle size on combustion efficiency is an important factor in combustion research. Gas-phase aluminum clusters in oxidizing environment constitute a relatively simple and extensively studied system. In an attempt to underscore the correlation between electronic structure, finite size effect, and reactivity in small aluminum clusters, reactions between aluminum, [Al(13)](-) cluster, and Teflon decomposition fragments were studied using theoretical calculations at the density functional theoretical level. The unimolecular rate constants calculated using transition state and Rice-Ramsperger-Kassel-Marcus theory show that reactions with COF and CF(2) species with aluminum are faster than those involving CF(3) and COF(2). The results show that the kinetic barriers along different exothermic reaction channels correlate with the trends in HOMO(R)-HOMO(TS) (HOMO denotes highest occupied molecular orbital) energy gap and related shifts of the HOMO levels of reactants. Overall reactions involving carbonyl fluoride species (COF and COF(2)) lead to CO elimination and fluorination of the Al cluster. The CF(3)/CF(2) fragments lead to stable multicenter Al-C bond formation on the fluorinated Al cluster surface. Temperature-, energy-, and pressure-dependent rate constants are provided for extrapolating the expected reaction kinetics to conditions similar to known combustion reactions.

O–H flipping vibrations of the Cage water hexamer: An ab initio study

In the Cage[1] isomer of the water hexamer, the free O–H bonds of the two end-cap water molecules can flip between “up” (u) and “down” (d) orientations, giving four conformers denoted uu, ud, du, and dd. Using the Moller–Plesset second order perturbation method and large basis sets, we calculate fully relaxed potential energy curves as a function of both u↔d torsional angles, denoted φ1, φ2. These predict du as the lowest conformer, with uu nearly degenerate and ud and dd at 30–40 and 50–70 cm−1 higher energy, respectively. Along φ1 the torsional barriers are about 200 cm−1, along φ2 between 80 and 110 cm−1. The torsional zero-point energies are high, the vibrational ground states are strongly delocalized and averaging of the cluster properties is important along both φ1 and φ2. The dipole moment components vary strongly along both φ1 and φ2: μa changes from +0.8 to +2.2 D, μb from +0.5 to +1.2 D, and μc from +1.4 to −0.9 D. The φ2 torsional fundamental of (H2O)6 is predicted in the range 65–72 cm−1 with ...

Intermolecular Energy Transfer Dynamics at a Hot-Spot Interface in RDX Crystals.

The phonon mediated vibrational up-pumping mechanisms assume an intact lattice and climbing of a vibrational ladder using strongly correlated multiphonon dynamics under equilibrium or near-equilibrium conditions. Important dynamic processes far from-equilibrium in regions of large temperature gradient after the onset of decomposition reactions in energetic solids are relatively unknown. In this work, we present a classical molecular dynamics (MD) simulation-based study of such processes using a nonreactive and a reactive potential to study a fully reacted and unreacted zone in RDX (1,3,5-trinitro-1,3,5-triazocyclohexane) crystal under nonequilibrium conditions. The energy transfer rate is evaluated as a function of temperature difference between the reacted and unreacted regions, and for different widths and cross-sectional area of unreacted RDX layers. Vibrational up-pumping processes probed using velocity autocorrelation functions indicate that the mechanisms at high-temperature interfaces are quite different from the standard phonon-based models proposed in current literature. In particular, the up-pumping of high-frequency vibrations are seen in the presence of small molecule collisions at the hot-spot interface with strong contributions from bending modes. It also explains some major difference in the order of decomposition of C-N and N-N bonds as seen in recent literature on initiation chemistry.

Linking molecular level chemistry to macroscopic combustion behavior for nano-energetic materials with halogen containing oxides

Coupling molecular scale reaction kinetics with macroscopic combustion behavior is critical to understanding the influences of intermediate chemistry on energy propagation, yet bridging this multi-scale gap is challenging. This study integrates ab initio quantum chemical calculations and condensed phase density functional theory to elucidate factors contributing to experimentally measured high flame speeds (i.e., >900 m∕s) associated with halogen based energetic composites, such as aluminum (Al) and iodine pentoxide (I2O5). Experiments show a direct correlation between apparent activation energy and flame speed suggesting that flame speed is directly influenced by chemical kinetics. Toward this end, the first principle simulations resolve key exothermic surface and intermediate chemistries contributing toward the kinetics that promote high flame speeds. Linking molecular level exothermicity to macroscopic experimental investigations provides insight into the unique role of the alumina oxide shell passivating aluminum particles. In the case of Al reacting with I2O5, the alumina shell promotes exothermic surface chemistries that reduce activation energy and increase flame speed. This finding is in contrast to Al reaction with metal oxides that show the alumina shell does not participate exothermically in the reaction.

Understanding Nanoscale Wetting Using Dynamic Local Contact Angle Method

A multiscale quantum/classical-framework for hydrophobicity and UV absorption in heterogeneous coatings is presented. Atomistic water droplet simulations on coated oxide surface are used to define nanoscale contact-angles using a new numerical technique called the dynamic local contact angle (DLCA) method. The DLCA method is well suited to calculate macroscopic contact angles for polymeric and composite coatings. The accuracy of the method is tested for a series of common polymers and composites. In addition, the sensitivity of the contact angles towards functional groups and nanoscale roughness are tested using varying molecular structures. Fluorinated polyhedral oligomericsilsesquioxanes (F-POSS) molecular frameworks are used as a model system. Changes in contact angle and UV absorption spectrum as a function of hydrophobic chain length are calculated to test the feasibility of developing a virtual framework for new coating design connecting atomistic calculations to continuum level material properties.

Transport in aluminized RDX under shock compression explored using molecular dynamics simulations

Shock response of energetic materials is controlled by a combination of mechanical response, thermal, transport, and chemical properties. How these properties interplay in condensed-phase energetic materials is of fundamental interest for improving predictive capabilities. Due to unknown nature of chemistry during the evolution and growth of high-temperature regions within the energetic material (so called hot spots), the connection between reactive and unreactive equations of state contain a high degree of empiricism. In particular, chemistry in materials with high degree of heterogeneity such as aluminized HE is of interest. In order to identify shock compression states and transport properties in high-pressure/temperature (HP-HT) conditions, we use molecular dynamics (MD) simulations in conjunction with the multi-scale shock technique (MSST). Mean square displacement calculations enabled us to track the diffusivity of stable gas products. Among decomposition products, H2O and CO2 are found to be the dominant diffusing species under compression conditions. Heat transport and diffusion rates in decomposed RDX are compared and the comparison shows that around 2000 K, transport can be a major contribution during propagation of the reaction front.