Peak pressures in thick targets generated by reduced density projectiles

Method for calculating peak pressures in thick targets impacted by hypervelocity projectiles in meteoroid damage studie

Theoretical prediction of crater size for hypervelocity impact by reduced-density particles, 18 May 1966 - 17 August 1967

Theoretical prediction of crater size in Al alloy for hypervelocity impact by reduced density particle

Evaluations of Space Shielding

A general method of evaluating the efficiency of space vehicle shielding is developed and used to compare various active and passive systems for protection against ionizing radiation. Available permanent magnets are found useless for active shielding, and combined active-passive systems in general are determined to be inefficient. On the other hand, evaluations show that active electrostatic shielding may have possibilities for weight savings if electrical conditions (presently unknown) are favorable therefor in space. Further, a positive potential improvement is calculated for an active shielding system which utilizes superconducting Nb3Sn to provide a confined magnetic flux to deflect incident charged particles; this potential points toward substantial reductions in shield weight for the protection of large vehicles from highly energetic particles. Recommendations are made for further research, particularly for flight experiments to measure directionality of solar flare protons

Photoinduced hole hopping through tryptophans in proteins

Hole hopping through tryptophan/tyrosine chains enables rapid unidirectional charge transport over long distances. We have elucidated structural and dynamical factors controlling hopping speed and efficiency in two modified azurin constructs that include a rhenium(I) sensitizer, Re(His)(CO)3(dmp)+, and one or two tryptophans (W1, W2). Experimental kinetics investigations showed that the two closely spaced (3 to 4 Å) intervening tryptophans dramatically accelerated long-range electron transfer (ET) from CuI to the photoexcited sensitizer. In our theoretical work, we found that time-dependent density-functional theory (TDDFT) quantum mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) trajectories of low-lying triplet excited states of ReI(His)(CO)3(dmp)+–W1(–W2) exhibited crossings between sensitizer-localized (*Re) and charge-separated [ReI(His)(CO)3(dmp•–)/(W1•+ or W2•+)] (CS1 or CS2) states. Our analysis revealed that the distances, angles, and mutual orientations of ET-active cofactors fluctuate in a relatively narrow range in which the cofactors are strongly coupled, enabling adiabatic ET. Water-dominated electrostatic field fluctuations bring *Re and CS1 states to a crossing where *Re(CO)3(dmp)+←W1 ET occurs, and CS1 becomes the lowest triplet state. ET is promoted by solvation dynamics around *Re(CO)3(dmp)+(W1); and CS1 is stabilized by Re(dmp•–)/W1•+ electron/hole interaction and enhanced W1•+ solvation. The second hop, W1•+←W2, is facilitated by water fluctuations near the W1/W2 unit, taking place when the electrostatic potential at W2 drops well below that at W1•+. Insufficient solvation and reorganization around W2 make W1•+←W2 ET endergonic, shifting the equilibrium toward W1•+ and decreasing the charge-separation yield. We suggest that multiscale TDDFT/MM/MD is a suitable technique to model the simultaneous evolution of photogenerated excited-state manifolds

Tryptophan to Tryptophan Hole Hopping in an Azurin Construct.

Electron transfer (ET) between neutral and cationic tryptophan residues in the azurin construct [ReI(H126)(CO)3(dmp)](W124)(W122)CuI (dmp = 4,7-Me2-1,10-phenanthroline) was investigated by Born-Oppenheimer quantum-mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) simulations. We focused on W124•+ ← W122 ET, which is the middle step of the photochemical hole-hopping process *ReII(CO)3(dmp•-) ← W124 ← W122 ← CuI, where sequential hopping amounts to nearly 10,000-fold acceleration over single-step tunneling (ACS Cent. Sci. 2019, 5, 192-200). In accordance with experiments, UKS-DFT QM/MM/MD simulations identified forward and reverse steps of W124•+ ↔ W122 ET equilibrium, as well as back ET ReI(CO)3(dmp•-) → W124•+ that restores *ReII(CO)3(dmp•-). Strong electronic coupling between the two indoles (≥40 meV in the crossing region) makes the productive W124•+ ← W122 ET adiabatic. Energies of the two redox states are driven to degeneracy by fluctuations of the electrostatic potential at the two indoles, mainly caused by water solvation, with contributions from the protein dynamics in the W122 vicinity. ET probability depends on the orientation of Re(CO)3(dmp) relative to W124 and its rotation diminishes the hopping yield. Comparison with hole hopping in natural systems reveals structural and dynamics factors that are important for designing efficient hole-hopping processes

Tuning the collapse transition of weakly charged polymers by ion specific screening and adsorption

The experimentally observed swelling and collapse response of weakly charged polymers to the addition of specific salts displays quite convoluted behavior that is not easy to categorize. Here we use a minimalistic implicit solvent / explicit salt simulation model with a focus on ion-specific interactions between ions and a single weakly charged polyelectrolyte to qualitatively explain the observed effects. In particular, we demonstrate ion-specific screening and bridging effects cause collapse at low salt concentrations whereas the same strong ion-specific direct interactions drive re-entrant swelling at high concentrations. Consistently with experiments, a distinct salt concentration at which the salting-out power of anions inverts from the reverse to direct Hofmeister series is observed. At this, so called 'isospheric point', the ion-specific effects vanish. Furthermore, with additional simplifying assumptions, an ion-specific mean-field model is developed for the collapse transition which quantitatively agrees with the simulations. Our work demonstrates the sensitivity of the structural behavior of charged polymers to the addition of specific salt and shall be useful for further guidance of experiments

Semiclassical Hybrid Approach to Condensed Phase Molecular Dynamics: Application to the I2Kr17 Cluster

We study the vibrational decoherence dynamics of an iodine molecule in a finite krypton cluster comprising the first solvation shell. A normal mode analysis allows us to successively increase the complexity of the description. For the ground state dynamics, comparison with experimental matrix results shows that already four degrees of freedom are sufficient to capture the main decoherence mechanism. For electronically excited iodine, we model the vibrational dynamics of initial Schrödinger cat-like states by the semiclassical hybrid dynamics [F. Grossmann, J. Chem. Phys. 125, 014111 (2006)] and full quantum calculations, where available. Good agreement of the results is found for a reduced model with three degrees of freedom. We find non-Gaussian distortions of the bath density matrix, which is a necessary condition, if Schrödinger cat-like states in the bath are to be identified. However, in contrast to the experiment [D. Segale et al., J. Chem. Phys. 122, 111104 (2005)], we observe only incoherent superpositions of bath vibrational states