Quantum Communications at NASA Space Communication & Navigation (SCaN)
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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Insights and Observations From Operating A Geostationary Laser Communication Relay Mission: Operational Lessons From NASA’S Laser Communications Relay Demonstration and Associated Optical Ground Stations
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Laser Communications↗
Intersubunit communication in the dihydroorotase-aspartate transcarbamoylase complex of Aquifex aeolicus : Intersubunit Communication in a Pyrimidine Biosynthetic Complex
Aspartate transcarbamoylase and dihydroorotase, enzymes that catalyze the second and third step in de novo pyrimidine biosynthesis, are associated in dodecameric complexes in Aquifex aeolicus and many other organisms. The architecture of the dodecamer is ideally suited to channel the intermediate, carbamoyl aspartate from its site of synthesis on the ATC subunit to the active site of DHO, which catalyzes the next step in the pathway, because both reactions occur within a large, internal solvent-filled cavity. Channeling usually requires that the reactions of the enzymes are coordinated so that the rate of synthesis of the intermediate matches its rate of utilization. The linkage between the ATC and DHO subunits was demonstrated by showing that the binding of the bisubstrate analog, N-phosphonacetyl-L-aspartate to the ATC subunit inhibits the activity of the distal DHO subunit. Structural studies identified a DHO loop, loop A, interdigitating between the ATC domains that would be expected to interfere with domain closure essential for ATC catalysis. Mutation of the DHO residues in loop A that penetrate deeply between the two ATC domains inhibits the ATC activity by interfering with the normal reciprocal linkage between the two enzymes. Moreover, a synthetic peptide that mimics that part of the DHO loop that binds between the two ATC domains was found to be an allosteric or noncompletive ATC inhibitor (K i = 22 μM). A model is proposed suggesting that loop A is an important component of the functional linkage between the enzymes.
Evans, Hedeel Guy↗
Communication: Ultraviolet photodissociation dynamics of the simplest Criegee intermediate CH{sub 2}OO
The velocity and angular distributions of O {sup 1}D photofragments arising from UV excitation of the CH{sub 2}OO intermediate on the B {sup 1}A′←X {sup 1}A′ transition are characterized using velocity map ion imaging. The anisotropic angular distribution yields the orientation of the transition dipole moment, which reflects the π*←π character of the electronic transition associated with the COO group. The total kinetic energy release distributions obtained at several photolysis wavelengths provide detail on the internal energy distribution of the formaldehyde cofragments and the dissociation energy of CH{sub 2}OO X {sup 1}A′ to O {sup 1}D + H{sub 2}CO X {sup 1}A{sub 1}. A common termination of the total kinetic energy distributions, after accounting for the different excitation energies, gives an upper limit for the CH{sub 2}OO X {sup 1}A′ dissociation energy of D{sub 0}≤ 54 kcal mol{sup −1}, which is compared with theoretical predictions including high level multi-reference ab initio calculations.
74 ATOMIC AND MOLECULAR PHYSICS↗
Communication: Helium nanodroplet isolation and rovibrational spectroscopy of hydroxymethylene
Hydroxymethylene (HCOH) and its d{sub 1}-isotopologue (HCOD) are isolated in low temperature helium nanodroplets following pyrolysis of glyoxylic acid. Transitions identified in the infrared spectrum are assigned exclusively to the trans-conformation based on previously reported anharmonic frequency computations [P. R. Schreiner, H. P. Reisenauer, F. C. Pickard, A. C. Simmonett, W. D. Allen, E. Mátyus, and A. G. Császár, Nature 453, 906 (2008); L. Koziol, Y. M. Wang, B. J. Braams, J. M. Bowman, and A. I. Krylov, J. Chem. Phys. 128, 204310 (2008)]. For the OH(D) and CH stretches, a- and b-type transitions are observed, and when taken in conjunction with CCSD(T)/cc-pVTZ computations, lower limits to the vibrational band origins are determined. The relative intensities of the a- and b-type transitions provide the orientation of the transition dipole moment in the inertial frame. The He nanodroplet data are in excellent agreement with anharmonic frequency computations reported here and elsewhere, confirming an appreciable Ar-matrix shift of the OH and OD stretches and strong anharmonic resonance interactions in the high-frequency stretch regions of the mid-infrared.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: The description of strong correlation within self-consistent Green's function second-order perturbation theory
We report an implementation of self-consistent Green's function many-body theory within a second-order approximation (GF2) for application with molecular systems. This is done by iterative solution of the Dyson equation expressed in matrix form in an atomic orbital basis, where the Green's function and self-energy are built on the imaginary frequency and imaginary time domain, respectively, and fast Fourier transform is used to efficiently transform these quantities as needed. We apply this method to several archetypical examples of strong correlation, such as a H{sub 32} finite lattice that displays a highly multireference electronic ground state even at equilibrium lattice spacing. In all cases, GF2 gives a physically meaningful description of the metal to insulator transition in these systems, without resorting to spin-symmetry breaking. Our results show that self-consistent Green's function many-body theory offers a viable route to describing strong correlations while remaining within a computationally tractable single-particle formalism.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Modeling charge-sign asymmetric solvation free energies with nonlinear boundary conditions
We show that charge-sign-dependent asymmetric hydration can be modeled accurately using linear Poisson theory after replacing the standard electric-displacement boundary condition with a simple nonlinear boundary condition. Using a single multiplicative scaling factor to determine atomic radii from molecular dynamics Lennard-Jones parameters, the new model accurately reproduces MD free-energy calculations of hydration asymmetries for: (i) monatomic ions, (ii) titratable amino acids in both their protonated and unprotonated states, and (iii) the Mobley “bracelet” and “rod” test problems [D. L. Mobley, A. E. Barber II, C. J. Fennell, and K. A. Dill, “Charge asymmetries in hydration of polar solutes,” J. Phys. Chem. B 112, 2405–2414 (2008)]. Remarkably, the model also justifies the use of linear response expressions for charging free energies. Our boundary-element method implementation demonstrates the ease with which other continuum-electrostatic solvers can be extended to include asymmetry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Energy-dependent resonance broadening in symmetric and asymmetric molecular junctions from an ab initio non-equilibrium Green's function approach
The electronic structure of organic-inorganic interfaces often features resonances originating from discrete molecular orbitals coupled to continuum lead states. An example is molecular junction, individual molecules bridging electrodes, where the shape and peak energy of such resonances dictate junction conductance, thermopower, I-V characteristics, and related transport properties. In molecular junctions where off-resonance coherent tunneling dominates transport, resonance peaks in the transmission function are often assumed to be Lorentzian functions with an energy-independent broadening parameter Γ. Here we define a new energy-dependent resonance broadening function, Γ(E), based on diagonalization of non-Hermitian matrices, which can describe resonances of a more complex, non-Lorentzian nature and can be decomposed into components associated with the left and right leads, respectively. We compute this quantity via an ab initio non-equilibrium Green's function (NEGF) approach based on density functional theory (DFT) for both symmetric and asymmetric molecular junctions, and show that our definition of Γ(E), when combined with Breit-Wigner formula, reproduces the transmission calculated from DFT-NEGF. Through a series of examples, we illustrate how this approach can shed new light on experiments and understanding of junction transport properties in terms of molecular orbitals.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Towards first principles theory of relaxation in supercooled liquids formulated in terms of cooperative motion
A general theory of the long time, low temperature dynamics of glass-forming fluids remains elusive despite the almost 20 years since the famous pronouncement by the Nobel Laureate P. W. Anderson, “The deepest and most interesting unsolved problem in solid state theory is probably the theory of the nature of glass and the glass transition” [Science 267, 1615 (1995)]. While recent work indicates that Adam-Gibbs theory (AGT) provides a framework for computing the structural relaxation time of supercooled fluids and for analyzing the properties of the cooperatively rearranging dynamical strings observed in low temperature molecular dynamics simulations, the heuristic nature of AGT has impeded general acceptance due to the lack of a first principles derivation [G. Adam and J. H. Gibbs, J. Chem. Phys. 43, 139 (1965)]. This deficiency is rectified here by a statistical mechanical derivation of AGT that uses transition state theory and the assumption that the transition state is composed of elementary excitations of a string-like form. The strings are assumed to form in equilibrium with the mobile particles in the fluid. Hence, transition state theory requires the strings to be in mutual equilibrium and thus to have the size distribution of a self-assembling system, in accord with the simulations and analyses of Douglas and co-workers. The average relaxation rate is computed as a grand canonical ensemble average over all string sizes, and use of the previously determined relation between configurational entropy and the average cluster size in several model equilibrium self-associating systems produces the AGT expression in a manner enabling further extensions and more fundamental tests of the assumptions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Dominance of extreme statistics in a prototype many-body Brownian ratchet
Many forms of cell motility rely on Brownian ratchet mechanisms that involve multiple stochastic processes. We present a computational and theoretical study of the nonequilibrium statistical dynamics of such a many-body ratchet, in the specific form of a growing polymer gel that pushes a diffusing obstacle. We find that oft-neglected correlations among constituent filaments impact steady-state kinetics and significantly deplete the gel's density within molecular distances of its leading edge. These behaviors are captured quantitatively by a self-consistent theory for extreme fluctuations in filaments' spatial distribution.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: On the stability of ice 0, ice i, and I h
Using ab initio methods, we examine the stability of ice 0, a recently proposed tetragonal form of ice implicated in the homogeneous freezing of water [J. Russo, F. Romano, and H. Tanaka, Nat. Mater. 13, 670 (2014)]. Vibrational frequencies are computed across the complete Brillouin Zone using Density Functional Theory (DFT), to confirm mechanical stability and quantify the free energy of ice 0 relative to ice I h . The robustness of this result is tested via dispersion corrected semi-local and hybrid DFT, and Quantum Monte-Carlo calculation of lattice energies. Results indicate that popular molecular models only slightly overestimate the stability of ice zero. In addition, we study all possible realisations of proton disorder within the ice zero unit cell, and identify the ground state as ferroelectric. Comparisons are made to other low density metastable forms of ice, suggesting that the ice i structure [C. J. Fennel and J. D. Gezelter, J. Chem. Theory Comput. 1, 662 (2005)] may be equally relevant to ice formation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Active space decomposition with multiple sites: Density matrix renormalization group algorithm
We extend the active space decomposition method, recently developed by us, to more than two active sites using the density matrix renormalization group algorithm. The fragment wave functions are described by complete or restricted active-space wave functions. Numerical results are shown on a benzene pentamer and a perylene diimide trimer. It is found that the truncation errors in our method decrease almost exponentially with respect to the number of renormalization states M, allowing for numerically exact calculations (to a few μE{sub h} or less) with M = 128 in both cases. This rapid convergence is because the renormalization steps are used only for the interfragment electron correlation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Theoretical prediction of free-energy landscapes for complex self-assembly
We present a technique for calculating free-energy profiles for the nucleation of multicomponent structures that contain as many species as building blocks. We find that a key factor is the topology of the graph describing the connectivity of the target assembly. By considering the designed interactions separately from weaker, incidental interactions, our approach yields predictions for the equilibrium yield and nucleation barriers. These predictions are in good agreement with corresponding Monte Carlo simulations. We show that a few fundamental properties of the connectivity graph determine the most prominent features of the assembly thermodynamics. Surprisingly, we find that polydispersity in the strengths of the designed interactions stabilizes intermediate structures and can be used to sculpt the free-energy landscape for self-assembly. Finally, we demonstrate that weak incidental interactions can preclude assembly at equilibrium due to the combinatorial possibilities for incorrect association.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Automatic code generation enables nuclear gradient computations for fully internally contracted multireference theory
Analytical nuclear gradients for fully internally contracted complete active space second-order perturbation theory (CASPT2) are reported. This implementation has been realized by an automated code generator that can handle spin-free formulas for the CASPT2 energy and its derivatives with respect to variations of molecular orbitals and reference coefficients. The underlying complete active space self-consistent field and the so-called Z-vector equations are solved using density fitting. The implementation has been applied to the vertical and adiabatic ionization potentials of the porphin molecule to illustrate its capability.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Water on hexagonal boron nitride from diffusion Monte Carlo
Despite a recent flurry of experimental and simulation studies, an accurate estimate of the interaction strength of water molecules with hexagonal boron nitride is lacking. Here, we report quantum Monte Carlo results for the adsorption of a water monomer on a periodic hexagonal boron nitride sheet, which yield a water monomer interaction energy of −84 ± 5 meV. We use the results to evaluate the performance of several widely used density functional theory (DFT) exchange correlation functionals and find that they all deviate substantially. Differences in interaction energies between different adsorption sites are however better reproduced by DFT.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: State-to-state dynamics of the Cl + H{sub 2}O → HCl + OH reaction: Energy flow into reaction coordinate and transition-state control of product energy disposal
Quantum state-to-state dynamics of a prototypical four-atom reaction, namely, Cl + H{sub 2}O → HCl + OH, is investigated for the first time in full dimensionality using a transition-state wave packet method. The state-to-state reactivity and its dependence on the reactant internal excitations are analyzed and found to share many similarities both energetically and dynamically with the H + H{sub 2}O → H{sub 2} + OH reaction. The strong enhancement of reactivity by the H{sub 2}O stretching vibrational excitations in both reactions is attributed to the favorable energy flow into the reaction coordinate near the transition state. On the other hand, the insensitivity of the product state distributions with regard to reactant internal excitation stems apparently from the transition-state control of product energy disposal.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Classical threshold law for ion-neutral-neutral three-body recombination
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Pérez-Ríos, Jesús↗