Pulsed-field ionization zero electron kinetic energy spectrum of the ground electronic state of BeOBe+.

PubMed

Antonov, Ivan O; Barker, Beau J; Heaven, Michael C

2011-01-28

The ground electronic state of BeOBe(+) was probed using the pulsed-field ionization zero electron kinetic energy photoelectron technique. Spectra were rotationally resolved and transitions to the zero-point level, the symmetric stretch fundamental and first two bending vibrational levels were observed. The rotational state symmetry selection rules confirm that the ground electronic state of the cation is (2)Σ(g)(+). Detachment of an electron from the HOMO of neutral BeOBe results in little change in the vibrational or rotational constants, indicating that this orbital is nonbonding in nature. The ionization energy of BeOBe [65480(4) cm(-1)] was refined over previous measurements. Results from recent theoretical calculations for BeOBe(+) (multireference configuration interaction) were found to be in good agreement with the experimental data.

The ground state tunneling splitting and the zero point energy of malonaldehyde: a quantum Monte Carlo determination.

PubMed

Viel, Alexandra; Coutinho-Neto, Maurício D; Manthe, Uwe

2007-01-14

Quantum dynamics calculations of the ground state tunneling splitting and of the zero point energy of malonaldehyde on the full dimensional potential energy surface proposed by Yagi et al. [J. Chem. Phys. 1154, 10647 (2001)] are reported. The exact diffusion Monte Carlo and the projection operator imaginary time spectral evolution methods are used to compute accurate benchmark results for this 21-dimensional ab initio potential energy surface. A tunneling splitting of 25.7+/-0.3 cm-1 is obtained, and the vibrational ground state energy is found to be 15 122+/-4 cm-1. Isotopic substitution of the tunneling hydrogen modifies the tunneling splitting down to 3.21+/-0.09 cm-1 and the vibrational ground state energy to 14 385+/-2 cm-1. The computed tunneling splittings are slightly higher than the experimental values as expected from the potential energy surface which slightly underestimates the barrier height, and they are slightly lower than the results from the instanton theory obtained using the same potential energy surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoobler, Preston Reece; Turney, Justin Matthew; Schaefer III, Henry

The n-propylperoxy radical has been described as a molecule of critical importance to studies of low temperature combustion. Ab initio methods were used to study this three-carbon alkylperoxy radical, normal propylperoxy. Reliable CCSD(T)/ANO0 geometries were predicted for the molecule's five rotamers. For each rotamer, energetic predictions were made using basis sets as large as the cc-pV5Z in conjunction with coupled cluster levels of theory up to CCSDT(Q). Along with the extrapolations, corrections for relativistic effects, zero-point vibrational energies, and diagonal Born--Oppenheimer corrections were used to further refine energies. The results indicate that the lowest conformer is the gauche-gauche (GG) rotamermore » followed by the gauche-trans (0.12 kcal mol^-1 above GG), trans-gauche (0.44 kcal mol^-1), gauche'-gauche (0.47 kcal mol^-1), and trans-trans (0.57 kcal mol^-1). Fundamental vibrational frequencies were obtained using second-order vibrational perturbation theory (VPT2). This is the first time anharmonic frequencies have been computed for this system. The most intense IR features include all but one of the C-H stretches. The O-O fundamental (1063 cm^-1 for the GG structure) also has a significant IR intensity, 19.6 km mol^-1. The anharmonicity effects on the potential energy surface were also used to compute vibrationally averaged r_g,0 K bond lengths, accounting for zero-point vibrations present within the molecule.« less

Using an internal coordinate Gaussian basis and a space-fixed Cartesian coordinate kinetic energy operator to compute a vibrational spectrum with rectangular collocation.

PubMed

Manzhos, Sergei; Carrington, Tucker

2016-12-14

We demonstrate that it is possible to use basis functions that depend on curvilinear internal coordinates to compute vibrational energy levels without deriving a kinetic energy operator (KEO) and without numerically computing coefficients of a KEO. This is done by using a space-fixed KEO and computing KEO matrix elements numerically. Whenever one has an excellent basis, more accurate solutions to the Schrödinger equation can be obtained by computing the KEO, potential, and overlap matrix elements numerically. Using a Gaussian basis and bond coordinates, we compute vibrational energy levels of formaldehyde. We show, for the first time, that it is possible with a Gaussian basis to solve a six-dimensional vibrational Schrödinger equation. For the zero-point energy (ZPE) and the lowest 50 vibrational transitions of H 2 CO, we obtain a mean absolute error of less than 1 cm -1 ; with 200 000 collocation points and 40 000 basis functions, most errors are less than 0.4 cm -1 .

Using an internal coordinate Gaussian basis and a space-fixed Cartesian coordinate kinetic energy operator to compute a vibrational spectrum with rectangular collocation

NASA Astrophysics Data System (ADS)

Manzhos, Sergei; Carrington, Tucker

2016-12-01

We demonstrate that it is possible to use basis functions that depend on curvilinear internal coordinates to compute vibrational energy levels without deriving a kinetic energy operator (KEO) and without numerically computing coefficients of a KEO. This is done by using a space-fixed KEO and computing KEO matrix elements numerically. Whenever one has an excellent basis, more accurate solutions to the Schrödinger equation can be obtained by computing the KEO, potential, and overlap matrix elements numerically. Using a Gaussian basis and bond coordinates, we compute vibrational energy levels of formaldehyde. We show, for the first time, that it is possible with a Gaussian basis to solve a six-dimensional vibrational Schrödinger equation. For the zero-point energy (ZPE) and the lowest 50 vibrational transitions of H2CO, we obtain a mean absolute error of less than 1 cm-1; with 200 000 collocation points and 40 000 basis functions, most errors are less than 0.4 cm-1.

Zero-point energy effects in anion solvation shells.

PubMed

Habershon, Scott

2014-05-21

By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

Uncertainties in scaling factors for ab initio vibrational zero-point energies

NASA Astrophysics Data System (ADS)

Irikura, Karl K.; Johnson, Russell D.; Kacker, Raghu N.; Kessel, Rüdiger

2009-03-01

Vibrational zero-point energies (ZPEs) determined from ab initio calculations are often scaled by empirical factors. An empirical scaling factor partially compensates for the effects arising from vibrational anharmonicity and incomplete treatment of electron correlation. These effects are not random but are systematic. We report scaling factors for 32 combinations of theory and basis set, intended for predicting ZPEs from computed harmonic frequencies. An empirical scaling factor carries uncertainty. We quantify and report, for the first time, the uncertainties associated with scaling factors for ZPE. The uncertainties are larger than generally acknowledged; the scaling factors have only two significant digits. For example, the scaling factor for B3LYP/6-31G(d) is 0.9757±0.0224 (standard uncertainty). The uncertainties in the scaling factors lead to corresponding uncertainties in predicted ZPEs. The proposed method for quantifying the uncertainties associated with scaling factors is based upon the Guide to the Expression of Uncertainty in Measurement, published by the International Organization for Standardization. We also present a new reference set of 60 diatomic and 15 polyatomic "experimental" ZPEs that includes estimated uncertainties.

Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

NASA Astrophysics Data System (ADS)

Han, Huixian; Li, Anyang; Guo, Hua

2014-12-01

A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) electronic state has been constructed by fitting ˜37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm-1. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm-1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

Effect of transverse vibrations of fissile nuclei on the angular and spin distributions of low-energy fission fragments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bunakov, V. E.; Kadmensky, S. G., E-mail: kadmensky@phys.vsu.ru; Lyubashevsky, D. E.

2016-05-15

It is shown that A. Bohr’s classic theory of angular distributions of fragments originating from low-energy fission should be supplemented with quantum corrections based on the involvement of a superposition of a very large number of angular momenta L{sub m} in the description of the relative motion of fragments flying apart along the straight line coincidentwith the symmetry axis. It is revealed that quantum zero-point wriggling-type vibrations of the fissile system in the vicinity of its scission point are a source of these angular momenta and of high fragment spins observed experimentally.

Investigating the ground-state rotamers of n-propylperoxy radical.

PubMed

Hoobler, Preston R; Turney, Justin M; Schaefer, Henry F

2016-11-07

The n-propylperoxy radical has been described as a molecule of critical importance to studies of low temperature combustion. Ab initio methods were used to study this three-carbon alkylperoxy radical, normal propylperoxy. Reliable CCSD(T) (coupled-cluster theory, incorporating single, double, and perturbative triple)/ANO0 geometries were predicted for the molecule's five rotamers. For each rotamer, energetic predictions were made using basis sets as large as the cc-pV5Z in conjunction with coupled cluster levels of theory up to CCSDT(Q). Along with the extrapolations, corrections for relativistic effects, zero-point vibrational energies, and diagonal Born-Oppenheimer corrections were used to further refine energies. The results indicate that the lowest conformer is the gauche-gauche (GG) rotamer followed by the gauche-trans (0.12 kcal mol -1 above GG), trans-gauche (0.44 kcal mol -1 ), gauche'-gauche (0.47 kcal mol -1 ), and trans-trans (0.57 kcal mol -1 ). Fundamental vibrational frequencies were obtained using second-order vibrational perturbation theory. This is the first time anharmonic frequencies have been computed for this system. The most intense IR features include all but one of the C-H stretches. The O-O fundamental (1063 cm -1 for the GG structure) also has a significant IR intensity, 19.6 km mol -1 . The anharmonicity effects on the potential energy surface were also used to compute vibrationally averaged r g,0K bond lengths, accounting for zero-point vibrations present within the molecule.

Investigating the Ground-State Rotamers of n-Propylperoxy Radical

DOE PAGES

Hoobler, Preston Reece; Turney, Justin Matthew; Schaefer III, Henry

2016-11-01

The n-propylperoxy radical has been described as a molecule of critical importance to studies of low temperature combustion. Ab initio methods were used to study this three-carbon alkylperoxy radical, normal propylperoxy. Reliable CCSD(T)/ANO0 geometries were predicted for the molecule's five rotamers. For each rotamer, energetic predictions were made using basis sets as large as the cc-pV5Z in conjunction with coupled cluster levels of theory up to CCSDT(Q). Along with the extrapolations, corrections for relativistic effects, zero-point vibrational energies, and diagonal Born--Oppenheimer corrections were used to further refine energies. The results indicate that the lowest conformer is the gauche-gauche (GG) rotamermore » followed by the gauche-trans (0.12 kcal mol^-1 above GG), trans-gauche (0.44 kcal mol^-1), gauche'-gauche (0.47 kcal mol^-1), and trans-trans (0.57 kcal mol^-1). Fundamental vibrational frequencies were obtained using second-order vibrational perturbation theory (VPT2). This is the first time anharmonic frequencies have been computed for this system. The most intense IR features include all but one of the C-H stretches. The O-O fundamental (1063 cm^-1 for the GG structure) also has a significant IR intensity, 19.6 km mol^-1. The anharmonicity effects on the potential energy surface were also used to compute vibrationally averaged r_g,0 K bond lengths, accounting for zero-point vibrations present within the molecule.« less

Investigating the ground-state rotamers of n-propylperoxy radical

NASA Astrophysics Data System (ADS)

Hoobler, Preston R.; Turney, Justin M.; Schaefer, Henry F.

2016-11-01

The n-propylperoxy radical has been described as a molecule of critical importance to studies of low temperature combustion. Ab initio methods were used to study this three-carbon alkylperoxy radical, normal propylperoxy. Reliable CCSD(T) (coupled-cluster theory, incorporating single, double, and perturbative triple)/ANO0 geometries were predicted for the molecule's five rotamers. For each rotamer, energetic predictions were made using basis sets as large as the cc-pV5Z in conjunction with coupled cluster levels of theory up to CCSDT(Q). Along with the extrapolations, corrections for relativistic effects, zero-point vibrational energies, and diagonal Born-Oppenheimer corrections were used to further refine energies. The results indicate that the lowest conformer is the gauche-gauche (GG) rotamer followed by the gauche-trans (0.12 kcal mol-1 above GG), trans-gauche (0.44 kcal mol-1), gauche'-gauche (0.47 kcal mol-1), and trans-trans (0.57 kcal mol-1). Fundamental vibrational frequencies were obtained using second-order vibrational perturbation theory. This is the first time anharmonic frequencies have been computed for this system. The most intense IR features include all but one of the C-H stretches. The O-O fundamental (1063 cm-1 for the GG structure) also has a significant IR intensity, 19.6 km mol-1. The anharmonicity effects on the potential energy surface were also used to compute vibrationally averaged rg,0K bond lengths, accounting for zero-point vibrations present within the molecule.

Full-dimensional quantum calculations of the dissociation energy, zero-point, and 10 K properties of H7+/D7+ clusters using an ab initio potential energy surface.

PubMed

Barragán, Patricia; Pérez de Tudela, Ricardo; Qu, Chen; Prosmiti, Rita; Bowman, Joel M

2013-07-14

Diffusion Monte Carlo (DMC) and path-integral Monte Carlo computations of the vibrational ground state and 10 K equilibrium state properties of the H7 (+)/D7 (+) cations are presented, using an ab initio full-dimensional potential energy surface. The DMC zero-point energies of dissociated fragments H5 (+)(D5 (+))+H2(D2) are also calculated and from these results and the electronic dissociation energy, dissociation energies, D0, of 752 ± 15 and 980 ± 14 cm(-1) are reported for H7 (+) and D7 (+), respectively. Due to the known error in the electronic dissociation energy of the potential surface, these quantities are underestimated by roughly 65 cm(-1). These values are rigorously determined for first time, and compared with previous theoretical estimates from electronic structure calculations using standard harmonic analysis, and available experimental measurements. Probability density distributions are also computed for the ground vibrational and 10 K state of H7 (+) and D7 (+). These are qualitatively described as a central H3 (+)/D3 (+) core surrounded by "solvent" H2/D2 molecules that nearly freely rotate.

Detailed study of the water trimer potential energy surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fowler, J.E.; Schaefer, H.F. III

The potential energy surface of the water trimer has been studied through the use of ab initio quantum mechanical methods. Five stationary points were located, including one minimum and two transition states. All geometries were optimized at levels up to the double-[Zeta] plus polarization plus diffuse (DZP + diff) single and double excitation coupled cluster (CCSD) level of theory. CCSD single energy points were obtained for the minimum, two transition states, and the water monomer using the triple-[Zeta] plus double polarization plus diffuse (TZ2P + diff) basis at the geometries predicted by the DZP + diff CCSD method. Reported aremore » the following: geometrical parameters, total and relative energies, harmonic vibrational frequencies and infrared intensities for the minimum, and zero point vibrational energies for the minimum, two transition states, and three separated water molecules. 27 refs., 5 figs., 10 tabs.« less

The vibrationally adiabatic torsional potential energy surface of trans-stilbene

NASA Astrophysics Data System (ADS)

Chowdary, Praveen D.; Martinez, Todd J.; Gruebele, Martin

2007-05-01

The effect of vibrational Zero Point Energy (ZPE) on the torsional barriers of trans-stilbene is studied in the adiabatic approximation. The two torsional modes corresponding to phenyl rotation are explicitly separated, and the remaining modes are treated as normal coordinates. ZPE reduces the adiabatic barrier along the in-phase torsion from 198 to 13 cm -1. A one-dimensional adiabatic potential for the anti-phase torsion, including the ZPE of the in-phase torsion, reduces the adiabatic barrier from 260 to 58 cm -1. Comparison with recent electronic structure benchmark calculations suggests that vibrational corrections play a significant role in trans-stilbene's experimentally observed planar structure.

Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water-dimer III: Mixed Jacobi-valence parametrization and benchmark results for the zero point energy, vibrationally excited states, and infrared spectrum.

PubMed

Vendrell, Oriol; Brill, Michael; Gatti, Fabien; Lauvergnat, David; Meyer, Hans-Dieter

2009-06-21

Quantum dynamical calculations are reported for the zero point energy, several low-lying vibrational states, and the infrared spectrum of the H(5)O(2)(+) cation. The calculations are performed by the multiconfiguration time-dependent Hartree (MCTDH) method. A new vector parametrization based on a mixed Jacobi-valence description of the system is presented. With this parametrization the potential energy surface coupling is reduced with respect to a full Jacobi description, providing a better convergence of the n-mode representation of the potential. However, new coupling terms appear in the kinetic energy operator. These terms are derived and discussed. A mode-combination scheme based on six combined coordinates is used, and the representation of the 15-dimensional potential in terms of a six-combined mode cluster expansion including up to some 7-dimensional grids is discussed. A statistical analysis of the accuracy of the n-mode representation of the potential at all orders is performed. Benchmark, fully converged results are reported for the zero point energy, which lie within the statistical uncertainty of the reference diffusion Monte Carlo result for this system. Some low-lying vibrationally excited eigenstates are computed by block improved relaxation, illustrating the applicability of the approach to large systems. Benchmark calculations of the linear infrared spectrum are provided, and convergence with increasing size of the time-dependent basis and as a function of the order of the n-mode representation is studied. The calculations presented here make use of recent developments in the parallel version of the MCTDH code, which are briefly discussed. We also show that the infrared spectrum can be computed, to a very good approximation, within D(2d) symmetry, instead of the G(16) symmetry used before, in which the complete rotation of one water molecule with respect to the other is allowed, thus simplifying the dynamical problem.

Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Huixian; School of Physics, Northwest University, Xi’an, Shaanxi 710069; Li, Anyang

2014-12-28

A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S{sub 0}) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm{sup −1}. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies upmore » to 12 700 cm{sup −1} above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.« less

An ab initio potential energy surface for the formic acid dimer: zero-point energy, selected anharmonic fundamental energies, and ground-state tunneling splitting calculated in relaxed 1-4-mode subspaces.

PubMed

Qu, Chen; Bowman, Joel M

2016-09-14

We report a full-dimensional, permutationally invariant potential energy surface (PES) for the cyclic formic acid dimer. This PES is a least-squares fit to 13475 CCSD(T)-F12a/haTZ (VTZ for H and aVTZ for C and O) energies. The energy-weighted, root-mean-square fitting error is 11 cm -1 and the barrier for the double-proton transfer on the PES is 2848 cm -1 , in good agreement with the directly-calculated ab initio value of 2853 cm -1 . The zero-point vibrational energy of 15 337 ± 7 cm -1 is obtained from diffusion Monte Carlo calculations. Energies of fundamentals of fifteen modes are calculated using the vibrational self-consistent field and virtual-state configuration interaction method. The ground-state tunneling splitting is computed using a reduced-dimensional Hamiltonian with relaxed potentials. The highest-level, four-mode coupled calculation gives a tunneling splitting of 0.037 cm -1 , which is roughly twice the experimental value. The tunneling splittings of (DCOOH) 2 and (DCOOD) 2 from one to three mode calculations are, as expected, smaller than that for (HCOOH) 2 and consistent with experiment.

Ignition of Ionic Liquids. Volume 2

DTIC Science & Technology

2010-09-01

TOFMS time-of-flight-mass-spectrometry TS transition state VUV vacuum ultraviolet ZPE zero-point energy Approved for public...energies ( ZPEs ) were scaled by a factor of 0.9613 and 0.9804, respectively, and when necessary intrinsic reaction coordinate (IRC) calculations were...oscillations in the PE reflect the vibration of the DNB molecule, including ZPE . The trajectory shows three dissociation steps, eliminating NO2 followed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engel, Edgar A., E-mail: eae32@cam.ac.uk; Needs, Richard J.; Monserrat, Bartomeu

Surface energies of hexagonal and cubic water ice are calculated using first-principles quantum mechanical methods, including an accurate description of anharmonic nuclear vibrations. We consider two proton-orderings of the hexagonal and cubic ice basal surfaces and three proton-orderings of hexagonal ice prism surfaces, finding that vibrations reduce the surface energies by more than 10%. We compare our vibrational densities of states to recent sum frequency generation absorption measurements and identify surface proton-orderings of experimental ice samples and the origins of characteristic absorption peaks. We also calculate zero point quantum vibrational corrections to the surface electronic band gaps, which range frommore » −1.2 eV for the cubic ice basal surface up to −1.4 eV for the hexagonal ice prism surface. The vibrational corrections to the surface band gaps are up to 12% smaller than for bulk ice.« less

Zero-Point Energy Leakage in Quantum Thermal Bath Molecular Dynamics Simulations.

PubMed

Brieuc, Fabien; Bronstein, Yael; Dammak, Hichem; Depondt, Philippe; Finocchi, Fabio; Hayoun, Marc

2016-12-13

The quantum thermal bath (QTB) has been presented as an alternative to path-integral-based methods to introduce nuclear quantum effects in molecular dynamics simulations. The method has proved to be efficient, yielding accurate results for various systems. However, the QTB method is prone to zero-point energy leakage (ZPEL) in highly anharmonic systems. This is a well-known problem in methods based on classical trajectories where part of the energy of the high-frequency modes is transferred to the low-frequency modes leading to a wrong energy distribution. In some cases, the ZPEL can have dramatic consequences on the properties of the system. Thus, we investigate the ZPEL by testing the QTB method on selected systems with increasing complexity in order to study the conditions and the parameters that influence the leakage. We also analyze the consequences of the ZPEL on the structural and vibrational properties of the system. We find that the leakage is particularly dependent on the damping coefficient and that increasing its value can reduce and, in some cases, completely remove the ZPEL. When using sufficiently high values for the damping coefficient, the expected energy distribution among the vibrational modes is ensured. In this case, the QTB method gives very encouraging results. In particular, the structural properties are well-reproduced. The dynamical properties should be regarded with caution although valuable information can still be extracted from the vibrational spectrum, even for large values of the damping term.

XZP + 1d and XZP + 1d-DKH basis sets for second-row elements: application to CCSD(T) zero-point vibrational energy and atomization energy calculations.

PubMed

Campos, Cesar T; Jorge, Francisco E; Alves, Júlia M A

2012-09-01

Recently, segmented all-electron contracted double, triple, quadruple, quintuple, and sextuple zeta valence plus polarization function (XZP, X = D, T, Q, 5, and 6) basis sets for the elements from H to Ar were constructed for use in conjunction with nonrelativistic and Douglas-Kroll-Hess Hamiltonians. In this work, in order to obtain a better description of some molecular properties, the XZP sets for the second-row elements were augmented with high-exponent d "inner polarization functions," which were optimized in the molecular environment at the second-order Møller-Plesset level. At the coupled cluster level of theory, the inclusion of tight d functions for these elements was found to be essential to improve the agreement between theoretical and experimental zero-point vibrational energies (ZPVEs) and atomization energies. For all of the molecules studied, the ZPVE errors were always smaller than 0.5 %. The atomization energies were also improved by applying corrections due to core/valence correlation and atomic spin-orbit effects. This led to estimates for the atomization energies of various compounds in the gaseous phase. The largest error (1.2 kcal mol(-1)) was found for SiH(4).

Vibrational self-consistent field theory using optimized curvilinear coordinates.

PubMed

Bulik, Ireneusz W; Frisch, Michael J; Vaccaro, Patrick H

2017-07-28

A vibrational SCF model is presented in which the functions forming the single-mode functions in the product wavefunction are expressed in terms of internal coordinates and the coordinates used for each mode are optimized variationally. This model involves no approximations to the kinetic energy operator and does not require a Taylor-series expansion of the potential. The non-linear optimization of coordinates is found to give much better product wavefunctions than the limited variations considered in most previous applications of SCF methods to vibrational problems. The approach is tested using published potential energy surfaces for water, ammonia, and formaldehyde. Variational flexibility allowed in the current ansätze results in excellent zero-point energies expressed through single-product states and accurate fundamental transition frequencies realized by short configuration-interaction expansions. Fully variational optimization of single-product states for excited vibrational levels also is discussed. The highlighted methodology constitutes an excellent starting point for more sophisticated treatments, as the bulk characteristics of many-mode coupling are accounted for efficiently in terms of compact wavefunctions (as evident from the accurate prediction of transition frequencies).

Surprising performance for vibrational frequencies of the distinguishable clusters with singles and doubles (DCSD) and MP2.5 approximations

NASA Astrophysics Data System (ADS)

Kesharwani, Manoj K.; Sylvetsky, Nitai; Martin, Jan M. L.

2017-11-01

We show that the DCSD (distinguishable clusters with all singles and doubles) correlation method permits the calculation of vibrational spectra at near-CCSD(T) quality but at no more than CCSD cost, and with comparatively inexpensive analytical gradients. For systems dominated by a single reference configuration, even MP2.5 is a viable alternative, at MP3 cost. MP2.5 performance for vibrational frequencies is comparable to double hybrids such as DSD-PBEP86-D3BJ, but without resorting to empirical parameters. DCSD is also quite suitable for computing zero-point vibrational energies in computational thermochemistry.

Communication: THz absorption spectrum of the CO2-H2O complex: observation and assignment of intermolecular van der Waals vibrations.

PubMed

Andersen, J; Heimdal, J; Mahler, D W; Nelander, B; Larsen, R Wugt

2014-03-07

Terahertz absorption spectra have been recorded for the weakly bound CO2-H2O complex embedded in cryogenic neon matrices at 2.8 K. The three high-frequency van der Waals vibrational transitions associated with out-of-plane wagging, in-plane rocking, and torsional motion of the isotopic H2O subunit have been assigned and provide crucial observables for benchmark theoretical descriptions of this systems' flat intermolecular potential energy surface. A (semi)-empirical value for the zero-point energy of 273 ± 15 cm(-1) from the class of intermolecular van der Waals vibrations is proposed and the combination with high-level quantum chemical calculations provides a value of 726 ± 15 cm(-1) for the dissociation energy D0.

Identification of bearing faults using time domain zero-crossings

NASA Astrophysics Data System (ADS)

William, P. E.; Hoffman, M. W.

2011-11-01

In this paper, zero-crossing characteristic features are employed for early detection and identification of single point bearing defects in rotating machinery. As a result of bearing defects, characteristic defect frequencies appear in the machine vibration signal, normally requiring spectral analysis or envelope analysis to identify the defect type. Zero-crossing features are extracted directly from the time domain vibration signal using only the duration between successive zero-crossing intervals and do not require estimation of the rotational frequency. The features are a time domain representation of the composite vibration signature in the spectral domain. Features are normalized by the length of the observation window and classification is performed using a multilayer feedforward neural network. The model was evaluated on vibration data recorded using an accelerometer mounted on an induction motor housing subjected to a number of single point defects with different severity levels.

"Vibrational bonding": a new type of chemical bond is discovered.

PubMed

Rhodes, Christopher J; Macrae, Roderick M

2015-01-01

A long-sought but elusive new type of chemical bond, occurring on a minimum-free, purely repulsive potential energy surface, has recently been convincingly shown to be possible on the basis of high-level quantum-chemical calculations. This type of bond, termed a vibrational bond, forms because the total energy, including the dynamical energy of the nuclei, is lower than the total energy of the dissociated products, including their vibrational zero-point energy. For this to be the case, the ZPE of the product molecule must be very high, which is ensured by replacing a conventional hydrogen atom with its light isotope muonium (Mu, mass = 1/9 u) in the system Br-H-Br, a natural transition state in the reaction between Br and HBr. A paramagnetic species observed in the reaction Mu +Br2 has been proposed as a first experimental sighting of this species, but definitive identification remains challenging.

Frequency and zero-point vibrational energy scale factors for double-hybrid density functionals (and other selected methods): can anharmonic force fields be avoided?

PubMed

Kesharwani, Manoj K; Brauer, Brina; Martin, Jan M L

2015-03-05

We have obtained uniform frequency scaling factors λ(harm) (for harmonic frequencies), λ(fund) (for fundamentals), and λ(ZPVE) (for zero-point vibrational energies (ZPVEs)) for the Weigend-Ahlrichs and other selected basis sets for MP2, SCS-MP2, and a variety of DFT functionals including double hybrids. For selected levels of theory, we have also obtained scaling factors for true anharmonic fundamentals and ZPVEs obtained from quartic force fields. For harmonic frequencies, the double hybrids B2PLYP, B2GP-PLYP, and DSD-PBEP86 clearly yield the best performance at RMSD = 10-12 cm(-1) for def2-TZVP and larger basis sets, compared to 5 cm(-1) at the CCSD(T) basis set limit. For ZPVEs, again, the double hybrids are the best performers, reaching root-mean-square deviations (RMSDs) as low as 0.05 kcal/mol, but even mainstream functionals like B3LYP can get down to 0.10 kcal/mol. Explicitly anharmonic ZPVEs only are marginally more accurate. For fundamentals, however, simple uniform scaling is clearly inadequate.

Revisiting Adiabatic Switching for Initial Conditions in Quasi-Classical Trajectory Calculations: Application to CH4.

PubMed

Qu, Chen; Bowman, Joel M

2016-07-14

Semiclassical quantization of vibrational energies, using adiabatic switching (AS), is applied to CH4 using a recent ab initio potential energy surface, for which exact quantum calculations of vibrational energies are available. Details of the present calculations, which employ a harmonic normal-mode zeroth-order Hamiltonian, emphasize the importance of transforming to the Eckart frame during the propagation of the adiabatically switched Hamiltonian. The AS energies for the zero-point, and fundamental excitations of two modes are in good agreement with the quantum ones. The use of AS in the context of quasi-classical trajectory calculations is revisited, following previous work reported in 1995, which did not recommend the procedure. We come to a different conclusion here.

Analytic second derivatives of the energy in the fragment molecular orbital method

NASA Astrophysics Data System (ADS)

Nakata, Hiroya; Nagata, Takeshi; Fedorov, Dmitri G.; Yokojima, Satoshi; Kitaura, Kazuo; Nakamura, Shinichiro

2013-04-01

We developed the analytic second derivatives of the energy for the fragment molecular orbital (FMO) method. First we derived the analytic expressions and then introduced some approximations related to the first and second order coupled perturbed Hartree-Fock equations. We developed a parallel program for the FMO Hessian with approximations in GAMESS and used it to calculate infrared (IR) spectra and Gibbs free energies and to locate the transition states in SN2 reactions. The accuracy of the Hessian is demonstrated in comparison to ab initio results for polypeptides and a water cluster. By using the two residues per fragment division, we achieved the accuracy of 3 cm-1 in the reduced mean square deviation of vibrational frequencies from ab initio for all three polyalanine isomers, while the zero point energy had the error not exceeding 0.3 kcal/mol. The role of the secondary structure on IR spectra, zero point energies, and Gibbs free energies is discussed.

A practical method to avoid zero-point leak in molecular dynamics calculations: application to the water dimer.

PubMed

Czakó, Gábor; Kaledin, Alexey L; Bowman, Joel M

2010-04-28

We report the implementation of a previously suggested method to constrain a molecular system to have mode-specific vibrational energy greater than or equal to the zero-point energy in quasiclassical trajectory calculations [J. M. Bowman et al., J. Chem. Phys. 91, 2859 (1989); W. H. Miller et al., J. Chem. Phys. 91, 2863 (1989)]. The implementation is made practical by using a technique described recently [G. Czako and J. M. Bowman, J. Chem. Phys. 131, 244302 (2009)], where a normal-mode analysis is performed during the course of a trajectory and which gives only real-valued frequencies. The method is applied to the water dimer, where its effectiveness is shown by computing mode energies as a function of integration time. Radial distribution functions are also calculated using constrained quasiclassical and standard classical molecular dynamics at low temperature and at 300 K and compared to rigorous quantum path integral calculations.

Synthesis, spectroscopic investigation and computational study of 3-(1-(((methoxycarbonyl)oxy)imino)ethyl)-2H-chromen-2-one

NASA Astrophysics Data System (ADS)

Gokula Krishnan, K.; Sivakumar, R.; Thanikachalam, V.; Saleem, H.; Arockia doss, M.

2015-06-01

The molecular structure and vibrational modes of 3-acetylcoumarin oxime carbonate (abbreviated as 3-ACOC) have been investigated by FT-IR, FT-Raman, NMR spectra and also by computational methods using HF and B3LYP with 6-311++G(d,p) basis set. The optimized geometric parameters (bond lengths, bond angles and dihedral angles) were in good agreement with the corresponding experimental values of 3-ACOC. The calculated vibrational frequencies of normal modes from DFT method matched well with the experimental values. The complete assignments were made on the basis of the total energy distribution (TED) of the vibrational modes. NMR (1H and 13C) chemical shifts were calculated by GIAO method and the results were compared with the experimental values. The other parameters like dipole moment, polarizability, first order hyperpolarizability, zero-point vibrational energy, EHOMO, ELUMO, heat capacity and entropy have also been computed.

Direct observation of vibrational energy dispersal via methyl torsions.

PubMed

Gardner, Adrian M; Tuttle, William D; Whalley, Laura E; Wright, Timothy G

2018-02-28

Explicit evidence for the role of methyl rotor levels in promoting energy dispersal is reported. A set of coupled zero-order vibration/vibration-torsion (vibtor) levels in the S 1 state of para -fluorotoluene ( p FT) are investigated. Two-dimensional laser-induced fluorescence (2D-LIF) and two-dimensional zero-kinetic-energy (2D-ZEKE) spectra are reported, and the assignment of the main features in both sets of spectra reveals that the methyl torsion is instrumental in providing a route for coupling between vibrational levels of different symmetry classes. We find that there is very localized, and selective, dissipation of energy via doorway states, and that, in addition to an increase in the density of states, a critical role of the methyl group is a relaxation of symmetry constraints compared to direct vibrational coupling.

A DFT study of thermodynamic properties of C36 and C14 Fe2Zr Laves phases

NASA Astrophysics Data System (ADS)

Ali, Kawsar; Ghosh, P. S.; Arya, A. K.

2018-04-01

Fe-Zr alloys are promising materials for metallic waste immobilization in nuclear industry. C36 and C14 Fe2Zr Laves phases are frequently observed in Fe-Zr alloys that can host radionuclides. The phonon dispersions of C36 and C14 Fe2Zr Laves phases shows that both intermetallics are dynamically stable. The Helmholtz free energy, vibrational entropy, internal energy and specific heat at constant volume has been calculated. The zero point energies of C36 and C14 phases are 9.23 and 9.91 kJ/mole, respectively. The vibrational free energy becomes negative at 250 K and 270 K. The high temperature specific heat at constant volume of both intermetallics is 74 J/K/mole.

Zero kinetic energy photoelectron spectroscopy of triphenylene.

PubMed

Harthcock, Colin; Zhang, Jie; Kong, Wei

2014-06-28

We report vibrational information of both the first electronically excited state and the ground cationic state of jet-cooled triphenylene via the techniques of resonantly enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectroscopy. The first excited electronic state S1 of the neutral molecule is of A1' symmetry and is therefore electric dipole forbidden in the D3h group. Consequently, there are no observable Franck-Condon allowed totally symmetric a1' vibrational bands in the REMPI spectrum. All observed vibrational transitions are due to Herzberg-Teller vibronic coupling to the E' third electronically excited state S3. The assignment of all vibrational bands as e' symmetry is based on comparisons with calculations using the time dependent density functional theory and spectroscopic simulations. When an electron is eliminated, the molecular frame undergoes Jahn-Teller distortion, lowering the point group to C2v and resulting in two nearly degenerate electronic states of A2 and B1 symmetry. Here we follow a crude treatment by assuming that all e' vibrational modes resolve into b2 and a1 modes in the C2v molecular frame. Some observed ZEKE transitions are tentatively assigned, and the adiabatic ionization threshold is determined to be 63 365 ± 7 cm(-1). The observed ZEKE spectra contain a consistent pattern, with a cluster of transitions centered near the same vibrational level of the cation as that of the intermediate state, roughly consistent with the propensity rule. However, complete assignment of the detailed vibrational structure due to Jahn-Teller coupling requires much more extensive calculations, which will be performed in the future.

Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

NASA Astrophysics Data System (ADS)

Loffreda, David

2006-05-01

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.

On-the-Fly ab Initio Semiclassical Calculation of Glycine Vibrational Spectrum

PubMed Central

2017-01-01

We present an on-the-fly ab initio semiclassical study of vibrational energy levels of glycine, calculated by Fourier transform of the wavepacket correlation function. It is based on a multiple coherent states approach integrated with monodromy matrix regularization for chaotic dynamics. All four lowest-energy glycine conformers are investigated by means of single-trajectory semiclassical spectra obtained upon classical evolution of on-the-fly trajectories with harmonic zero-point energy. For the most stable conformer I, direct dynamics trajectories are also run for each vibrational mode with energy equal to the first harmonic excitation. An analysis of trajectories evolved up to 50 000 atomic time units demonstrates that, in this time span, conformers II and III can be considered as isolated species, while conformers I and IV show a pretty facile interconversion. Therefore, previous perturbative studies based on the assumption of isolated conformers are often reliable but might be not completely appropriate in the case of conformer IV and conformer I for which interconversion occurs promptly. PMID:28489368

Vibrational structure of vinyl chloride cation studied by using one-photon zero-kinetic energy photoelectron spectroscopy.

PubMed

Zhang, Ping; Li, Juan; Mo, Yuxiang

2007-09-06

The vibrational structure of vinyl chloride cation, CH(2)CHCl+ (X(2)A' '), has been studied by vacuum ultraviolet (VUV) zero-kinetic energy (ZEKE) photoelectron spectroscopy. Among nine symmetric vibrational modes, the fundamental frequencies of six modes have been determined. The first overtone of the out-of-plane CH(2) twist vibrational mode has been also measured. In addition to these, the combination and overtone bands of the above vibrational modes about 4500 cm(-1) above the ground state have been observed in the ZEKE spectrum. The vibrational band intensities of the ZEKE spectrum can be described approximately by the Franck-Condon factors with harmonic approximation. The ZEKE spectrum has been assigned based on the harmonic frequencies and Franck-Condon factors from theoretical calculations. The ionization energy (IE) of CH(2)CHCl is determined as 80705.5 +/- 2.5 (cm(-1)) or 10.0062 +/- 0.0003 (eV).

Observation of b 2 symmetry vibrational levels of the SO 2C 1B 2 state: Vibrational level staggering, Coriolis interactions, and rotation-vibration constants

DOE PAGES

Park, G. Barratt; Jiang, Jun; Saladrigas, Catherine A.; ...

2016-04-14

Here, the C 1B 2 state of SO 2 has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. However, low-lying levels with odd quanta of antisymmetric stretch (b 2 vibrational symmetry) have not previously been observed because transitions into these levels from the zero-point level of the X ~ state are vibronically forbidden. We use IR-UV double resonance to observe the b 2 vibrational levels of the C state below 1600 cm –1 of vibrational excitation. This enables a direct characterization of the vibrational level staggering that results frommore » the double-minimum potential. In addition, it allows us to deperturb the strong c-axis Coriolis interactions between levels of a 1 and b 2 vibrational symmetry, and to determine accurately the vibrational dependence of the rotational constants in the distorted C electronic state.« less

Observation of b 2 symmetry vibrational levels of the SO 2C 1B 2 state: Vibrational level staggering, Coriolis interactions, and rotation-vibration constants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, G. Barratt; Jiang, Jun; Saladrigas, Catherine A.

Here, the C 1B 2 state of SO 2 has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. However, low-lying levels with odd quanta of antisymmetric stretch (b 2 vibrational symmetry) have not previously been observed because transitions into these levels from the zero-point level of the X ~ state are vibronically forbidden. We use IR-UV double resonance to observe the b 2 vibrational levels of the C state below 1600 cm –1 of vibrational excitation. This enables a direct characterization of the vibrational level staggering that results frommore » the double-minimum potential. In addition, it allows us to deperturb the strong c-axis Coriolis interactions between levels of a 1 and b 2 vibrational symmetry, and to determine accurately the vibrational dependence of the rotational constants in the distorted C electronic state.« less

Effects of zero point vibration on the reaction dynamics of water dimer cations following ionization.

PubMed

Tachikawa, Hiroto

2017-06-30

Reactions of water dimer cation (H2O)2+ following ionization have been investigated by means of a direct ab initio molecular dynamics method. In particular, the effects of zero point vibration and zero point energy (ZPE) on the reaction mechanism were considered in this work. Trajectories were run on two electronic potential energy surfaces (PESs) of (H2O)2+: ground state ( 2 A″-like state) and the first excited state ( 2 A'-like state). All trajectories on the ground-state PES lead to the proton-transferred product: H 2 O + (Wd)-H 2 O(Wa) → OH(Wd)-H 3 O + (Wa), where Wd and Wa refer to the proton donor and acceptor water molecules, respectively. Time of proton transfer (PT) varied widely from 15 to 40 fs (average time of PT = 30.9 fs). The trajectories on the excited-state PES gave two products: an intermediate complex with a face-to-face structure (H 2 O-OH 2 ) + and a PT product. However, the proton was transferred to the opposite direction, and the reverse PT was found on the excited-state PES: H 2 O(Wd)-H 2 O + (Wa) → H 3 O + (Wd)-OH(Wa). This difference occurred because the ionizing water molecule in the dimer switched between the ground and excited states. The reaction mechanism of (H2O)2+ and the effects of ZPE are discussed on the basis of the results. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

A rotamer energy level study of sulfuric acid.

PubMed

Partanen, Lauri; Pesonen, Janne; Sjöholm, Elina; Halonen, Lauri

2013-10-14

It is a common approach in quantum chemical calculations for polyatomic molecules to rigidly constrain some of the degrees of freedom in order to make the calculations computationally feasible. However, the presence of the rigid constraints also affects the kinetic energy operator resulting in the frozen mode correction, originally derived by Pesonen [J. Chem. Phys. 139, 144310 (2013)]. In this study, we compare the effects of this correction to several different approximations to the kinetic energy operator used in the literature, in the specific case of the rotamer energy levels of sulfuric acid. The two stable conformers of sulfuric acid are connected by the rotations of the O-S-O-H dihedral angles and possess C2 and Cs symmetry in the order of increasing energy. Our results show that of the models tested, the largest differences with the frozen mode corrected values were obtained by simply omitting the passive degrees of freedom. For the lowest 17 excited states, this inappropriate treatment introduces an increase of 9.6 cm(-1) on average, with an increase of 8.7 cm(-1) in the zero-point energies. With our two-dimensional potential energy surface calculated at the CCSD(T)-F12a/VDZ-F12 level, we observe a radical shift in the density of states compared to the harmonic picture, combined with an increase in zero point energy. Thus, we conclude that the quantum mechanical inclusion of the different conformers of sulfuric acid have a significant effect on its vibrational partition function, suggesting that it will also have an impact on the computational values of the thermodynamic properties of any reactions where sulfuric acid plays a role. Finally, we also considered the effect of the anharmonicities for the other vibrational degrees of freedom with a VSCF-calculation at the DF-MP2-F12/VTZ-F12 level of theory but found that the inclusion of the other conformer had the more important effect on the vibrational partition function.

Energy dissipation in fragmented geomaterials associated with impacting oscillators

NASA Astrophysics Data System (ADS)

Khudyakov, Maxim; Pasternak, Elena; Dyskin, Arcady

2016-04-01

In wave propagation through fragmented geomaterials forced by periodic loadings, the elements (fragments) strike against each other when passing through the neutral position (position with zero mutual rotation), quickly damping the oscillations. Essentially the impacts act as shock absorbers albeit localised at the neutral points. In order to analyse the vibrations of and wave propagation in such structures, a differential equation of a forced harmonic oscillator was investigated, where the each time the system passes through the neutral point the velocity gets reduced by multiplying it with the restitution coefficient which characterise the impact of the fragments. In forced vibrations the impact times depend on both the forced oscillations and the restitution coefficient and form an irregular sequence. Numerical solution of the differential equation was performed using Mathematica software. Along with vibration diagrams, the dependence of the energy dissipation on the ratio of the forcing frequency to the natural frequency was obtained. For small positive values of the restitution coefficient (less than 0.5), the asymmetric oscillations were found, and the phase of the forced vibrations determined the direction of the asymmetry. Also, at some values of the forcing frequencies and the restitution coefficient chaotic behaviour was found.

Many Molecular Properties from One Kernel in Chemical Space

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramakrishnan, Raghunathan; von Lilienfeld, O. Anatole

We introduce property-independent kernels for machine learning modeling of arbitrarily many molecular properties. The kernels encode molecular structures for training sets of varying size, as well as similarity measures sufficiently diffuse in chemical space to sample over all training molecules. Corresponding molecular reference properties provided, they enable the instantaneous generation of ML models which can systematically be improved through the addition of more data. This idea is exemplified for single kernel based modeling of internal energy, enthalpy, free energy, heat capacity, polarizability, electronic spread, zero-point vibrational energy, energies of frontier orbitals, HOMOLUMO gap, and the highest fundamental vibrational wavenumber. Modelsmore » of these properties are trained and tested using 112 kilo organic molecules of similar size. Resulting models are discussed as well as the kernels’ use for generating and using other property models.« less

Cation-Cation pi-pi Stacking in Small Ionic Clusters of 1,2,4-Triazolium (Preprint)

DTIC Science & Technology

2007-07-12

Figure 1 is 1.5 kcal/mol lower than that of the neutral one. Including zero point energies ( ZPE ) obtained with MP2/aug-cc-pVDZ harmonic vibrational...the ionic tetramer is lower than that of the neutral tetramer by 6.0, 7.6 and 8.0 kcal/mol, respectively. Including ZPE , these three values become

Electronic torsional sound in linear atomic chains: Chemical energy transport at 1000 km/s

NASA Astrophysics Data System (ADS)

Kurnosov, Arkady A.; Rubtsov, Igor V.; Maksymov, Andrii O.; Burin, Alexander L.

2016-07-01

We investigate entirely electronic torsional vibrational modes in linear cumulene chains. The carbon nuclei of a cumulene are positioned along the primary axis so that they can participate only in the transverse and longitudinal motions. However, the interatomic electronic clouds behave as a torsion spring with remarkable torsional stiffness. The collective dynamics of these clouds can be described in terms of electronic vibrational quanta, which we name torsitons. It is shown that the group velocity of the wavepacket of torsitons is much higher than the typical speed of sound, because of the small mass of participating electrons compared to the atomic mass. For the same reason, the maximum energy of the torsitons in cumulenes is as high as a few electronvolts, while the minimum possible energy is evaluated as a few hundred wavenumbers and this minimum is associated with asymmetry of zero point atomic vibrations. Theory predictions are consistent with the time-dependent density functional theory calculations. Molecular systems for experimental evaluation of the predictions are proposed.

Vibrational and thermal properties of β-HMX and TATB from dispersion corrected density functional theory

NASA Astrophysics Data System (ADS)

Landerville, Aaron C.; Oleynik, Ivan I.

2017-01-01

Dispersion Corrected Density Functional Theory (DFT+vdW) calculations are performed to predict vibrational and thermal properties of the bulk energetic materials (EMs) β-octahydrocyclotetramethylene-tetranitramine (β-HMX) and triaminotrinitrobenzene (TATB). DFT+vdW calculations of pressure-dependent crystal structure and the hydrostatic equation of state are followed by frozen-phonon calculations of their respective vibration spectra at each pressure. These are then used under the quasi-harmonic approximation to obtain zero-point and thermal free energy contributions to the pressure, resulting in pressure-volume-temperature (PVT) EOS for each material that are in excellent agreement with experiment. Heat capacities, and coefficients of thermal expansion as functions of temperature are also calculated and compared with experiment.

Low-rank canonical-tensor decomposition of potential energy surfaces: application to grid-based diagrammatic vibrational Green's function theory

NASA Astrophysics Data System (ADS)

Rai, Prashant; Sargsyan, Khachik; Najm, Habib; Hermes, Matthew R.; Hirata, So

2017-09-01

A new method is proposed for a fast evaluation of high-dimensional integrals of potential energy surfaces (PES) that arise in many areas of quantum dynamics. It decomposes a PES into a canonical low-rank tensor format, reducing its integral into a relatively short sum of products of low-dimensional integrals. The decomposition is achieved by the alternating least squares (ALS) algorithm, requiring only a small number of single-point energy evaluations. Therefore, it eradicates a force-constant evaluation as the hotspot of many quantum dynamics simulations and also possibly lifts the curse of dimensionality. This general method is applied to the anharmonic vibrational zero-point and transition energy calculations of molecules using the second-order diagrammatic vibrational many-body Green's function (XVH2) theory with a harmonic-approximation reference. In this application, high dimensional PES and Green's functions are both subjected to a low-rank decomposition. Evaluating the molecular integrals over a low-rank PES and Green's functions as sums of low-dimensional integrals using the Gauss-Hermite quadrature, this canonical-tensor-decomposition-based XVH2 (CT-XVH2) achieves an accuracy of 0.1 cm-1 or higher and nearly an order of magnitude speedup as compared with the original algorithm using force constants for water and formaldehyde.

Theoretical study on the dissociation energies, ionization potentials and electron affinities of three perfluoroalkyl iodides

NASA Astrophysics Data System (ADS)

Cheng, Li; Shen, Zuochun; Lu, Jianye; Gao, Huide; Lü, Zhiwei

2005-11-01

Dissociation energies, ionization potentials and electron affinities of three perfluoroalkyl iodides, CF 3I, C 2F 5I, and i-C 3F 7I are calculated accurately with B3LYP, MP n ( n = 2-4), QCISD, QCISD(T), CCSD, and CCSD(T) methods. Calculations are performed by using large-core correlation-consistent pseudopotential basis set (SDB-aug-cc-pVTZ) for iodine atom. In all energy calculations, the zero point vibration energy is corrected. And the basis set superposition error is corrected by counterpoise method in the calculation of dissociation energy. Theoretical results are compared with the experimental values.

Thermal properties of graphene from path-integral simulations

NASA Astrophysics Data System (ADS)

Herrero, Carlos P.; Ramírez, Rafael

2018-03-01

Thermal properties of graphene monolayers are studied by path-integral molecular dynamics simulations, which take into account the quantization of vibrational modes in the crystalline membrane and allow one to consider anharmonic effects in these properties. This system was studied at temperatures in the range from 12 to 2000 K and zero external stress, by describing the interatomic interactions through the LCBOPII effective potential. We analyze the internal energy and specific heat and compare the results derived from the simulations with those yielded by a harmonic approximation for the vibrational modes. This approximation turns out to be rather precise up to temperatures of about 400 K. At higher temperatures, we observe an influence of the elastic energy due to the thermal expansion of the graphene sheet. Zero-point and thermal effects on the in-plane and "real" surface of graphene are discussed. The thermal expansion coefficient α of the real area is found to be positive at all temperatures, in contrast to the expansion coefficient αp of the in-plane area, which is negative at low temperatures and becomes positive for T ≳ 1000 K.

Structure and spectral features of H+(H2O)7: Eigen versus Zundel forms.

PubMed

Shin, Ilgyou; Park, Mina; Min, Seung Kyu; Lee, Eun Cheol; Suh, Seung Bum; Kim, Kwang S

2006-12-21

The two dimensional (2D) to three dimensional (3D) transition for the protonated water cluster has been controversial, in particular, for H(+)(H(2)O)(7). For H(+)(H(2)O)(7) the 3D structure is predicted to be lower in energy than the 2D structure at most levels of theory without zero-point energy (ZPE) correction. On the other hand, with ZPE correction it is predicted to be either 2D or 3D depending on the calculational levels. Although the ZPE correction favors the 3D structure at the level of coupled cluster theory with singles, doubles, and perturbative triples excitations [CCSD(T)] using the aug-cc-pVDZ basis set, the result based on the anharmonic zero-point vibrational energy correction favors the 2D structure. Therefore, the authors investigated the energies based on the complete basis set limit scheme (which we devised in an unbiased way) at the resolution of the identity approximation Moller-Plesset second order perturbation theory and CCSD(T) levels, and found that the 2D structure has the lowest energy for H(+)(H(2)O)(7) [though nearly isoenergetic to the 3D structure for D(+)(D(2)O)(7)]. This structure has the Zundel-type configuration, but it shows the quantum probabilistic distribution including some of the Eigen-type configuration. The vibrational spectra of MP2/aug-cc-pVDZ calculations and Car-Parrinello molecular dynamics simulations, taking into account the thermal and dynamic effects, show that the 2D Zundel-type form is in good agreement with experiments.

Structure and spectral features of H+(H2O)7: Eigen versus Zundel forms

NASA Astrophysics Data System (ADS)

Shin, Ilgyou; Park, Mina; Min, Seung Kyu; Lee, Eun Cheol; Suh, Seung Bum; Kim, Kwang S.

2006-12-01

The two dimensional (2D) to three dimensional (3D) transition for the protonated water cluster has been controversial, in particular, for H+(H2O)7. For H+(H2O)7 the 3D structure is predicted to be lower in energy than the 2D structure at most levels of theory without zero-point energy (ZPE) correction. On the other hand, with ZPE correction it is predicted to be either 2D or 3D depending on the calculational levels. Although the ZPE correction favors the 3D structure at the level of coupled cluster theory with singles, doubles, and perturbative triples excitations [CCSD(T)] using the aug-cc-pVDZ basis set, the result based on the anharmonic zero-point vibrational energy correction favors the 2D structure. Therefore, the authors investigated the energies based on the complete basis set limit scheme (which we devised in an unbiased way) at the resolution of the identity approximation Møller-Plesset second order perturbation theory and CCSD(T) levels, and found that the 2D structure has the lowest energy for H+(H2O)7 [though nearly isoenergetic to the 3D structure for D+(D2O)7]. This structure has the Zundel-type configuration, but it shows the quantum probabilistic distribution including some of the Eigen-type configuration. The vibrational spectra of MP2/aug-cc-pVDZ calculations and Car-Parrinello molecular dynamics simulations, taking into account the thermal and dynamic effects, show that the 2D Zundel-type form is in good agreement with experiments.

MULTIMODE quantum calculations of vibrational energies and IR spectrum of the NO⁺(H₂O) cluster using accurate potential energy and dipole moment surfaces.

PubMed

Homayoon, Zahra

2014-09-28

A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO(+)(H2O) cluster is reported. The PES is based on fitting of roughly 32,000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO(+)(H2O) and NO(+)(D2O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO(+)(H2O) and NO(+)(D2O) using the MULTIMODE program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO(+)(H2O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water "antisymmetric" stretching mode with the low-frequency intermolecular modes results in intensity borrowing.

MULTIMODE quantum calculations of vibrational energies and IR spectrum of the NO+(H2O) cluster using accurate potential energy and dipole moment surfaces

NASA Astrophysics Data System (ADS)

Homayoon, Zahra

2014-09-01

A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO+(H2O) cluster is reported. The PES is based on fitting of roughly 32 000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO+(H2O) and NO+(D2O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO+(H2O) and NO+(D2O) using the MULTIMODE program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO+(H2O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water "antisymmetric" stretching mode with the low-frequency intermolecular modes results in intensity borrowing.

Spectroscopic (FT-IR and FT-Raman) investigation, first order hyperpolarizability, NBO, HOMO-LUMO and MEP analysis of 6-nitrochromone by ab initio and density functional theory calculations

NASA Astrophysics Data System (ADS)

Senthil kumar, J.; Jeyavijayan, S.; Arivazhagan, M.

2015-02-01

The vibrational spectral analysis is carried out using FT-Raman and FT-IR spectroscopy in the range 3500-50 cm-1 and 4000-400 cm-1, respectively, for 6-nitrochromone (6NC). The molecular structure, fundamental vibrational frequencies and intensity of the vibrational bands are interpreted with the aid of structure optimization and normal coordinates force field calculation based on ab initio HF and DFT gradient calculations employing the HF/6-311++G(d,p) and B3LYP/6-311++G(d,p) basis set. Stability of the molecule has been analyzed using NBO analysis. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Thermodynamic properties like entropy, heat capacity, zero-point energy and Mulliken's charge analysis have been calculated for the 6NC. The complete assignments were performed on the basis of total energy distribution (TED) of the vibrational modes with scaled quantum mechanical (SQM) method. The MEP map shows the negative potential sites are on oxygen atoms as well as the positive potential sites are around the hydrogen atoms.

Ab initio theoretical calculations of the electronic excitation energies of small water clusters.

PubMed

Tachikawa, Hiroto; Yabushita, Akihiro; Kawasaki, Masahiro

2011-12-14

A direct ab initio molecular dynamics method has been applied to a water monomer and water clusters (H(2)O)(n) (n = 1-3) to elucidate the effects of zero-point energy (ZPE) vibration on the absorption spectra of water clusters. Static ab initio calculations without ZPE showed that the first electronic transitions of (H(2)O)(n), (1)B(1)←(1)A(1), are blue-shifted as a function of cluster size (n): 7.38 eV (n = 1), 7.58 eV (n = 2) and 8.01 eV (n = 3). The inclusion of the ZPE vibration strongly affects the excitation energies of a water dimer, and a long red-tail appears in the range of 6.42-6.90 eV due to the structural flexibility of a water dimer. The ultraviolet photodissociation of water clusters and water ice surfaces is relevant to these results.

Ab initio calculation of reaction energies. III. Basis set dependence of relative energies on the FH2 and H2CO potential energy surfaces

NASA Astrophysics Data System (ADS)

Frisch, Michael J.; Binkley, J. Stephen; Schaefer, Henry F., III

1984-08-01

The relative energies of the stationary points on the FH2 and H2CO nuclear potential energy surfaces relevant to the hydrogen atom abstraction, H2 elimination and 1,2-hydrogen shift reactions have been examined using fourth-order Møller-Plesset perturbation theory and a variety of basis sets. The theoretical absolute zero activation energy for the F+H2→FH+H reaction is in better agreement with experiment than previous theoretical studies, and part of the disagreement between earlier theoretical calculations and experiment is found to result from the use of assumed rather than calculated zero-point vibrational energies. The fourth-order reaction energy for the elimination of hydrogen from formaldehyde is within 2 kcal mol-1 of the experimental value using the largest basis set considered. The qualitative features of the H2CO surface are unchanged by expansion of the basis set beyond the polarized triple-zeta level, but diffuse functions and several sets of polarization functions are found to be necessary for quantitative accuracy in predicted reaction and activation energies. Basis sets and levels of perturbation theory which represent good compromises between computational efficiency and accuracy are recommended.

Electronic torsional sound in linear atomic chains: Chemical energy transport at 1000 km/s

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurnosov, Arkady A.; Rubtsov, Igor V.; Maksymov, Andrii O.

2016-07-21

We investigate entirely electronic torsional vibrational modes in linear cumulene chains. The carbon nuclei of a cumulene are positioned along the primary axis so that they can participate only in the transverse and longitudinal motions. However, the interatomic electronic clouds behave as a torsion spring with remarkable torsional stiffness. The collective dynamics of these clouds can be described in terms of electronic vibrational quanta, which we name torsitons. It is shown that the group velocity of the wavepacket of torsitons is much higher than the typical speed of sound, because of the small mass of participating electrons compared to themore » atomic mass. For the same reason, the maximum energy of the torsitons in cumulenes is as high as a few electronvolts, while the minimum possible energy is evaluated as a few hundred wavenumbers and this minimum is associated with asymmetry of zero point atomic vibrations. Theory predictions are consistent with the time-dependent density functional theory calculations. Molecular systems for experimental evaluation of the predictions are proposed.« less

Theoretical Analysis of Optical Absorption and Emission in Mixed Noble Metal Nanoclusters.

PubMed

Day, Paul N; Pachter, Ruth; Nguyen, Kiet A

2018-04-26

In this work, we studied theoretically two hybrid gold-silver clusters, which were reported to have dual-band emission, using density functional theory (DFT) and linear and quadratic response time-dependent DFT (TDDFT). Hybrid functionals were found to successfully predict absorption and emission, although explanation of the NIR emission from the larger cluster (cluster 1) requires significant vibrational excitation in the final state. For the smaller cluster (cluster 2), the Δ H(0-0) value calculated for the T1 → S0 transition, using the PBE0 functional, is in good agreement with the measured NIR emission, and the calculated T2 → S0 value is in fair agreement with the measured visible emission. The calculated T1 → S0 phosphorescence Δ H(0-0) for cluster 1 is close to the measured visible emission energy. In order for the calculated phosphorescence for cluster 1 to agree with the intense NIR emission reported experimentally, the vibrational energy of the final state (S0) is required to be about 0.7 eV greater than the zero-point vibrational energy.

Very highly excited vibrational states of LiCN using a discrete variable representation

NASA Astrophysics Data System (ADS)

Henderson, James R.; Tennyson, Jonathan

Calculations are presented for the lowest 900 vibrational (J = 0) states of the LiCN floppy system for a two dimensional potential energy surface (rCN frozen). Most of these states lie well above the barrier separating the two linear isomers of the molecule and the point where the classical dynamics of the system becomes chaotic. Analysis of the wavefunctions of individual states in the high energy region shows that while most have an irregular nodal structure, a significant number of states appear regular - corresponding to solutions of standard, 'mode localized' hamiltonians. Motions corresponding in zero-order to Li-CN and Li-NC normal modes as well as free rotor states are identified. The distribution of level spacings is also studied and yields results in good agreement with those obtained by analysing nodal structures.

Can two H2 molecules be inserted into C60 - an accurate first-principles exploration of structural, energetic and vibrational properties of the 2H2@C60 complex

NASA Astrophysics Data System (ADS)

Dolgonos, Grygoriy A.; Peslherbe, Gilles H.

2016-10-01

The 2H2@C60 minimum structure of C2 symmetry has been fully characterized at the density-fitting local second-order Møller-Plesset (DF-LMP2) level of theory. Its uncorrected and zero-point energy (ZPE) corrected complexation energies equal 1.9 and 6.2 kcal/mol, respectively, confirming the instability of the complex. This structure exhibits the largest intermolecular host-guest and guest-guest separations among all the complexes studied in this work. The calculated infrared spectrum of 2H2@C60 does not show any frequency shifts for the modes associated with radial or tangential displacements in C60 (except for one mode), but shows a weak red Hsbnd H vibrational frequency shift.

Delay-controlled primary and stochastic resonances of the SD oscillator with stiffness nonlinearities

NASA Astrophysics Data System (ADS)

Yang, Tao; Cao, Qingjie

2018-03-01

This work presents analytical studies of the stiffness nonlinearities SD (smooth and discontinuous) oscillator under displacement and velocity feedback control with a time delay. The SD oscillator can capture the qualitative characteristics of quasi-zero-stiffness and negative-stiffness. We focus mainly on the primary resonance of the quasi-zero-stiffness SD oscillator and the stochastic resonance (SR) of the negative-stiffness SD oscillator. Using the averaging method, we have been analyzed the amplitude response of the quasi-zero-stiffness SD oscillator. In this regard, the optimum time delay for changing the control intensity according to the optimization standard proposed can be obtained. For the optimum time delay, increasing the displacement feedback intensity is advantageous to suppress the vibrations in resonant regime where vibration isolation is needed, however, increasing the velocity feedback intensity is advantageous to strengthen the vibrations. Moreover, the effects of time-delayed feedback on the SR of the negative-stiffness SD oscillator are investigated under harmonic forcing and Gaussian white noise, based on the Langevin and Fokker-Planck approaches. The time-delayed feedback can enhance the SR phenomenon where vibrational energy harvesting is needed. This paper established the relationship between the parameters and vibration properties of a stiffness nonlinearities SD which provides the guidance for optimizing time-delayed control for vibration isolation and vibrational energy harvesting of the nonlinear systems.

A Systematic Approach for Computing Zero-Point Energy, Quantum Partition Function, and Tunneling Effect Based on Kleinert's Variational Perturbation Theory.

PubMed

Wong, Kin-Yiu; Gao, Jiali

2008-09-09

In this paper, we describe an automated integration-free path-integral (AIF-PI) method, based on Kleinert's variational perturbation (KP) theory, to treat internuclear quantum-statistical effects in molecular systems. We have developed an analytical method to obtain the centroid potential as a function of the variational parameter in the KP theory, which avoids numerical difficulties in path-integral Monte Carlo or molecular dynamics simulations, especially at the limit of zero-temperature. Consequently, the variational calculations using the KP theory can be efficiently carried out beyond the first order, i.e., the Giachetti-Tognetti-Feynman-Kleinert variational approach, for realistic chemical applications. By making use of the approximation of independent instantaneous normal modes (INM), the AIF-PI method can readily be applied to many-body systems. Previously, we have shown that in the INM approximation, the AIF-PI method is accurate for computing the quantum partition function of a water molecule (3 degrees of freedom) and the quantum correction factor for the collinear H(3) reaction rate (2 degrees of freedom). In this work, the accuracy and properties of the KP theory are further investigated by using the first three order perturbations on an asymmetric double-well potential, the bond vibrations of H(2), HF, and HCl represented by the Morse potential, and a proton-transfer barrier modeled by the Eckart potential. The zero-point energy, quantum partition function, and tunneling factor for these systems have been determined and are found to be in excellent agreement with the exact quantum results. Using our new analytical results at the zero-temperature limit, we show that the minimum value of the computed centroid potential in the KP theory is in excellent agreement with the ground state energy (zero-point energy) and the position of the centroid potential minimum is the expectation value of particle position in wave mechanics. The fast convergent property of the KP theory is further examined in comparison with results from the traditional Rayleigh-Ritz variational approach and Rayleigh-Schrödinger perturbation theory in wave mechanics. The present method can be used for thermodynamic and quantum dynamic calculations, including to systematically determine the exact value of zero-point energy and to study kinetic isotope effects for chemical reactions in solution and in enzymes.

Binding matter with antimatter: the covalent positron bond.

PubMed

Charry, Jorge Alfonso; Varella, Marcio T Do N; Reyes, Andrés

2018-05-16

We report sufficient theoretical evidence of the energy stability of the e⁺H₂²⁻ molecule, formed by two H⁻ anions and one positron. Analysis of the electronic and positronic densities of the latter compound undoubtedly points out the formation of a positronic covalent bond between the otherwise repelling hydride anions. The lower limit for the bonding energy of the e⁺H₂²⁻ molecule is 74 kJ/mol (0.77 eV), accounting for the zero-point vibrational correction. The formation of a non electronic covalent bond is fundamentally distinct from positron attachment to stable molecules, as the latter process is characterized by a positron affinity, analogous to the electron affinity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Full-dimensional quantum calculations of the vibrational states of H5(+).

PubMed

Song, Hongwei; Lee, Soo-Ying; Yang, Minghui; Lu, Yunpeng

2013-03-28

Full-dimensional quantum calculations of the vibrational states of H5(+) have been performed on the accurate potential energy surface developed by Xie et al. [J. Chem. Phys. 122, 224307 (2005)]. The zero point energies of H5(+), H4D(+), D4H(+), and D5(+) and their ground-state geometries are presented and compared with earlier theoretical results. The first 10 low-lying excited states of H5(+) are assigned to the fundamental, overtone, and combination of the H2-H3(+) stretch, the shared proton hopping and the out-of-plane torsion. The ground-state torsional tunneling splitting, the fundamental of the photon hopping mode and the first overtone of the torsion mode are 87.3 cm(-1), 354.4 cm(-1), and 444.0 cm(-1), respectively. All of these values agree well with the diffusion Monte Carlo and multi-configuration time-dependent Hartree results where available.

Effects of electron doping on the stability of the metal hydride NaH

NASA Astrophysics Data System (ADS)

Olea-Amezcua, M. A.; Rivas-Silva, J. F.; de la Peña-Seaman, O.; Heid, R.; Bohnen, K. P.

2017-04-01

Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1-x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

A Smart Load Interface and Voltage Regulator for Electrostatic Vibration Energy Harvester

NASA Astrophysics Data System (ADS)

Bedier, Mohammed; Basset, Philippe; Galayko, Dimitri

2016-11-01

This paper presents a new implementation in ams 0.35μm HV technology of a complete energy management system for an electrostatic vibrational energy harvester (e-VEH). It is based on the Bennet's doubler architecture and includes a load voltage regulator (LVR) and a smart Load Interface (LI) that are self-controlled with internal voltages for maximum power point tracking (MMPT). The CMOS implementation makes use of an energy harvester that is capable of producing up to 1.8μW at harmonic excitation, given its internal voltage is kept within its optimum. An intermediate LI stage and its controller makes use of a high side switch with zero static power level shifter, and a low power hysteresis comparator. A full circuit level simulation with a VHDL-AMS model of the e-VEH presented was successfully achieved, indicating that the proposed load interface controller consumes less than 100nW average power. Moreover, a LVR regulates the buffer and discharge the harvested energy into a generic resistive load maintaining the voltage within a nominal value of 2 Volts.

The dissociative chemisorption of methane on Ni(100) and Ni(111): Classical and quantum studies based on the reaction path Hamiltonian

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mastromatteo, Michael; Jackson, Bret, E-mail: jackson@chem.umass.edu

Electronic structure methods based on density functional theory are used to construct a reaction path Hamiltonian for CH{sub 4} dissociation on the Ni(100) and Ni(111) surfaces. Both quantum and quasi-classical trajectory approaches are used to compute dissociative sticking probabilities, including all molecular degrees of freedom and the effects of lattice motion. Both approaches show a large enhancement in sticking when the incident molecule is vibrationally excited, and both can reproduce the mode specificity observed in experiments. However, the quasi-classical calculations significantly overestimate the ground state dissociative sticking at all energies, and the magnitude of the enhancement in sticking with vibrationalmore » excitation is much smaller than that computed using the quantum approach or observed in the experiments. The origin of this behavior is an unphysical flow of zero point energy from the nine normal vibrational modes into the reaction coordinate, giving large values for reaction at energies below the activation energy. Perturbative assumptions made in the quantum studies are shown to be accurate at all energies studied.« less

Mixed quantum/classical investigation of the photodissociation of NH3(Ã) and a practical method for maintaining zero-point energy in classical trajectories

NASA Astrophysics Data System (ADS)

Bonhommeau, David; Truhlar, Donald G.

2008-07-01

The photodissociation dynamics of ammonia upon excitation of the out-of-plane bending mode (mode ν2 with n2=0,…,6 quanta of vibration) in the à electronic state is investigated by means of several mixed quantum/classical methods, and the calculated final-state properties are compared to experiments. Five mixed quantum/classical methods are tested: one mean-field approach (the coherent switching with decay of mixing method), two surface-hopping methods [the fewest switches with time uncertainty (FSTU) and FSTU with stochastic decay (FSTU/SD) methods], and two surface-hopping methods with zero-point energy (ZPE) maintenance [the FSTU /SD+trajectory projection onto ZPE orbit (TRAPZ) and FSTU /SD+minimal TRAPZ (mTRAPZ) methods]. We found a qualitative difference between final NH2 internal energy distributions obtained for n2=0 and n2>1, as observed in experiments. Distributions obtained for n2=1 present an intermediate behavior between distributions obtained for smaller and larger n2 values. The dynamics is found to be highly electronically nonadiabatic with all these methods. NH2 internal energy distributions may have a negative energy tail when the ZPE is not maintained throughout the dynamics. The original TRAPZ method was designed to maintain ZPE in classical trajectories, but we find that it leads to unphysically high internal vibrational energies. The mTRAPZ method, which is new in this work and provides a general method for maintaining ZPE in either single-surface or multisurface trajectories, does not lead to unphysical results and is much less time consuming. The effect of maintaining ZPE in mixed quantum/classical dynamics is discussed in terms of agreement with experimental findings. The dynamics for n2=0 and n2=6 are also analyzed to reveal details not available from experiment, in particular, the time required for quenching of electronic excitation and the adiabatic energy gap and geometry at the time of quenching.

Mixed quantum/classical investigation of the photodissociation of NH3(A) and a practical method for maintaining zero-point energy in classical trajectories.

PubMed

Bonhommeau, David; Truhlar, Donald G

2008-07-07

The photodissociation dynamics of ammonia upon excitation of the out-of-plane bending mode (mode nu(2) with n(2)=0,[ellipsis (horizontal)],6 quanta of vibration) in the A electronic state is investigated by means of several mixed quantum/classical methods, and the calculated final-state properties are compared to experiments. Five mixed quantum/classical methods are tested: one mean-field approach (the coherent switching with decay of mixing method), two surface-hopping methods [the fewest switches with time uncertainty (FSTU) and FSTU with stochastic decay (FSTU/SD) methods], and two surface-hopping methods with zero-point energy (ZPE) maintenance [the FSTUSD+trajectory projection onto ZPE orbit (TRAPZ) and FSTUSD+minimal TRAPZ (mTRAPZ) methods]. We found a qualitative difference between final NH(2) internal energy distributions obtained for n(2)=0 and n(2)>1, as observed in experiments. Distributions obtained for n(2)=1 present an intermediate behavior between distributions obtained for smaller and larger n(2) values. The dynamics is found to be highly electronically nonadiabatic with all these methods. NH(2) internal energy distributions may have a negative energy tail when the ZPE is not maintained throughout the dynamics. The original TRAPZ method was designed to maintain ZPE in classical trajectories, but we find that it leads to unphysically high internal vibrational energies. The mTRAPZ method, which is new in this work and provides a general method for maintaining ZPE in either single-surface or multisurface trajectories, does not lead to unphysical results and is much less time consuming. The effect of maintaining ZPE in mixed quantum/classical dynamics is discussed in terms of agreement with experimental findings. The dynamics for n(2)=0 and n(2)=6 are also analyzed to reveal details not available from experiment, in particular, the time required for quenching of electronic excitation and the adiabatic energy gap and geometry at the time of quenching.

Explicitly correlated coupled cluster calculations for propadienylidene (H(2)CCC).

PubMed

Botschwina, Peter; Oswald, Rainer

2010-09-16

Propadienylidene (H(2)CCC), a reactive carbene of interest to combustion processes and astrochemistry, has been studied by explicitly correlated coupled cluster theory at the CCSD(T)-F12x (x = a, b) level. Vibrational configuration interaction (VCI) has been employed to calculate accurate wavenumbers for the fundamental vibrations of H(2)CCC, D(2)CCC, and HDCCC. The symmetric CH stretching vibration of H(2)CCC is predicted to occur at ν(1) = 2984 cm(-1). Absorptions observed by argon matrix infrared spectroscopy at 3049.5 and 3059.6 cm(-1) are reassigned to the combination tone ν(2) + ν(4), which interacts with ν(1) and is predicted to have a higher intensity than the latter. Furthermore, IR bands detected at 865.4 and 868.8 cm(-1) are assigned to ν(6)(HDCCC), and those observed at 904.0 and 909.8 cm(-1) are assigned to the out-of-plane bending vibration ν(8)(HDCCC). An accurate value of 79.8 +/- 0.2 kJ mol(-1) is recommended for the zero-point vibrational energy of H(2)CCC.

Trajectory Calculations for Bergman Cyclization Predict H/D Kinetic Isotope Effects Due to Nonstatistical Dynamics in the Product.

PubMed

Doubleday, Charles; Boguslav, Mayla; Howell, Caronae; Korotkin, Scott D; Shaked, David

2016-06-22

An unusual H/D kinetic isotope effect (KIE) is described, in which isotopic selectivity arises primarily from nonstatistical dynamics in the product. In DFT-based quasiclassical trajectories of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy, and 28% of nascent p-benzyne recrosses back to the enediyne on a vibrational time scale. The competing process of intramolecular vibrational redistribution (IVR) in p-benzyne is too slow to prevent this. Deuteration increases the rate of IVR, which decreases the fraction of recrossing and increases the yield of statistical (trapable) p-benzyne, 2. Trapable yields for three isotopomers of 2 range from 72% to 86%. The resulting KIEs for Bergman cyclization differ substantially from KIEs predicted by transition state theory, which suggests that IVR in this reaction can be studied by conventional KIEs. Leakage of vibrational zero point energy (ZPE) into the reaction coordinate was probed by trajectories in which initial ZPE in the CH/CD stretching modes was reduced by 25%. This did not change the predicted KIEs.

Ultra-low-frequency vertical vibration isolator based on a two-stage beam structure for absolute gravimetry.

PubMed

Wang, G; Wu, K; Hu, H; Li, G; Wang, L J

2016-10-01

To reduce seismic and environmental vibration noise, ultra-low-frequency vertical vibration isolation systems play an important role in absolute gravimetry. For this purpose, an isolator based on a two-stage beam structure is proposed and demonstrated. The isolator has a simpler and more robust structure than the present ultra-low-frequency vertical active vibration isolators. In the system, two beams are connected to a frame using flexural pivots. The upper beam is suspended from the frame with a normal hex spring and the lower beam is suspended from the upper one using a zero-length spring. The pivot of the upper beam is not vertically above the pivot of the lower beam. With this special design, the attachment points of the zero-length spring to the beams can be moved to adjust the effective stiffness. A photoelectric detector is used to detect the angle between the two beams, and a voice coil actuator attached to the upper beam is controlled by a feedback circuit to keep the angle at a fixed value. The system can achieve a natural period of 100 s by carefully moving the attachment points of the zero-length spring to the beams and tuning the feedback parameters. The system has been used as an inertial reference in the T-1 absolute gravimeter. The experiment results demonstrate that the system has significant vibration isolation performance that holds promise in applications such as absolute gravimeters.

Ultra-low-frequency vertical vibration isolator based on a two-stage beam structure for absolute gravimetry

NASA Astrophysics Data System (ADS)

Wang, G.; Wu, K.; Hu, H.; Li, G.; Wang, L. J.

2016-10-01

To reduce seismic and environmental vibration noise, ultra-low-frequency vertical vibration isolation systems play an important role in absolute gravimetry. For this purpose, an isolator based on a two-stage beam structure is proposed and demonstrated. The isolator has a simpler and more robust structure than the present ultra-low-frequency vertical active vibration isolators. In the system, two beams are connected to a frame using flexural pivots. The upper beam is suspended from the frame with a normal hex spring and the lower beam is suspended from the upper one using a zero-length spring. The pivot of the upper beam is not vertically above the pivot of the lower beam. With this special design, the attachment points of the zero-length spring to the beams can be moved to adjust the effective stiffness. A photoelectric detector is used to detect the angle between the two beams, and a voice coil actuator attached to the upper beam is controlled by a feedback circuit to keep the angle at a fixed value. The system can achieve a natural period of 100 s by carefully moving the attachment points of the zero-length spring to the beams and tuning the feedback parameters. The system has been used as an inertial reference in the T-1 absolute gravimeter. The experiment results demonstrate that the system has significant vibration isolation performance that holds promise in applications such as absolute gravimeters.

The role of large-amplitude motions in the spectroscopy and dynamics of H{sub 5}{sup +}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Zhou; McCoy, Anne B., E-mail: mccoy@chemistry.ohio-state.edu

2014-03-21

Protonated hydrogen dimer, H{sub 5}{sup +}, is the intermediate in the astrochemically important proton transfer reaction between H{sub 3}{sup +} and H{sub 2}. To understand the mechanism for this process, we focus on how large amplitude motions in H{sub 5}{sup +} result in scrambling of the five hydrogen atoms in the collision complex. To this end, the one-dimensional zero-point corrected potential surfaces were mapped out as functions of reaction coordinates for the H{sub 3}{sup +} + H{sub 2} collision using minimized energy path diffusion Monte Carlo [C. E. Hinkle and A. B. McCoy, J. Phys. Chem. Lett. 1, 562 (2010)].more » In this study, the previously developed approach was extended to allow for the investigation of selected excited states that are expected to be involved in the proton scrambling dynamics. Specifically, excited states in the shared proton motion between the two H{sub 2} groups, and in the outer H{sub 2} bending motions were investigated. Of particular interest is the minimum distance between H{sub 3}{sup +} and H{sub 2} at which all five hydrogen atoms become free to exchange. In addition, this diffusion Monte Carlo-based approach was used to determine the zero-point energy E{sub 0}, the dissociation energy D{sub 0}, and excitation energies associated with the vibrational motions that were investigated. The evolution of the wave functions was also studied, with a focus on how the intramolecular vibrations in H{sub 5}{sup +} evolve into motions of H{sub 3}{sup +} or H{sub 2}. In the case of the proton scrambling, we find that the relevant transition states become fully accessible at separations between H{sub 3}{sup +} and H{sub 2} of approximately 2.15 Å, a distance that is accessed by the excited states of H{sub 5}{sup +} with two or more quanta in the shared proton stretch. The implications of this finding on the vibrational spectroscopy of H{sub 5}{sup +} are also discussed.« less

DFT studies on the multi-channel reaction of CH3S+NO2

NASA Astrophysics Data System (ADS)

Tang, Yi-Zhen; Sun, Hao; Pan, Ya-Ru; Pan, Xiu-Mei; Wang, Rong-Shun

The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero-point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6-311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6-311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO.

Quasiclassical trajectory studies of the O(3P) + CX4(vk = 0, 1) → OXv + CX3(n1n2n3n4) [X = H and D] reactions on an ab initio potential energy surface.

PubMed

Czakó, Gábor; Liu, Rui; Yang, Minghui; Bowman, Joel M; Guo, Hua

2013-08-01

We report quasiclassical trajectory calculations of the integral and differential cross sections and the mode-specific product state distributions for the "central-barrier" O((3)P) + CH4/CD4(vk = 0, 1) [k = 1, 2, 3, 4] reactions using a full-dimensional ab initio potential energy surface. The mode-specific vibrational distributions for the polyatomic methyl products are obtained by doing a normal-mode analysis in the Eckart frame, followed by standard histogram binning (HB) and energy-based Gaussian binning (1GB). The reactant bending excitations slightly enhance the reactivity, whereas stretching excitations activate the reaction more efficiently. None of the reactant vibrational excitations is as efficient as an equivalent amount of translational energy to promote the reactions. The excitation functions without product zero-point energy (ZPE) constraint are in good agreement with previous 8-dimensional quantum mechanical (QM) results for the ground-state and stretching-excited O + CH4 reactions, whereas for the bending-excited reactions the soft ZPE constraint, which is applied to the sum of the product vibrational energies, provides better agreement with the QM cross sections. All angular distributions show the dominance of backward scattering indicating a direct rebound mechanism, in agreement with experiment. The title reactions produce mainly OH/OD(v = 0) products for all the initial states. HB significantly overestimates the populations of OH/OD(v = 1), especially in the energetic threshold regions, whereas 1GB provides physically correct results. The CH3/CD3 vibrational distributions show dominant populations for ground (v = 0), umbrella-excited (v2 = 1, 2), in-plane-bending-excited (v4 = 1), and v2 + v4 methyl product states. Neither translational energy nor reactant vibrational excitation transfers significantly into product vibrations.

Spectroscopic study on deuterated benzenes. III. Vibronic structure and dynamics in the S1 state

NASA Astrophysics Data System (ADS)

Kunishige, Sachi; Katori, Toshiharu; Kawabata, Megumi; Yamanaka, Takaya; Baba, Masaaki

2015-12-01

We observed the fluorescence excitation spectra and mass-selected resonance enhanced multiphoton ionization (REMPI) excitation spectra for the 6 01 , 6 01 10 1 , and 6 01 10 2 bands of the S1←S0 transition of jet-cooled deuterated benzene and assigned the vibronic bands of C6D6 and C6HD5. The 60 1 10 n (n = 0, 1, 2) and 00 0 transition energies were found to be dependent only on the number of D atoms (ND), which was reflected by the zero-point energy of each H/D isotopomer. In some isotopomers some bands, such as those of out-of-plane vibrations mixed with 611n, make the spectra complex. These included the 611021n level or combination bands with ν12 which are allowed because of reduced molecular symmetry. From the lifetime measurements of each vibronic band, some enhancement of the nonradiative intramolecular vibrational redistribution (IVR) process was observed. It was also found that the threshold excess energy of "channel three" was higher than the 6112 levels, which were similar for all the H/D isotopomers. We suggest that the channel three nonradiative process could be caused mainly by in-plane processes such as IVR and internal conversion at the high vibrational levels in the S1 state of benzene, although the out-of-plane vibrations might contribute to some degree.

F + H/sub 2/ potential energy surface: the ecstasy and the agony

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaefer, H.F. III

1985-12-05

This account surveys 14 years of more or less continuing theoretical research on the FH/sub 2/ potential energy hypersurface. Early encouragement concerning the ability of theory to reliably characterize the entrance barrier for F + H/sub 2/ ..-->.. FH + H has more recently been sobered by the realization that very high levels of theory are required for this task. The importance of zero-point vibrational corrections and tunneling corrections in reliable predictions of the same activation energy is discussed. In contrast, the barrier height of H + FH ..-->.. HF + H three-center exchange stands as a prominent early successmore » of ab initio molecular electronic structure theory. 90 references, 4 figures, 6 tables.« less

Probing the global potential energy minimum of (CH2O)2: THz absorption spectrum of (CH2O)2 in solid neon and para-hydrogen.

PubMed

Andersen, J; Voute, A; Mihrin, D; Heimdal, J; Berg, R W; Torsson, M; Wugt Larsen, R

2017-06-28

The true global potential energy minimum configuration of the formaldehyde dimer (CH 2 O) 2 , including the presence of a single or a double weak intermolecular CH⋯O hydrogen bond motif, has been a long-standing subject among both experimentalists and theoreticians as two different energy minima conformations of C s and C 2h symmetry have almost identical energies. The present work demonstrates how the class of large-amplitude hydrogen bond vibrational motion probed in the THz region provides excellent direct spectroscopic observables for these weak intermolecular CH⋯O hydrogen bond motifs. The combination of concentration dependency measurements, observed isotopic spectral shifts associated with H/D substitutions and dedicated annealing procedures, enables the unambiguous assignment of three large-amplitude infrared active hydrogen bond vibrational modes for the non-planar C s configuration of (CH 2 O) 2 embedded in cryogenic neon and enriched para-hydrogen matrices. A (semi)-empirical value for the change of vibrational zero-point energy of 5.5 ± 0.3 kJ mol -1 is proposed for the dimerization process. These THz spectroscopic observations are complemented by CCSD(T)-F12/aug-cc-pV5Z (electronic energies) and MP2/aug-cc-pVQZ (force fields) electronic structure calculations yielding a (semi)-empirical value of 13.7 ± 0.3 kJ mol -1 for the dissociation energy D 0 of this global potential energy minimum.

Probing the global potential energy minimum of (CH2O)2: THz absorption spectrum of (CH2O)2 in solid neon and para-hydrogen

NASA Astrophysics Data System (ADS)

Andersen, J.; Voute, A.; Mihrin, D.; Heimdal, J.; Berg, R. W.; Torsson, M.; Wugt Larsen, R.

2017-06-01

The true global potential energy minimum configuration of the formaldehyde dimer (CH2O)2, including the presence of a single or a double weak intermolecular CH⋯O hydrogen bond motif, has been a long-standing subject among both experimentalists and theoreticians as two different energy minima conformations of Cs and C2h symmetry have almost identical energies. The present work demonstrates how the class of large-amplitude hydrogen bond vibrational motion probed in the THz region provides excellent direct spectroscopic observables for these weak intermolecular CH⋯O hydrogen bond motifs. The combination of concentration dependency measurements, observed isotopic spectral shifts associated with H/D substitutions and dedicated annealing procedures, enables the unambiguous assignment of three large-amplitude infrared active hydrogen bond vibrational modes for the non-planar Cs configuration of (CH2O)2 embedded in cryogenic neon and enriched para-hydrogen matrices. A (semi)-empirical value for the change of vibrational zero-point energy of 5.5 ± 0.3 kJ mol-1 is proposed for the dimerization process. These THz spectroscopic observations are complemented by CCSD(T)-F12/aug-cc-pV5Z (electronic energies) and MP2/aug-cc-pVQZ (force fields) electronic structure calculations yielding a (semi)-empirical value of 13.7 ± 0.3 kJ mol-1 for the dissociation energy D0 of this global potential energy minimum.

Germylenes: structures, electron affinities, and singlet-triplet gaps of the conventional XGeCY(3) (X = H, F, Cl, Br, and I; Y = F and Cl) species and the unexpected cyclic XGeCY(3) (Y = Br and I) systems.

PubMed

Bundhun, Ashwini; Abdallah, Hassan H; Ramasami, Ponnadurai; Schaefer, Henry F

2010-12-23

A systematic investigation of the X-Ge-CY(3) (X = H, F, Cl, Br, and I; Y = F, Cl, Br, and I) species is carried out using density functional theory. The basis sets used for all atoms (except iodine) in this work are of double-ζ plus polarization quality with additional s- and p-type diffuse functions, and denoted DZP++. Vibrational frequency analyses are performed to evaluate zero-point energy corrections and to determine the nature of the stationary points located. Predicted are four different forms of neutral-anion separations: adiabatic electron affinity (EA(ad)), zero-point vibrational energy corrected EA(ad(ZPVE)), vertical electron affinity (EA(vert)), and vertical detachment energy (VDE). The electronegativity (χ) reactivity descriptor for the halogens (X = F, Cl, Br, and I) is used as a tool to assess the interrelated properties of these germylenes. The topological position of the halogen atom bound to the divalent germanium center is well correlated with the trend in the electron affinities and singlet-triplet gaps. For the expected XGeCY(3) structures (X = H, F, Cl, Br, and I; Y = F and Cl), the predicted trend in the electron affinities is well correlated with simpler germylene derivatives (J. Phys. Chem. A 2009, 113, 8080). The predicted EA(ad(ZPVE)) values with the BHLYP functional range from 1.66 eV (FGeCCl(3)) to 2.20 eV (IGeCF(3)), while the singlet-triplet splittings range from 1.28 eV (HGeCF(3)) to 2.22 eV (FGeCCl(3)). The XGeCY(3) (Y = Br and I) species are most often characterized by three-membered cyclic systems involving the divalent germanium atom, the carbon atom, and a halogen atom.

Alchemical and structural distribution based representation for universal quantum machine learning

NASA Astrophysics Data System (ADS)

Faber, Felix A.; Christensen, Anders S.; Huang, Bing; von Lilienfeld, O. Anatole

2018-06-01

We introduce a representation of any atom in any chemical environment for the automatized generation of universal kernel ridge regression-based quantum machine learning (QML) models of electronic properties, trained throughout chemical compound space. The representation is based on Gaussian distribution functions, scaled by power laws and explicitly accounting for structural as well as elemental degrees of freedom. The elemental components help us to lower the QML model's learning curve, and, through interpolation across the periodic table, even enable "alchemical extrapolation" to covalent bonding between elements not part of training. This point is demonstrated for the prediction of covalent binding in single, double, and triple bonds among main-group elements as well as for atomization energies in organic molecules. We present numerical evidence that resulting QML energy models, after training on a few thousand random training instances, reach chemical accuracy for out-of-sample compounds. Compound datasets studied include thousands of structurally and compositionally diverse organic molecules, non-covalently bonded protein side-chains, (H2O)40-clusters, and crystalline solids. Learning curves for QML models also indicate competitive predictive power for various other electronic ground state properties of organic molecules, calculated with hybrid density functional theory, including polarizability, heat-capacity, HOMO-LUMO eigenvalues and gap, zero point vibrational energy, dipole moment, and highest vibrational fundamental frequency.

Theoretical characterization of the minimum energy path for hydrogen atom addition to N2 - Implications for the unimolecular lifetime of HN2

NASA Technical Reports Server (NTRS)

Walch, Stephen P.; Duchovic, Ronald J.; Rohlfing, Celeste Mcmichael

1989-01-01

Results are reported from CASSCF externally contracted CI ab initio computations of the minimum-energy path for the addition of H to N2. The theoretical basis and numerical implementation of the computations are outlined, and the results are presented in extensive tables and graphs and characterized in detail. The zero-point-corrected barrier for HN2 dissociation is estimated as 8.5 kcal/mol, and the lifetime of the lowest-lying quasi-bound vibrational state of HN2 is found to be between 88 psec and 5.8 nsec (making experimental observation of this species very difficult).

Tunneling splitting in double-proton transfer: direct diagonalization results for porphycene.

PubMed

Smedarchina, Zorka; Siebrand, Willem; Fernández-Ramos, Antonio

2014-11-07

Zero-point and excited level splittings due to double-proton tunneling are calculated for porphycene and the results are compared with experiment. The calculation makes use of a multidimensional imaginary-mode Hamiltonian, diagonalized directly by an effective reduction of its dimensionality. Porphycene has a complex potential energy surface with nine stationary configurations that allow a variety of tunneling paths, many of which include classically accessible regions. A symmetry-based approach is used to show that the zero-point level, although located above the cis minimum, corresponds to concerted tunneling along a direct trans - trans path; a corresponding cis - cis path is predicted at higher energy. This supports the conclusion of a previous paper [Z. Smedarchina, W. Siebrand, and A. Fernández-Ramos, J. Chem. Phys. 127, 174513 (2007)] based on the instanton approach to a model Hamiltonian of correlated double-proton transfer. A multidimensional tunneling Hamiltonian is then generated, based on a double-minimum potential along the coordinate of concerted proton motion, which is newly evaluated at the RI-CC2/cc-pVTZ level of theory. To make it suitable for diagonalization, its dimensionality is reduced by treating fast weakly coupled modes in the adiabatic approximation. This results in a coordinate-dependent mass of tunneling, which is included in a unique Hermitian form into the kinetic energy operator. The reduced Hamiltonian contains three symmetric and one antisymmetric mode coupled to the tunneling mode and is diagonalized by a modified Jacobi-Davidson algorithm implemented in the Jadamilu software for sparse matrices. The results are in satisfactory agreement with the observed splitting of the zero-point level and several vibrational fundamentals after a partial reassignment, imposed by recently derived selection rules. They also agree well with instanton calculations based on the same Hamiltonian.

Refined energetic ordering for sulphate-water (n = 3-6) clusters using high-level electronic structure calculations

NASA Astrophysics Data System (ADS)

Lambrecht, Daniel S.; McCaslin, Laura; Xantheas, Sotiris S.; Epifanovsky, Evgeny; Head-Gordon, Martin

2012-10-01

This work reports refinements of the energetic ordering of the known low-energy structures of sulphate-water clusters ? (n = 3-6) using high-level electronic structure methods. Coupled cluster singles and doubles with perturbative triples (CCSD(T)) is used in combination with an estimate of basis set effects up to the complete basis set limit using second-order Møller-Plesset theory. Harmonic zero-point energy (ZPE), included at the B3LYP/6-311 + + G(3df,3pd) level, was found to have a significant effect on the energetic ordering. In fact, we show that the energetic ordering is a result of a delicate balance between the electronic and vibrational energies. Limitations of the ZPE calculations, both due to electronic structure errors, and use of the harmonic approximation, probably constitute the largest remaining errors. Due to the often small energy differences between cluster isomers, and the significant role of ZPE, deuteration can alter the relative energies of low-lying structures, and, when it is applied in conjunction with calculated harmonic ZPEs, even alters the global minimum for n = 5. Experiments on deuterated clusters, as well as more sophisticated vibrational calculations, may therefore be quite interesting.

Low-rank canonical-tensor decomposition of potential energy surfaces: application to grid-based diagrammatic vibrational Green's function theory

DOE PAGES

Rai, Prashant; Sargsyan, Khachik; Najm, Habib; ...

2017-03-07

Here, a new method is proposed for a fast evaluation of high-dimensional integrals of potential energy surfaces (PES) that arise in many areas of quantum dynamics. It decomposes a PES into a canonical low-rank tensor format, reducing its integral into a relatively short sum of products of low-dimensional integrals. The decomposition is achieved by the alternating least squares (ALS) algorithm, requiring only a small number of single-point energy evaluations. Therefore, it eradicates a force-constant evaluation as the hotspot of many quantum dynamics simulations and also possibly lifts the curse of dimensionality. This general method is applied to the anharmonic vibrationalmore » zero-point and transition energy calculations of molecules using the second-order diagrammatic vibrational many-body Green's function (XVH2) theory with a harmonic-approximation reference. In this application, high dimensional PES and Green's functions are both subjected to a low-rank decomposition. Evaluating the molecular integrals over a low-rank PES and Green's functions as sums of low-dimensional integrals using the Gauss–Hermite quadrature, this canonical-tensor-decomposition-based XVH2 (CT-XVH2) achieves an accuracy of 0.1 cm -1 or higher and nearly an order of magnitude speedup as compared with the original algorithm using force constants for water and formaldehyde.« less

Low-rank canonical-tensor decomposition of potential energy surfaces: application to grid-based diagrammatic vibrational Green's function theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rai, Prashant; Sargsyan, Khachik; Najm, Habib

Here, a new method is proposed for a fast evaluation of high-dimensional integrals of potential energy surfaces (PES) that arise in many areas of quantum dynamics. It decomposes a PES into a canonical low-rank tensor format, reducing its integral into a relatively short sum of products of low-dimensional integrals. The decomposition is achieved by the alternating least squares (ALS) algorithm, requiring only a small number of single-point energy evaluations. Therefore, it eradicates a force-constant evaluation as the hotspot of many quantum dynamics simulations and also possibly lifts the curse of dimensionality. This general method is applied to the anharmonic vibrationalmore » zero-point and transition energy calculations of molecules using the second-order diagrammatic vibrational many-body Green's function (XVH2) theory with a harmonic-approximation reference. In this application, high dimensional PES and Green's functions are both subjected to a low-rank decomposition. Evaluating the molecular integrals over a low-rank PES and Green's functions as sums of low-dimensional integrals using the Gauss–Hermite quadrature, this canonical-tensor-decomposition-based XVH2 (CT-XVH2) achieves an accuracy of 0.1 cm -1 or higher and nearly an order of magnitude speedup as compared with the original algorithm using force constants for water and formaldehyde.« less

A converged calculation of the energy barrier to internal rotation in the ethylene-sulfur dioxide dimer

NASA Astrophysics Data System (ADS)

Resende, Stella M.; De Almeida, Wagner B.; van Duijneveldt-van de Rijdt, Jeanne G. C. M.; van Duijneveldt, Frans B.

2001-08-01

Geometrical parameters for the equilibrium (MIN) and lowest saddle-point (TS) geometries of the C2H4⋯SO2 dimer, and the corresponding binding energies, were calculated using the Hartree-Fock and correlated levels of ab initio theory, in basis sets ranging from the D95(d,p) double-zeta basis set to the aug-cc-pVQZ correlation consistent basis set. An assessment of the effect of the basis set superposition error (BSSE) on these results was made. The dissociation energy from the lowest vibrational state was estimated to be 705±100 cm-1 at the basis set limit, which is well within the range expected from experiment. The barrier to internal rotation was found to be 53±5 cm-1, slightly higher than the (revised) experimental result of 43 cm-1, probably due to zero-point vibrational effects. Our results clearly show that, in direct contrast with recent ideas, the BSSE correction affects differentially the MIN and TS binding energies and so has to be included in the calculation of small energy barriers such as that in the C2H4⋯SO2 dimer. Previous reports of positive MP2 frozen-core binding energies for this complex in basis D95(d,p) are confirmed. The anomalies are shown to be an artifact arising from an incorrect removal of virtual orbitals by the default frozen-core option in the GAUSSIAN program.

Analysis of the A ∼ - X ∼ bands of the ethynyl radical near 1.48 μ m and re-evaluation of X ∼ state energies

NASA Astrophysics Data System (ADS)

Le, A. T.; Gross, Eisen C.; Hall, Gregory E.; Sears, Trevor J.

2018-07-01

We report the observation and analysis of spectra in part of the near-infrared spectrum of C2H, originating in rotational levels in the ground and lowest two excited bending vibrational levels of the ground X ˜ 2Σ+ state. In the analysis, we have combined present and previously reported high resolution spectroscopic data for the lower levels involved in the transitions to determine significantly improved molecular constants to describe the fine and hyperfine split rotational levels of the radical in the zero point, v2 = 1 and the 2Σ+ component of v2 = 2 . Two of the upper state vibronic levels involved had not been observed previously. The data and analysis indicate the electronic wavefunction character changes with bending vibrational excitation in the ground state and provide avenues for future measurements of reactivity of the radical as a function of vibrational excitation.

Applicability of Quantum Thermal Baths to Complex Many-Body Systems with Various Degrees of Anharmonicity.

PubMed

Hernández-Rojas, Javier; Calvo, Florent; Noya, Eva Gonzalez

2015-03-10

The semiclassical method of quantum thermal baths by colored noise thermostats has been used to simulate various atomic systems in the molecular and bulk limits, at finite temperature and in moderately to strongly anharmonic regimes. In all cases, the method performs relatively well against alternative approaches in predicting correct energetic properties, including in the presence of phase changes, provided that vibrational delocalization is not too strong-neon appearing already as an upper limiting case. In contrast, the dynamical behavior inferred from global indicators such as the root-mean-square bond length fluctuation index or the vibrational spectrum reveals more marked differences caused by zero-point energy leakage, except in the case of isolated molecules with well separated vibrational modes. To correct for such deficiencies and reduce the undesired transfer among modes, empirical modifications of the noise power spectral density were attempted to better describe thermal equilibrium but still failed when used as semiclassical preparation for microcanonical trajectories.

Analysis of the $$\\tilde{A}$$ - $$\\tilde{X}$$ bands of the Ethynyl Radical near 1.48 μ-m and Re-evaluation of ~X State Energies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Le, A T.; Gross, Eisen C.; Hall, Gregory E.

Here, we report the observation and analysis of spectra in part of the near-infrared spectrum of C 2H, originating in rotational levels in the ground and lowest two excited bending vibrational levels of the groundmore » $$\\tilde{X}$$ 2Σ+ state. In the analysis, we have combined present and previously reported high resolution spectroscopic data for the lower levels involved in the transitions to determine significantly improved molecular constants to describe the fine and hyperfine split rotational levels of the radical in the zero point, v 2 = 1 and the 2Σ+ component of v 2 = 2. Two of the upper state vibronic levels involved had not been observed previously. The data and analysis indicate the electronic wavefunction character changes with bending vibrational excitation in the ground state and provide avenues for future measurements of reactivity of the radical as a function of vibrational excitation.« less

Analysis of the $$\\tilde{A}$$ - $$\\tilde{X}$$ bands of the Ethynyl Radical near 1.48 μ-m and Re-evaluation of ~X State Energies

DOE PAGES

Le, A T.; Gross, Eisen C.; Hall, Gregory E.; ...

2018-05-15

Here, we report the observation and analysis of spectra in part of the near-infrared spectrum of C 2H, originating in rotational levels in the ground and lowest two excited bending vibrational levels of the groundmore » $$\\tilde{X}$$ 2Σ+ state. In the analysis, we have combined present and previously reported high resolution spectroscopic data for the lower levels involved in the transitions to determine significantly improved molecular constants to describe the fine and hyperfine split rotational levels of the radical in the zero point, v 2 = 1 and the 2Σ+ component of v 2 = 2. Two of the upper state vibronic levels involved had not been observed previously. The data and analysis indicate the electronic wavefunction character changes with bending vibrational excitation in the ground state and provide avenues for future measurements of reactivity of the radical as a function of vibrational excitation.« less

Vibration and Vibration-Torsion Levels of the S_{1} and Ground Cationic D_{0}^{+} States of Para-Fluorotoluene and Para-Xylene Below 1000 \\wn

NASA Astrophysics Data System (ADS)

Tuttle, William Duncan; Gardner, Adrian M.; Whalley, Laura E.; Wright, Timothy G.

2017-06-01

We have employed resonance-enhanced multiphoton ionisation (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy to investigate the first excited electronic singlet (S_{1}) state and the cationic ground state (D_{0}^{+}) of para-fluorotoluene (pFT) and para-xylene (pXyl). Spectra have been recorded via a large number of selected intermediate levels, to support assignment of the vibration and vibration-torsion levels in these molecules and to investigate possible couplings. The study of levels in this region builds upon previous work on the lower energy regions of pFT and pXyl and here we are interested in how vibration-torsion (vibtor) levels might combine and interact with vibrational ones, and so we consider the possible couplings which occur. Comparisons between the spectra of the two molecules show a close correspondence, and the influence of the second methyl rotor in para-xylene on the onset of intramolecular vibrational redistribution (IVR) in the S_{1} state is a point of interest. This has bearing on future work which will need to consider the role of both more flexible side chains of substituted benzene molecules, and multiple side chains. A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). A. M. Gardner, W. D. Tuttle, P. Groner and T. G. Wright, J. Chem. Phys., (2017, in press). W. D. Tuttle, A. M. Gardner, K. O'Regan, W. Malewicz and T. G. Wright, J. Chem. Phys., (2017, in press).

A global ab initio potential for HCN/HNC, exact vibrational energies, and comparison to experiment

NASA Technical Reports Server (NTRS)

Bentley, Joseph A.; Bowman, Joel M.; Gazdy, Bela; Lee, Timothy J.; Dateo, Christopher E.

1992-01-01

An ab initio (i.e., from first principles) calculation of vibrational energies of HCN and HNC is reported. The vibrational calculations were done with a new potential derived from a fit to 1124 ab initio electronic energies which were calculated using the highly accurate CCSD(T) coupled-cluster method in conjunction with a large atomic natural orbital basis set. The properties of this potential are presented, and the vibrational calculations are compared to experiment for 54 vibrational transitions, 39 of which are for zero total angular momentum, J = 0, and 15 of which are for J = 1. The level of agreement with experiment is unprecedented for a triatomic with two nonhydrogen atoms, and demonstrates the capability of the latest computational methods to give reliable predictions on a strongly bound triatomic molecule at very high levels of vibrational excitation.

A new potential energy surface for vibration-vibration coupling in HF-HF collisions. Formulation and quantal scattering calculations

NASA Astrophysics Data System (ADS)

Schwenke, David W.; Truhlar, Donald G.

1988-04-01

We present new ab initio calculations of the HF-HF interaction potential for the case where both molecules are simultaneously displaced from their equilibrium internuclear distance. These and previous ab initio calculations are then fit to a new analytic representation which is designed to be efficient to evaluate and to provide an especially faithful account of the forces along the vibrational coordinates. We use the new potential for two sets of quantal scattering calculations for collisions in three dimensions with total angular momentum zero. First we test that the angular harmonic representation of the anisotropy is adequate by comparing quantal rigid rotator calculations to those carried out for potentials involving higher angular harmonics and for which the expansion in angular harmonics is systematically increased to convergence. Then we carry out large-scale quantal calculations of vibration-vibration energy transfer including the coupling of both sets of vibrational and rotational coordinates. These calculations indicate that significant rotational energy transfer accompanies the vibration-to-vibration energy transfer process.

Spectroscopy of the UO+2 cation and the delayed ionization of UO2.

PubMed

Merritt, Jeremy M; Han, Jiande; Heaven, Michael C

2008-02-28

Vibronically resolved spectra for the UO+2 cation have been recorded using the pulsed field ionization zero electron kinetic energy (PFI-ZEKE) technique. For the ground state, long progressions in both the bending and symmetric stretch vibrations were observed. Bend and stretch progressions of the first electronically excited state were also observed, and the origin was found at an energy of 2678 cm(-1) above the ground state zero-point level. This observation is consistent with a recent theoretical prediction [Infante et al., J. Chem. Phys. 127, 124308 (2007)]. The ionization energy for UO2, derived from the PFI-ZEKE spectrum, namely, 6.127(1) eV, is in excellent agreement with the value obtained from an earlier photoionization efficiency measurement. Delayed ionization of UO2 in the gas phase has been reported previously [Han et al., J. Chem. Phys. 120, 5155 (2004)]. Here, we extend the characterization of the delayed ionization process by performing a quantitative study of the ionization rate as a function of the energy above the ionization threshold. The ionization rate was found to be 5 x 10(6) s(-1) at threshold, and increased linearly with increasing energy in the range investigated (0-1200 cm(-1)).

The Renner-Teller effect in HCCCl(+)(X̃(2)Π) studied by zero-kinetic energy photoelectron spectroscopy and ab initio calculations.

PubMed

Sun, Wei; Dai, Zuyang; Wang, Jia; Mo, Yuxiang

2015-05-21

The spin-vibronic energy levels of the chloroacetylene cation up to 4000 cm(-1) above the ground state have been measured using the one-photon zero-kinetic energy photoelectron spectroscopic method. The spin-vibronic energy levels have also been calculated using a diabatic model, in which the potential energy surfaces are expressed by expansions of internal coordinates, and the Hamiltonian matrix equation is solved using a variational method with harmonic basis functions. The calculated spin-vibronic energy levels are in good agreement with the experimental data. The Renner-Teller (RT) parameters describing the vibronic coupling for the H-C≡C bending mode (ε4), Cl-C≡C bending mode (ε5), the cross-mode vibronic coupling (ε45) of the two bending vibrations, and their vibrational frequencies (ω4 and ω5) have also been determined using an effective Hamiltonian matrix treatment. In comparison with the spin-orbit interaction, the RT effect in the H-C≡C bending (ε4) mode is strong, while the RT effect in the Cl-C≡C bending mode is weak. There is a strong cross-mode vibronic coupling of the two bending vibrations, which may be due to a vibronic resonance between the two bending vibrations. The spin-orbit energy splitting of the ground state has been determined for the first time and is found to be 209 ± 2 cm(-1).

Quantum-Chemical Study of the Adsorption of DMMP and Sarin on gamma-Al2O3

DTIC Science & Technology

2007-02-01

In this and in the following section, ∆Eads is not corrected for zero-point vibrational energy ( ZPE ); however, a counterpoise correction for basis set...Ångstroms and the bond angle is in degrees. Values in parentheses are BSSE-corrected (∆Eads C ) results. ∆Eads has not been corrected for ZPE . b 6-31G...sets. The ∆ Eads C values are given in parentheses. No ZPE corrections have been applied. e The basis sets used were 6-311G(df) for Sarin and for the Al

Ab Initio energetics of SiO bond cleavage.

PubMed

Hühn, Carolin; Erlebach, Andreas; Mey, Dorothea; Wondraczek, Lothar; Sierka, Marek

2017-10-15

A multilevel approach that combines high-level ab initio quantum chemical methods applied to a molecular model of a single, strain-free SiOSi bridge has been used to derive accurate energetics for SiO bond cleavage. The calculated SiO bond dissociation energy and the activation energy for water-assisted SiO bond cleavage of 624 and 163 kJ mol -1 , respectively, are in excellent agreement with values derived recently from experimental data. In addition, the activation energy for H 2 O-assisted SiO bond cleavage is found virtually independent of the amount of water molecules in the vicinity of the reaction site. The estimated reaction energy for this process including zero-point vibrational contribution is in the range of -5 to 19 kJ mol -1 . © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

A density functional theory study on the effect of zero-point energy corrections on the methanation profile on Fe(100).

PubMed

Govender, Ashriti; Ferré, Daniel Curulla; Niemantsverdriet, J W Hans

2012-04-23

The thermodynamics and kinetics of the surface hydrogenation of adsorbed atomic carbon to methane, following the reaction sequence C+4H(-->/<--)CH+3H(-->/<--)CH(2)+2H(-->/<--)CH(3)+H(-->/<--)CH(4), are studied on Fe(100) by means of density functional theory. An assessment is made on whether the adsorption energies and overall energy profile are affected when zero-point energy (ZPE) corrections are included. The C, CH and CH(2) species are most stable at the fourfold hollow site, while CH(3) prefers the twofold bridge site. Atomic hydrogen is adsorbed at both the twofold bridge and fourfold hollow sites. Methane is physisorbed on the surface and shows neither orientation nor site preference. It is easily desorbed to the gas phase once formed. The incorporation of ZPE corrections has a very slight, if any, effect on the adsorption energies and does not alter the trends with regards to the most stable adsorption sites. The successive addition of hydrogen to atomic carbon is endothermic up to the addition of the third hydrogen atom resulting in the methyl species, but exothermic in the final hydrogenation step, which leads to methane. The overall methanation reaction is endothermic when starting from atomic carbon and hydrogen on the surface. Zero-point energy corrections are rarely provided in the literature. Since they are derived from C-H bonds with characteristic vibrations on the order of 2500-3000 cm(-1), the equivalent ZPE of 1/2 hν is on the order of 0.2-0.3 eV and its effect on adsorption energy can in principle be significant. Particularly in reactions between CH(x) and H, the ZPE correction is expected to be significant, as additional C-H bonds are formed. In this instance, the methanation reaction energy of +0.77 eV increased to +1.45 eV with the inclusion of ZPE corrections, that is, less favourable. Therefore, it is crucial to include ZPE corrections when reporting reactions involving hydrogen-containing species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular structure of the trans and cis isomers of metal-free phthalocyanine studied by gas-phase electron diffraction and high-level quantum chemical calculations: NH tautomerization and calculated vibrational frequencies.

PubMed

Strenalyuk, Tatyana; Samdal, Svein; Volden, Hans Vidar

2008-05-29

The molecular structure of the trans isomer of metal-free phthalocyanine (H2Pc) is determined using the gas electron diffraction (GED) method and high-level quantum chemical calculations. B3LYP calculations employing the basis sets 6-31G**, 6-311++G**, and cc-pVTZ give two tautomeric isomers for the inner H atoms, a trans isomer having D2h symmetry and a cis isomer having C2v symmetry. The trans isomer is calculated to be 41.6 (B3LYP/6-311++G**, zero-point corrected) and 37.3 kJ/mol (B3LYP/cc-pVTZ, not zero-point corrected) more stable than the cis isomer. However, Hartree-Fock (HF) calculations using different basis sets predict that cis is preferred and that trans does not exist as a stable form of the molecule. The equilibrium composition in the gas phase at 471 degrees C (the temperature of the GED experiment) calculated at the B3LYP/6-311++G** level is 99.8% trans and 0.2% cis. This is in very good agreement with the GED data, which indicate that the mole fraction of the cis isomer is close to zero. The transition states for two mechanisms of the NH tautomerization have been characterized. A concerted mechanism where the two H atoms move simultaneously yields a transition state of D2h symmetry and an energy barrier of 95.8 kJ/mol. A two-step mechanism where a trans isomer is converted to a cis isomer, which is converted into another trans isomer, proceeds via two transition states of C(s) symmetry and an energy barrier of 64.2 kJ/mol according to the B3LYP/6-311++G** calculation. The molecular geometry determined from GED is in very good agreement with the geometry obtained from the quantum chemical calculations. Vibrational frequencies, IR, and Raman intensities have been calculated using B3LYP/6-311++G**. These calculations indicate that the molecule is rather flexible with six vibrational frequencies in the range of 20-84 cm(-1) for the trans isomer. The cis isomer might be detected by infrared matrix spectroscopy since the N-H stretching frequencies are very different for the two isomers.

Stochastic many-body perturbation theory for anharmonic molecular vibrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hermes, Matthew R.; Hirata, So, E-mail: sohirata@illinois.edu; CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012

2014-08-28

A new quantum Monte Carlo (QMC) method for anharmonic vibrational zero-point energies and transition frequencies is developed, which combines the diagrammatic vibrational many-body perturbation theory based on the Dyson equation with Monte Carlo integration. The infinite sums of the diagrammatic and thus size-consistent first- and second-order anharmonic corrections to the energy and self-energy are expressed as sums of a few m- or 2m-dimensional integrals of wave functions and a potential energy surface (PES) (m is the vibrational degrees of freedom). Each of these integrals is computed as the integrand (including the value of the PES) divided by the value ofmore » a judiciously chosen weight function evaluated on demand at geometries distributed randomly but according to the weight function via the Metropolis algorithm. In this way, the method completely avoids cumbersome evaluation and storage of high-order force constants necessary in the original formulation of the vibrational perturbation theory; it furthermore allows even higher-order force constants essentially up to an infinite order to be taken into account in a scalable, memory-efficient algorithm. The diagrammatic contributions to the frequency-dependent self-energies that are stochastically evaluated at discrete frequencies can be reliably interpolated, allowing the self-consistent solutions to the Dyson equation to be obtained. This method, therefore, can compute directly and stochastically the transition frequencies of fundamentals and overtones as well as their relative intensities as pole strengths, without fixed-node errors that plague some QMC. It is shown that, for an identical PES, the new method reproduces the correct deterministic values of the energies and frequencies within a few cm{sup −1} and pole strengths within a few thousandths. With the values of a PES evaluated on the fly at random geometries, the new method captures a noticeably greater proportion of anharmonic effects.« less

Properties of Coulomb crystals: rigorous results.

PubMed

Cioslowski, Jerzy

2008-04-28

Rigorous equalities and bounds for several properties of Coulomb crystals are presented. The energy e(N) per particle pair is shown to be a nondecreasing function of the particle number N for all clusters described by double-power-law pairwise-additive potentials epsilon(r) that are unbound at both r-->0 and r-->infinity. A lower bound for the ratio of the mean reciprocal crystal radius and e(N) is derived. The leading term in the asymptotic expression for the shell capacity that appears in the recently introduced approximate model of Coulomb crystals is obtained, providing in turn explicit large-N asymptotics for e(N) and the mean crystal radius. In addition, properties of the harmonic vibrational spectra are investigated, producing an upper bound for the zero-point energy.

The energy separation between the classical and nonclassical isomers of protonated acetylene - An extensive study in one- and n-particle space saturation

NASA Technical Reports Server (NTRS)

Lindh, Roland; Rice, Julia E.; Lee, Timothy J.

1991-01-01

The energy separation between the classical and nonclassical forms of protonated acetylene has been reinvestigated in light of the recent experimentally deduced lower bound to this value of 6.0 kcal/mol. The objective of the present study is to use state-of-the-art ab initio quantum mechanical methods to establish this energy difference to within chemical accuracy (i.e., about 1 kcal/mol). The one-particle basis sets include up to g-type functions and the electron correlation methods include single and double excitation coupled-cluster (CCSD), the CCSD(T) extension, multireference configuration interaction, and the averaged coupled-pair functional methods. A correction for zero-point vibrational energies has also been included, yielding a best estimate for the energy difference between the classical and nonclassical forms of 3.7 + or - 1.3 kcal/mol.

Complexes and saddle point structures, vibrational frequencies and relative energies of intermediates for CH2Br + HBr «-» CH3Br + Br

NASA Astrophysics Data System (ADS)

Espinosa-Garcia, J.

Ab initio molecular orbital theory was used to study parts of the reaction between the CH2Br radical and the HBr molecule, and two possibilities were analysed: attack on the hydrogen and attack on the bromine of the HBr molecule. Optimized geometries and harmonic vibrational frequencies were calculated at the second-order Moller-Plesset perturbation theory levels, and comparison with available experimental data was favourable. Then single-point calculations were performed at several higher levels of calculation. In the attack on the hydrogen of HBr, two stationary points were located on the direct hydrogen abstraction reaction path: a very weak hydrogen bonded complex of reactants, C···HBr, close to the reactants, followed by the saddle point (SP). The effects of level of calculation (method + basis set), spin projection, zeropoint energy, thermal corrections (298K), spin-orbit coupling and basis set superposition error (BSSE) on the energy changes were analysed. Taking the reaction enthalpy (298K) as reference, agreement with experiment was obtained only when high correlation energy and large basis sets were used. It was concluded that at room temperature (i.e., with zero-point energy and thermal corrections), when the BSSE was included, the complex disappears and the activation enthalpy (298K) ranges from 0.8kcal mol-1 to 1.4kcal mol-1 above the reactants, depending on the level of calculation. It was concluded also that this result is the balance of a complicated interplay of many factors, which are affected by uncertainties in the theoretical calculations. Finally, another possible complex (X complex), which involves the alkyl radical being attracted to the halogen end of HBr (C···BrH), was explored also. It was concluded that this X complex does not exist at room temperature.

Faraday instability in a near-critical fluid under weightlessness.

PubMed

Gandikota, G; Chatain, D; Amiroudine, S; Lyubimova, T; Beysens, D

2014-01-01

Experiments on near-critical hydrogen have been conducted under magnetic compensation of gravity to investigate the Faraday instability that arises at the liquid-vapor interface under zero-gravity conditions. We investigated such instability in the absence of stabilizing gravity. Under such conditions, vibration orients the interface and can destabilize it. The experiments confirm the existence of Faraday waves and demonstrate a transition from a square to a line pattern close to the critical point. They also show a transition very close to the critical point from Faraday to periodic layering of the vapor-liquid interface perpendicular to vibration. It was seen that the Faraday wave instability is favored when the liquid-vapor density difference is large enough (fluid far from the critical point), whereas periodic layering predominates for small difference in the liquid and vapor densities (close to the critical point). It was observed for the Faraday wave instability that the wavelength of the instability decreases as one approaches the critical point. The experimental results demonstrate good agreement to the dispersion relation for zero gravity except for temperatures very close to the critical point where a transition from a square pattern to a line pattern is detected, similarly to what is observed under 1g conditions.

Zero kinetic energy spectroscopy: mass-analyzed threshold ionization spectra of chromium sandwich complexes with alkylbenzenes, (η(6)-RPh)(2)Cr (R = Me, Et, i-Pr, t-Bu).

PubMed

Ketkov, Sergey Y; Selzle, Heinrich L; Cloke, F Geoffrey N; Markin, Gennady V; Shevelev, Yury A; Domrachev, Georgy A; Schlag, Edward W

2010-10-28

For over 25 years zero kinetic energy (ZEKE) spectroscopy has yielded a rich foundation of high-resolution results of molecular ions. This was based on the discovery in the late 60's of long-lived ion states throughout the ionization continuum of molecular ions. Here, an example is chosen from another fundamental system pioneered at this university. The mass-analyzed threshold ionization (MATI) spectra of jet-cooled chromium bisarene complexes (η(6)-RPh)(2)Cr (R = Me (1), Et (2), i-Pr (3), and t-Bu (4)) have been measured and interpreted on the basis of DFT calculations. The MATI spectra of complexes 1 and 2 appear to reveal features arising from ionizations of the isomers formed by the rotation of one arene ring relative to the other. The 1 and 2 MATI spectra show two intense peaks corresponding to the 0(0)(0) ionizations with inverse intensity ratios. As indicated by the DFT calculations, the intensity ratio change on going from 1 to 2 results from different isomers contributing to each MATI peak. The ionization energies corresponding to the 0(0)(0) peaks are 42746 ± 5 and 42809 ± 5 cm(-1) for compound 1 and 42379 ± 5 and 42463 ± 5 cm(-1) for complex 2. The 1 and 2 spectra show also the weaker features representing transitions to the vibrationally excited cationic levels, the signals of individual rotamers being detected and assigned on the basis of calculated vibrational frequencies. The MATI spectra of compounds 3 and 4 reveal only one strong peak because of close ionization potentials of the isomers contributing to the MATI signal. The 3 and 4 ionization energies are 42104 ± 5 and 41917 ± 5 cm(-1), respectively. The precise values of ionization energies obtained from the MATI spectra reveal a nonlinear dependence of the IE on the number of Me groups in the alkyl substituents of (η(6)-RPh)(2)Cr. This can be explained by an increase in the molecular zero point energies on methylation of the substituents.

Use of a single trajectory to study product energy partitioning in unimolecular dissociation: mass effects for halogenated alkanes.

PubMed

Sun, Lipeng; Park, Kyoyeon; Song, Kihyung; Setser, Donald W; Hase, William L

2006-02-14

A single trajectory (ST) direct dynamics approach is compared with quasiclassical trajectory (QCT) direct dynamics calculations for determining product energy partitioning in unimolecular dissociation. Three comparisons are made by simulating C(2)H(5)F-->HF + C(2)H(4) product energy partitioning for the MP26-31G(*) and MP26-311 + + G(**) potential energy surfaces (PESs) and using the MP26-31G(*) PES for C(2)H(5)F dissociation as a model to simulate CHCl(2)CCl(3)-->HCl + C(2)Cl(4) dissociation and its product energy partitioning. The trajectories are initiated at the transition state with fixed energy in reaction-coordinate translation E(t) (double dagger). The QCT simulations have zero-point energy (ZPE) in the vibrational modes orthogonal to the reaction coordinate, while there is no ZPE for the STs. A semiquantitative agreement is obtained between the ST and QCT average percent product energy partitionings. The ST approach is used to study mass effects for product energy partitioning in HX(X = F or Cl) elimination from halogenated alkanes by using the MP26-31G(*) PES for C(2)H(5)F dissociation and varying the masses of the C, H, and F atoms. There is, at most, only a small mass effect for partitioning of energy to HX vibration and rotation. In contrast, there are substantial mass effects for partitioning to relative translation and the polyatomic product's vibration and rotation. If the center of mass of the polyatomic product is located away from the C atom from which HX recoils, the polyatomic has substantial rotation energy. Polyatomic products, with heavy atoms such as Cl atoms replacing the H atoms, receive substantial vibration energy that is primarily transferred to the wag-bend motions. For E(t) (double dagger) of 1.0 kcalmol, the ST calculations give average percent partitionings to relative translation, polyatomic vibration, polyatomic rotation, HX vibration, and HX rotation of 74.9%, 6.8%, 1.5%, 14.4%, and 2.4% for C(2)H(5)F dissociation and 39.7%, 38.1%, 0.2%, 16.1%, and 5.9% for a model of CHCl(2)CCl(3) dissociation.

Zero-point corrections for isotropic coupling constants for cyclohexadienyl radical, C₆H₇ and C₆H₆Mu: beyond the bond length change approximation.

PubMed

Hudson, Bruce S; Chafetz, Suzanne K

2013-04-25

Zero-point vibrational level averaging for electron spin resonance (ESR) and muon spin resonance (µSR) hyperfine coupling constants (HFCCs) are computed for H and Mu isotopomers of the cyclohexadienyl radical. A local mode approximation previously developed for computation of the effect of replacement of H by D on ¹³C-NMR chemical shifts is used. DFT methods are used to compute the change in energy and HFCCs when the geometry is changed from the equilibrium values for the stretch and both bend degrees of freedom. This variation is then averaged over the probability distribution for each degree of freedom. The method is tested using data for the methylene group of C₆H₇, cyclohexadienyl radical and its Mu analog. Good agreement is found for the difference between the HFCCs for Mu and H of CHMu and that for H of CHMu and CH₂ of the parent radical methylene group. All three of these HFCCs are the same in the absence of the zero point average, a one-parameter fit of the static HFCC, a(0), can be computed. That value, 45.2 Gauss, is compared to the results of several fixed geometry electronic structure computations. The HFCC values for the ortho, meta and para H atoms are then discussed.

Non-Born-Oppenheimer calculations of the pure vibrational spectrum of HeH+.

PubMed

Pavanello, Michele; Bubin, Sergiy; Molski, Marcin; Adamowicz, Ludwik

2005-09-08

Very accurate calculations of the pure vibrational spectrum of the HeH(+) ion are reported. The method used does not assume the Born-Oppenheimer approximation, and the motion of both the electrons and the nuclei are treated on equal footing. In such an approach the vibrational motion cannot be decoupled from the motion of electrons, and thus the pure vibrational states are calculated as the states of the system with zero total angular momentum. The wave functions of the states are expanded in terms of explicitly correlated Gaussian basis functions multipled by even powers of the internuclear distance. The calculations yielded twelve bound states and corresponding eleven transition energies. Those are compared with the pure vibrational transition energies extracted from the experimental rovibrational spectrum.

On the non-Arrhenius temperature dependence of the interwell electron tunneling rate in quasi two dimensional organic quantum wells

NASA Astrophysics Data System (ADS)

Jeong, I. S.; Scott, K.; Donovan, K. J.; Wilson, E. G.

2000-11-01

The tunneling rate of photocreated charge carriers between layers in Langmuir-Blodgett multilayer structures is measured indirectly using the novel technique of bimolecular recombination quenching. The tunneling rate is measured as a function of the applied electrostatic potential difference between the layers as the temperature is varied between 300 and 4 K. This dependence is examined in light of the Marcus theory of charge transfer where the electrostatic potential replaces the chemical potential as the driving potential. The expectations of the Marcus theory are not met and the rate is effectively temperature independent, contrary to expectation. Other mechanisms are explored that may explain the lack of temperature dependence including the role of high frequency vibrations and the role of the zero point energy of those vibrations. The temperature dependence of the exciton dissociation probability is also examined.

A direct ab initio molecular dynamics (MD) study on the benzophenone-water 1 : 1 complex.

PubMed

Tachikawa, Hiroto; Iyama, Tetsuji; Kato, Kohichi

2009-07-28

Direct ab initio molecular dynamics (MD) method has been applied to a benzophenone-water 1 : 1 complex Bp(H(2)O) and free benzophenone (Bp) to elucidate the effects of zero-point energy (ZPE) vibration and temperature on the absorption spectra of Bp(H(2)O). The n-pi transition of free-Bp (S(1) state) was blue-shifted by the interaction with a water molecule, whereas three pi-pi transitions (S(2), S(3) and S(4)) were red-shifted. The effects of the ZPE vibration and temperature of Bp(H(2)O) increased the intensity of the n-pi transition of Bp(H(2)O) and caused broadening of the pi-pi transitions. In case of the temperature effect, the intensity of n-pi transition increases with increasing temperature. The electronic states of Bp(H(2)O) were discussed on the basis of the theoretical results.

Quantum dynamics study of H+NH3-->H2+NH2 reaction.

PubMed

Zhang, Xu Qiang; Cui, Qian; Zhang, John Z H; Han, Ke Li

2007-06-21

We report in this paper a quantum dynamics study for the reaction H+NH3-->NH2+H2 on the potential energy surface of Corchado and Espinosa-Garcia [J. Chem. Phys. 106, 4013 (1997)]. The quantum dynamics calculation employs the semirigid vibrating rotor target model [J. Z. H. Zhang, J. Chem. Phys. 111, 3929 (1999)] and time-dependent wave packet method to propagate the wave function. Initial state-specific reaction probabilities are obtained, and an energy correction scheme is employed to account for zero point energy changes for the neglected degrees of freedom in the dynamics treatment. Tunneling effect is observed in the energy dependency of reaction probability, similar to those found in H+CH4 reaction. The influence of rovibrational excitation on reaction probability and stereodynamical effect are investigated. Reaction rate constants from the initial ground state are calculated and are compared to those from the transition state theory and experimental measurement.

On energetic prerequisites of attracting electrons

NASA Astrophysics Data System (ADS)

Sundholm, Dage

2014-06-01

The internal reorganization energy and the zero-point vibrational energy (ZPE) of fractionally charged molecules embedded in molecular materials are discussed. The theory for isolated open quantum systems is taken as the starting point. It is shown that for isolated molecules the internal reorganization-energy function and its slope, i.e., the chemical potential of an open molecular system are monotonically decreasing functions with respect to increasing amount of negative excess charge (q) in the range of q = [0, 1]. Calculations of the ZPE for fractionally charged molecules show that the ZPE may have a minimum for fractional occupation. The calculations show that the internal reorganization energy and changes in the ZPE are of the same order of magnitude with different behavior as a function of the excess charge. The sum of the contributions might favor molecules with fractional occupation of the molecular units and partial delocalization of the excess electrons in solid-state materials also when considering Coulomb repulsion between the excess electrons. The fractional electrons are then coherently distributed on many molecules of the solid-state material forming a condensate of attracting electrons, which is crucial for the superconducting state.

DFT studies on the mechanism of the reaction of C2H5S with NO2

NASA Astrophysics Data System (ADS)

Tang, Yi-Zhen; Sun, Hao; Pan, Ya-Ru; Pan, Xiu-Mei; Wang, Rong-Shun

The mechanisms for the reaction of C2H5S with NO2 are investigated at the QCISD(T)/6-311++G(d, p)//B3LYP/6-311++G(d, p) level on both single and triple potential energy surfaces. The geometries, vibrational frequencies and zero-point energy (ZPE) corrections of all stationary points involved in the title reaction are calculated at the B3LYP/6-311++G(d, p) level. The results show that the reaction is more predominant on the single potential energy surface, while it is negligible on the triple potential energy surface. Without barrier height in the whole process, the major channel is R ? C2H5SONO (IM1 and IM2) ? P1 (C2H5SO+NO). With much heat released in the formation of C2H5SNO2 (IM3) and the transition state involved in the subsequent step more stable than reactants, P4 (CH3CHS + t-HONO) is subdominant product energetically.

On energetic prerequisites of attracting electrons.

PubMed

Sundholm, Dage

2014-06-21

The internal reorganization energy and the zero-point vibrational energy (ZPE) of fractionally charged molecules embedded in molecular materials are discussed. The theory for isolated open quantum systems is taken as the starting point. It is shown that for isolated molecules the internal reorganization-energy function and its slope, i.e., the chemical potential of an open molecular system are monotonically decreasing functions with respect to increasing amount of negative excess charge (q) in the range of q = [0, 1]. Calculations of the ZPE for fractionally charged molecules show that the ZPE may have a minimum for fractional occupation. The calculations show that the internal reorganization energy and changes in the ZPE are of the same order of magnitude with different behavior as a function of the excess charge. The sum of the contributions might favor molecules with fractional occupation of the molecular units and partial delocalization of the excess electrons in solid-state materials also when considering Coulomb repulsion between the excess electrons. The fractional electrons are then coherently distributed on many molecules of the solid-state material forming a condensate of attracting electrons, which is crucial for the superconducting state.

Shear modulus of neutron star crust

NASA Astrophysics Data System (ADS)

Baiko, D. A.

2011-09-01

The shear modulus of solid neutron star crust is calculated by the thermodynamic perturbation theory, taking into account ion motion. At a given density, the crust is modelled as a body-centred cubic Coulomb crystal of fully ionized atomic nuclei of one type with a uniform charge-compensating electron background. Classic and quantum regimes of ion motion are considered. The calculations in the classic temperature range agree well with previous Monte Carlo simulations. At these temperatures, the shear modulus is given by the sum of a positive contribution due to the static lattice and a negative ∝ T contribution due to the ion motion. The quantum calculations are performed for the first time. The main result is that at low temperatures the contribution to the shear modulus due to the ion motion saturates at a constant value, associated with zero-point ion vibrations. Such behaviour is qualitatively similar to the zero-point ion motion contribution to the crystal energy. The quantum effects may be important for lighter elements at higher densities, where the ion plasma temperature is not entirely negligible compared to the typical Coulomb ion interaction energy. The results of numerical calculations are approximated by convenient fitting formulae. They should be used for precise neutron star oscillation modelling, a rapidly developing branch of stellar seismology.

Zero point energy leakage in condensed phase dynamics: An assessment of quantum simulation methods for liquid water

NASA Astrophysics Data System (ADS)

Habershon, Scott; Manolopoulos, David E.

2009-12-01

The approximate quantum mechanical ring polymer molecular dynamics (RPMD) and linearized semiclassical initial value representation (LSC-IVR) methods are compared and contrasted in a study of the dynamics of the flexible q-TIP4P/F water model at room temperature. For this water model, a RPMD simulation gives a diffusion coefficient that is only a few percent larger than the classical diffusion coefficient, whereas a LSC-IVR simulation gives a diffusion coefficient that is three times larger. We attribute this discrepancy to the unphysical leakage of initially quantized zero point energy (ZPE) from the intramolecular to the intermolecular modes of the liquid as the LSC-IVR simulation progresses. In spite of this problem, which is avoided by construction in RPMD, the LSC-IVR may still provide a useful approximation to certain short-time dynamical properties which are not so strongly affected by the ZPE leakage. We illustrate this with an application to the liquid water dipole absorption spectrum, for which the RPMD approximation breaks down at frequencies in the O-H stretching region owing to contamination from the internal modes of the ring polymer. The LSC-IVR does not suffer from this difficulty and it appears to provide quite a promising way to calculate condensed phase vibrational spectra.

Zero point energy leakage in condensed phase dynamics: an assessment of quantum simulation methods for liquid water.

PubMed

Habershon, Scott; Manolopoulos, David E

2009-12-28

The approximate quantum mechanical ring polymer molecular dynamics (RPMD) and linearized semiclassical initial value representation (LSC-IVR) methods are compared and contrasted in a study of the dynamics of the flexible q-TIP4P/F water model at room temperature. For this water model, a RPMD simulation gives a diffusion coefficient that is only a few percent larger than the classical diffusion coefficient, whereas a LSC-IVR simulation gives a diffusion coefficient that is three times larger. We attribute this discrepancy to the unphysical leakage of initially quantized zero point energy (ZPE) from the intramolecular to the intermolecular modes of the liquid as the LSC-IVR simulation progresses. In spite of this problem, which is avoided by construction in RPMD, the LSC-IVR may still provide a useful approximation to certain short-time dynamical properties which are not so strongly affected by the ZPE leakage. We illustrate this with an application to the liquid water dipole absorption spectrum, for which the RPMD approximation breaks down at frequencies in the O-H stretching region owing to contamination from the internal modes of the ring polymer. The LSC-IVR does not suffer from this difficulty and it appears to provide quite a promising way to calculate condensed phase vibrational spectra.

Ballistic induced pumping of hypersonic heat current in DNA nano wire

NASA Astrophysics Data System (ADS)

Behnia, Sohrab; Panahinia, Robabe

2016-12-01

Heat shuttling properties of DNA nano-wire driven by an external force against the spontaneous heat current direction in non-zero temperature bias (non averaged) have been studied. We examined the valid region of driving amplitude and frequency to have pumping state in terms of temperature bias and the system size. It was shown that DNA could act as a high efficiency thermal pump in the hypersonic region. Amplitude-dependent resonance frequencies of DNA indicating intrinsic base pair internal vibrations have been detected. Nonlinearity implies that by increasing the driven amplitude new vibration modes are detected. To verify the results, an analytical parallel investigation based on multifractal concept has been done. By using the geometric properties of the strange attractor of the system, the threshold value to transition to the pumping state for given external amplitude has been identified. It was shown that the system undergoes a phase transition in sliding point to the pumping state. Fractal dimension demonstrates that the ballistic transport is responsible for energy pumping in the system. In the forbidden band gap, DNA could transmit the energy by exceeding the threshold amplitude. Despite of success in energy pumping, in this framework, DNA could not act as a real cooler.

Experiments on active isolation using distributed PVDF error sensors

NASA Technical Reports Server (NTRS)

Lefebvre, S.; Guigou, C.; Fuller, C. R.

1992-01-01

A control system based on a two-channel narrow-band LMS algorithm is used to isolate periodic vibration at low frequencies on a structure composed of a rigid top plate mounted on a flexible receiving plate. The control performance of distributed PVDF error sensors and accelerometer point sensors is compared. For both sensors, high levels of global reduction, up to 32 dB, have been obtained. It is found that, by driving the PVDF strip output voltage to zero, the controller may force the structure to vibrate so that the integration of the strain under the length of the PVDF strip is zero. This ability of the PVDF sensors to act as spatial filters is especially relevant in active control of sound radiation. It is concluded that the PVDF sensors are flexible, nonfragile, and inexpensive and can be used as strain sensors for active control applications of vibration isolation and sound radiation.

Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on Lornoxicam by density functional theory

NASA Astrophysics Data System (ADS)

Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

2015-11-01

The Fourier transform infrared (FT-IR) and FT-Raman spectra of Lornoxicam were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameters, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p) and 6-31++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the Vibrational modes calculated using Vibrational Energy Distribution Analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and Lornoxicam is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis and the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like Entropy, Enthalpy, Specific heat capacity and zero vibrational energy have been calculated. Besides, molecular electrostatic potential (MEP) was investigated using theoretical calculations.

SCATTERING OF SLOW NEUTRONS FROM PROPANE GAS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strong, K.A.; Marshall, G.D.; Brugger, R.M.

1962-02-01

Measurements of the partial differential neutron scattering cross sections for room-temperature propane gas are reported. These measurements were made at incident energies of 0.0l01, 0.0254, 0.0736, and 0.102 ev at seven scattering angles between 16.3 and 84.7 deg using the Materials Testing Reactor phased chopper velocity selector. The data are convented to the scattering-law presentation and compared with three theoretical calculations: The ideal gas, using an effective mass obtained from an average of the mass tensors for the three types of H atoms in propane, gives poor agreement. The Krieger-Nelkin approximation, which includes the effect of zero-point vibrations, gives limitedmore » agreement for energy transfer less than 0.5 k/sub b/T at intermediate momentum transfers. At large momentum transfers where vibrational effects become important it underestimates the cross section. A modification of the Krieger- Nelkin theory that includes the effects of single-quantum transitions from the three lowest vibratlonal states gives better agreement. The discrepancies still present at large momentum and energy transfers are attributed to an uncertainty in the methylgroup barrier height for the three lowest energy modes, to the harmonlc oscillator approximation for these modes, and to the approximate molecular orientation averaging used in the calculation. (auth)« less

Quantum mechanical characterization of the He4ICl weakly bound complex.

PubMed

Valdés, Álvaro; Prosmiti, Rita

2013-08-15

Vibrational calculations are performed for the 12-dimensional He4ICl van der Waals complex using the multiconfiguration time-dependent Hartree (MCTDH) method. The potential energy surface of the cluster is represented as a sum of the triatomic He-ICl ab initio parametrized terms plus the He-He interactions. The topology of the potential presents higher anisotropy compared to the one with a homonuclear dopant, and this is clearly reflected in the structure and energetics of the low-lying conformers of the system. In order to take advantage of the MCTDH method, natural potential fits are employed for the potential energy operator, and also, a mode combination scheme is introduced in order to speed up the computations. Zero-point energy, binding energies, and vibrationally averaged structures of different isomers of the He4ICl cluster are obtained. The present results predict that the (3,1,0) structure, involving three He atoms in the near T-shaped and one He atom in the linear configurations, to be the most stable one in accord with recent experimental findings. Comparisons with previous theoretical and experimental data are presented, and the stability of the high-order conformers is discussed in connection with the multiple minima (global and local) of the underlying potential surface.

On the Lowest Ro-Vibrational States of Protonated Methane: Experiment and Analytical Model

NASA Astrophysics Data System (ADS)

Schmiedt, Hanno; Jensen, Per; Asvany, Oskar; Schlemmer, Stephan

2016-06-01

Protonated methane, CH_5^+, is the prototype of an extremely floppy molecule. To the best of our knowledge all barriers are surmountable in the rovibrational ground state; the large amount of zero-point vibrational energy leads to large amplitude motions for many degrees of freedom. Low resolution but broad band vibrational spectroscopy [1] revealed an extremely wide range of C-H stretching vibrations. Comparison with theoretical IR spectra supported the structural motif of a CH_3 tripod and an H_2 moiety, bound to the central carbon atom by a 3c2e bond. In a more dynamic picture the five protons surround the central carbon atom without significant restrictions on the H-C-H bending or H_n-C torsional motions. The large-amplitude internal motions preclude a simple theoretical description of the type possible for more conventional molecules, such as the related spherical-top methane molecule. Recent high-resolution ro-vibrational spectra obtained in cold ion trap experiments [2] show that the observed CH_5^+ transitions belong to a very well-defined energy level scheme describing the lowest rotational and vibrational states of this enigmatic molecule. Here we analyse the experimental ground state combination differences and associate them with the motional states of CH_5^+ allowed by Fermi-Dirac statistics. A model Hamiltonian for unrestricted internal rotations in CH_5^+ yields a simple analytical expression for the energy eigenvalues, expressed in terms of new quantum numbers describing the free internal rotation. These results are compared to the experimental combination differences and the validity of the model will be discussed together with the underlying assumptions. [1] O. Asvany, P. Kumar, I. Hegemann, B. Redlich, S. Schlemmer and D. Marx, Science 309, (2005) 1219-1222 [2] O. Asvany, K.M.T. Yamada, S. Brünken, A. Potapov, S. Schlemmer, Science 347 (2015) 1346-1349

Attitude and vibration control of a satellite containing flexible solar arrays by using reaction wheels, and piezoelectric transducers as sensors and actuators

NASA Astrophysics Data System (ADS)

da Fonseca, Ijar M.; Rade, Domingos A.; Goes, Luiz C. S.; de Paula Sales, Thiago

2017-10-01

The primary purpose of this paper is to provide insight into control-structure interaction for satellites comprising flexible appendages and internal moving components. The physical model considered herein aiming to attend such purpose is a rigid-flexible satellite consisting of a rigid platform containing two rotating flexible solar panels. The solar panels rotation is assumed to be in a sun-synchronous configuration mode. The panels contain surface-bonded piezoelectric patches that can be used either as sensors for the elastic displacements or as actuators to counteract the vibration motion. It is assumed that in the normal mode operation the satellite platform points towards the Earth while the solar arrays rotate so as to follow the Sun. The vehicle moves in a low Earth polar orbit. The technique used to obtain the mathematical model combines the Lagrangian formulation with the Finite Elements Method used to describe the dynamics of the solar panel. The gravity-gradient torque as well as the torque due to the interaction of the Earth magnetic field and the satellite internal residual magnetic moment is included as environmental perturbations. The actuators are three reaction wheels for attitude control and piezoelectric actuators to control the flexible motion of the solar arrays. Computer simulations are performed using the MATLAB® software package. The following on-orbit satellite operating configurations are object of analysis: i) Satellite pointing towards the Earth (Earth acquisition maneuver) by considering the initial conditions in the elastic displacement equal to zero, aiming the assessment of the flexible modes excitation by the referred maneuver; ii) the satellite pointing towards the Earth with the assumption of an initial condition different from zero for the flexible motion such that the attitude alterations are checked against the elastic motion disturbance; and iii) attitude acquisition accomplished by taking into account initial conditions different from zero for both attitude and elastic vibrations. Additionally, the control efforts for the three cases are compared. Results indicate that the attitude control is able to excite the solar panels' vibration modes and vice-versa. The piezoelectric vibration control shows significant performance improvement when compared to contributions of the attitude control to the vibration damping.

The 700-1500 cm{sup −1} region of the S{sub 1} (A{sup ~1}B{sub 2}) state of toluene studied with resonance-enhanced multiphoton ionization (REMPI), zero-kinetic-energy (ZEKE) spectroscopy, and time-resolved slow-electron velocity-map imaging (tr-SEVI) spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gardner, Adrian M.; Green, Alistair M.; Tamé-Reyes, Victor M.

We report (nanosecond) resonance-enhanced multiphoton ionization (REMPI), (nanosecond) zero-kinetic-energy (ZEKE) and (picosecond) time-resolved slow-electron velocity map imaging (tr-SEVI) spectra of fully hydrogenated toluene (Tol-h{sub 8}) and the deuterated-methyl group isotopologue (α{sub 3}-Tol-d{sub 3}). Vibrational assignments are made making use of the activity observed in the ZEKE and tr-SEVI spectra, together with the results from quantum chemical and previous experimental results. Here, we examine the 700–1500 cm{sup −1} region of the REMPI spectrum, extending our previous work on the region ≤700 cm{sup −1}. We provide assignments for the majority of the S{sub 1} and cation bands observed, and in particular wemore » gain insight regarding a number of regions where vibrations are coupled via Fermi resonance. We also gain insight into intramolecular vibrational redistribution in this molecule.« less

Electronic conductance of a poly(p-phenylene)-like nanowire in the presence of thermal atomic vibrations

NASA Astrophysics Data System (ADS)

Shariati, Ashrafalsadat; Rabani, Hassan; Mardaani, Mohammad

2017-10-01

We present a theoretical method based on Green’s function technique and tight-binding approach as well as harmonic approximation in order to calculate the coherent electronic conductance of an extended poly(p-phenylene) oligomer in the presence of thermal atomic vibrations. We study two proposed mass-spring models for atomic vibrations: one, including rigid benzene rings connected to each other by vibrating bonds; and in another, the bonds along the oligomer vibrate even in the benzene rings. The electron-phonon (e-ph) interaction influences the electron hopping energies linearly with respect to atomic displacements. The model shows that the conductance spectra exhibit some new energy gaps in the presence of e-ph interaction even at zero temperature. The conductance is more affected by e-ph interaction when the atomic vibrations are supposed to be present in the benzene rings. At the edges of the band energy and central gap, the phonon-assisted phenomena can be observed. Generally, the increasing e-ph interaction strength as well as temperature destroys the electronic conductance especially in the resonance region.

Low-temperature vibrational dynamics of fused silica and binary silicate glasses

NASA Astrophysics Data System (ADS)

Cai, Ling; Shi, Ying; Hrdina, Ken; Moore, Lisa; Wu, Jingshi; Daemen, Luke L.; Cheng, Yongqiang

2018-02-01

Inelastic neutron scattering was used to study the vibrational dynamics of fused silica and its mixed binary glasses that were doped with either TiO2 or K2O . The energy transfer was measured from zero to 180 meV where the so-called Boson peaks (BP) at low energy and molecular vibrations at high energy are included. Although most of the vibrational spectra at the high energy resemble those reported in earlier literature, a defect-mode-like peak is observed for the doped binary systems near 120 meV . At very low temperature, the BP intensity increases rapidly with temperature and then, at higher temperature, the peak intensity decreases. As a result, a maximum is observed in the temperature dependence of the BP intensity. This maximum was shown in all four samples, but the pure SiO2 sample shows the highest intensity peak and the lowest temperature for peak position. Broadband energy spectra reveal a shift of intensity from BP to the more localized modes at higher energy. Temperature evolution of BP and its relationship with heat conduction and thermal expansion are discussed.

Soft Computing Approach to Evaluate and Predict Blast-Induced Ground Vibration

NASA Astrophysics Data System (ADS)

Khandelwal, Manoj

2010-05-01

Drilling and blasting is still one of the major economical operations to excavate a rock mass. The consumption of explosive has been increased many folds in recent years. These explosives are mainly used for the exploitation of minerals in mining industry or the removal of undesirable rockmass for community development. The amount of chemical energy converted into mechanical energy to fragment and displace the rockmass is minimal. Only 20 to 30% of this explosive energy is utilized for the actual fragmentation and displacement of rockmass and rest of the energy is wasted in undesirable ill effects, like, ground vibration, air over pressure, fly rock, back break, noise, etc. Ground vibration induced due to blasting is very crucial and critical as compared to other ill effects due to involvement of public residing in the close vicinity of mining sites, regulating and ground vibration standards setting agencies together with mine owners and environmentalists and ecologists. Also, with the emphasis shifting towards eco-friendly, sustainable and geo-environmental activities, the field of ground vibration have now become an important and imperative parameter for safe and smooth running of any mining and civil project. The ground vibration is a wave motion, spreading outward from the blast like ripples spreading outwards due to impact of a stone dropped into a pond of water. As the vibration passes through the surface structures, it induces vibrations in those structures also. Sometimes, due to high ground vibration level, dwellings may get damaged and there is always confrontation between mine management and the people residing in the surroundings of the mine area. There is number of vibration predictors available suggested by different researchers. All the predictors estimate the PPV based on mainly two parameters (maximum charge used per delay and distance between blast face to monitoring point). However, few predictors considered attenuation/damping factor too. For the same excavation site, different predictors give different values of safe PPV vis-à-vis safe charge per delay. There is no uniformity in the predicted result by different predictors. All vibration predictor equations have their site specific constants. Therefore, they cannot be used in a generalized way with confidence and zero level of risk. To overcome on this aspect new soft computing tools like artificial neural network (ANN) has attracted because of its ability to learn from the pattern acquainted before. ANN has the ability to learn from patterns acquainted before. It is a highly interconnected network of a large number of processing elements called neurons in an architecture inspired by the brain. ANN can be massively parallel and hence said to exhibit parallel distributed processing. Once, the network has been trained, with sufficient number of sample data sets, it can make reliable and trustworthy predictions on the basis of its previous learning, about the output related to new input data set of similar pattern. This paper deals the application of ANN for the prediction of ground vibration by taking into consideration of maximum charge per delay and distance between blast face to monitoring point. To investigate the appropriateness of this approach, the predictions by ANN have been also compared with other vibration predictor equations.

Rotational state modification and fast ortho-para conversion of H2 trapped within the highly anisotropic potential of Pd(210)

NASA Astrophysics Data System (ADS)

Ohno, S.; Ivanov, D.; Ogura, S.; Wilde, M.; Arguelles, E. F.; Diño, W. A.; Kasai, H.; Fukutani, K.

2018-02-01

The rotational state and ortho-para conversion of H2 on a Pd(210) surface is investigated with rotational-state-selective temperature-programmed desorption (RS-TPD) and theoretical calculations. The isotope dependence of TPD shows a higher desorption energy for D2 than that for H2, which is ascribed to the rotational and zero-point vibrational energies. The RS-TPD data show that the desorption energy of H2(J =1 ) (J : rotational quantum number) is higher than that of H2(J =0 ). This is due to the orientationally anisotropic potential confining the adsorbed H2, which is in agreement with theoretical calculations. Furthermore, the H2 desorption intensity ratio in J =1 and J =0 indicates fast ortho-para conversion in the adsorption state, which we estimate to be of the order of 1 s.

A new ab initio potential energy surface of LiClH (1A') system and quantum dynamics calculation for Li + HCl (v = 0, j = 0-2) → LiCl + H reaction

NASA Astrophysics Data System (ADS)

Tan, Rui Shan; Zhai, Huan Chen; Yan, Wei; Gao, Feng; Lin, Shi Ying

2017-04-01

A new ab initio potential energy surface (PES) for the ground state of Li + HCl reactive system has been constructed by three-dimensional cubic spline interpolation of 36 654 ab initio points computed at the MRCI+Q/aug-cc-pV5Z level of theory. The title reaction is found to be exothermic by 5.63 kcal/mol (9 kcal/mol with zero point energy corrections), which is very close to the experimental data. The barrier height, which is 2.99 kcal/mol (0.93 kcal/mol for the vibrationally adiabatic barrier height), and the depth of van der Waals minimum located near the entrance channel are also in excellent agreement with the experimental findings. This study also identified two more van der Waals minima. The integral cross sections, rate constants, and their dependence on initial rotational states are calculated using an exact quantum wave packet method on the new PES. They are also in excellent agreement with the experimental measurements.

Role of zero-point effects in stabilizing the ground state structure of bulk Fe2P

NASA Astrophysics Data System (ADS)

Bhat, Soumya S.; Gupta, Kapil; Bhattacharjee, Satadeep; Lee, Seung-Cheol

2018-05-01

Structural stability of Fe2P is investigated in detail using first-principles calculations based on density functional theory. While the orthorhombic C23 phase is found to be energetically more stable, the experiments suggest it to be hexagonal C22 phase. In the present study, we show that in order to obtain the correct ground state structure of Fe2P from the first-principles based methods it is utmost necessary to consider the zero-point effects such as zero-point vibrations and spin fluctuations. This study demonstrates an exceptional case where a bulk material is stabilized by quantum effects, which are usually important in low-dimensional materials. Our results also indicate the possibility of magnetic field induced structural quantum phase transition in Fe2P, which should form the basis for further theoretical and experimental efforts.

Communication: A new ab initio potential energy surface for HCl-H2O, diffusion Monte Carlo calculations of D0 and a delocalized zero-point wavefunction.

PubMed

Mancini, John S; Bowman, Joel M

2013-03-28

We report a global, full-dimensional, ab initio potential energy surface describing the HCl-H2O dimer. The potential is constructed from a permutationally invariant fit, using Morse-like variables, to over 44,000 CCSD(T)-F12b∕aug-cc-pVTZ energies. The surface describes the complex and dissociated monomers with a total RMS fitting error of 24 cm(-1). The normal modes of the minima, low-energy saddle point and separated monomers, the double minimum isomerization pathway and electronic dissociation energy are accurately described by the surface. Rigorous quantum mechanical diffusion Monte Carlo (DMC) calculations are performed to determine the zero-point energy and wavefunction of the complex and the separated fragments. The calculated zero-point energies together with a De value calculated from CCSD(T) with a complete basis set extrapolation gives a D0 value of 1348 ± 3 cm(-1), in good agreement with the recent experimentally reported value of 1334 ± 10 cm(-1) [B. E. Casterline, A. K. Mollner, L. C. Ch'ng, and H. Reisler, J. Phys. Chem. A 114, 9774 (2010)]. Examination of the DMC wavefunction allows for confident characterization of the zero-point geometry to be dominant at the C(2v) double-well saddle point and not the C(s) global minimum. Additional support for the delocalized zero-point geometry is given by numerical solutions to the 1D Schrödinger equation along the imaginary-frequency out-of-plane bending mode, where the zero-point energy is calculated to be 52 cm(-1) above the isomerization barrier. The D0 of the fully deuterated isotopologue is calculated to be 1476 ± 3 cm(-1), which we hope will stand as a benchmark for future experimental work.

Accurate ab initio binding energies of the benzene dimer.

PubMed

Park, Young Choon; Lee, Jae Shin

2006-04-20

Accurate binding energies of the benzene dimer at the T and parallel displaced (PD) configurations were determined using the single- and double-coupled cluster method with perturbative triple correction (CCSD(T)) with correlation-consistent basis sets and an effective basis set extrapolation scheme recently devised. The difference between the estimated CCSD(T) basis set limit electronic binding energies for the T and PD shapes appears to amount to more than 0.3 kcal/mol, indicating the PD shape is a more stable configuration than the T shape for this dimer in the gas phase. This conclusion is further strengthened when a vibrational zero-point correction to the electronic binding energies of this dimer is made, which increases the difference between the two configurations to 0.4-0.5 kcal/mol. The binding energies of 2.4 and 2.8 kcal/mol for the T and PD configurations are in good accord with the previous experimental result from ionization potential measurement.

Communication: Understanding molecular representations in machine learning: The role of uniqueness and target similarity

NASA Astrophysics Data System (ADS)

Huang, Bing; von Lilienfeld, O. Anatole

2016-10-01

The predictive accuracy of Machine Learning (ML) models of molecular properties depends on the choice of the molecular representation. Inspired by the postulates of quantum mechanics, we introduce a hierarchy of representations which meet uniqueness and target similarity criteria. To systematically control target similarity, we simply rely on interatomic many body expansions, as implemented in universal force-fields, including Bonding, Angular (BA), and higher order terms. Addition of higher order contributions systematically increases similarity to the true potential energy and predictive accuracy of the resulting ML models. We report numerical evidence for the performance of BAML models trained on molecular properties pre-calculated at electron-correlated and density functional theory level of theory for thousands of small organic molecules. Properties studied include enthalpies and free energies of atomization, heat capacity, zero-point vibrational energies, dipole-moment, polarizability, HOMO/LUMO energies and gap, ionization potential, electron affinity, and electronic excitations. After training, BAML predicts energies or electronic properties of out-of-sample molecules with unprecedented accuracy and speed.

Zero-point energy constraint in quasi-classical trajectory calculations.

PubMed

Xie, Zhen; Bowman, Joel M

2006-04-27

A method to constrain the zero-point energy in quasi-classical trajectory calculations is proposed and applied to the Henon-Heiles system. The main idea of this method is to smoothly eliminate the coupling terms in the Hamiltonian as the energy of any mode falls below a specified value.

Ar(n)HF van der Waals clusters revisited: II. Energetics and HF vibrational frequency shifts from diffusion Monte Carlo calculations on additive and nonadditive potential-energy surfaces for n=1-12.

PubMed

Jiang, Hao; Xu, Minzhong; Hutson, Jeremy M; Bacić, Zlatko

2005-08-01

The ground-state energies and HF vibrational frequency shifts of Ar(n)HF clusters have been calculated on the nonadditive potential-energy surfaces (PESs) for n=2-7 and on the pairwise-additive PESs for the clusters with n=1-12, using the diffusion Monte Carlo (DMC) method. For n>3, the calculations have been performed for the lowest-energy isomer and several higher-lying isomers which are the closest in energy. They provide information about the isomer dependence of the HF redshift, and enable direct comparison with the experimental data recently obtained in helium nanodroplets. The agreement between theory and experiment is excellent, in particular, for the nonadditive DMC redshifts. The relative, incremental redshifts are reproduced accurately even at the lower level of theory, i.e., the DMC and quantum five-dimensional (rigid Ar(n)) calculations on the pairwise-additive PESs. The nonadditive interactions make a significant contribution to the frequency shift, on the order of 10%-12%, and have to be included in the PESs in order for the theory to yield accurate magnitude of the HF redshift. The energy gaps between the DMC ground states of the cluster isomers are very different from the energy separation of their respective minima on the PES, due to the considerable variations in the intermolecular zero-point energy of different Ar(n)HF isomers.

Intramolecular Vibrational Energy Redistribution (ivr) in Selected S_{1} Levels above 1000 cm^{-1} in Para-Fluorotoluene

NASA Astrophysics Data System (ADS)

Whalley, Laura E.; Gardner, Adrian M.; Tuttle, William Duncan; Davies, Julia A.; Reid, Katharine L.; Wright, Timothy G.

2017-06-01

With increasing vibrational wavenumber, the density of states of a molecule is expected to rise dramatically, especially so when low wavenumber torsions (internal rotations) are present, as in the case of para-fluorotoluene (pFT). This in turn is expected to lead to more opportunities for coupling between vibrational modes, which is the driving force for intramolecular vibrational energy redistribution (IVR). Previous studies at higher energies have focussed on the two close lying vibrational levels at 1200 cm^{-1} in the S_{1} electronic state of pFT which were assigned to two zero-order bright states (ZOBSs), whose characters predominantly involve C-CH_{3} and C-F stretching modes. A surprising result of these studies was that the photoelectron spectra showed evidence that IVR is more extensive following excitation of the C-F mode than it is following excitation of the C-CH_{3} mode, despite these levels being separated by only 35 cm^{-1}. This observation provides evidence that the IVR dynamics are mode-specific, which in turn may be a consequence of the IVR route being dependent on couplings to nearby states that are only available to the C-F mode. In this work, in order to further investigate this behaviour, we have employed resonance-enhanced multiphoton ionisation (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy to probe S_{1} levels above 1000 cm^{-1} in pFT. Such ZEKE spectra have been recorded via a number of S_{1} intermediate levels allowing the character and coupling between vibrations to be unravelled; the consequence of this coupling will be discussed with a view to understanding any IVR dynamics seen. C. J. Hammond, V. L. Ayles, D. E. Bergeron, K. L. Reid and T. G. Wright, J. Chem. Phys., 125, 124308 (2006) J. A. Davies, A. M. Green, A. M. Gardner, C. D. Withers, T. G. Wright and K. L. Reid, Phys. Chem. Chem. Phys., 16, 430 (2014)

Infrared spectra of N2O-(ortho-D2)N and N2O-(HD)N clusters trapped in bulk solid parahydrogen.

PubMed

Lorenz, Britney D; Anderson, David T

2007-05-14

High-resolution infrared spectra of the clusters N2O-(ortho-D2)N and N2O-(HD)N, N=1-4, isolated in bulk solid parahydrogen at liquid helium temperatures are studied in the 2225 cm-1 region of the nu3 antisymmetric stretch of N2O. The clusters form during vapor deposition of separate gas streams of a precooled hydrogen mixture (ortho-D2para-H2 or HDpara-H2) and N2O onto a BaF2 optical substrate held at approximately 2.5 K in a sample-in-vacuum liquid helium cryostat. The cluster spectra reveal the N2O nu3 vibrational frequency shifts to higher energy as a function of N, and the shifts are larger for ortho-D2 compared to HD. These vibrational shifts result from the reduced translational zero-point energy for N2O solvated by the heavier hydrogen isotopomers. These spectra allow the N=0 peak at 2221.634 cm-1, corresponding to the nu3 vibrational frequency of N2O isolated in pure solid parahydrogen, to be assigned. The intensity of the N=0 absorption feature displays a strong temperature dependence, suggesting that significant structural changes occur in the parahydrogen solvation environment of N2O in the 1.8-4.9 K temperature range studied.

Simulation of the photodetachment spectrum of HHfO- using coupled-cluster calculations

NASA Astrophysics Data System (ADS)

Mok, Daniel K. W.; Dyke, John M.; Lee, Edmond P. F.

2016-12-01

The photodetachment spectrum of HHfO- was simulated using restricted-spin coupled-cluster single-double plus perturbative triple {RCCSD(T)} calculations performed on the ground electronic states of HHfO and HHfO-, employing basis sets of up to quintuple-zeta quality. The computed RCCSD(T) electron affinity of 1.67 ± 0.02 eV at the complete basis set limit, including Hf 5s25p6 core correlation and zero-point energy corrections, agrees well with the experimental value of 1.70 ± 0.05 eV from a recent photodetachment study [X. Li et al., J. Chem. Phys. 136, 154306 (2012)]. For the simulation, Franck-Condon factors were computed which included allowances for anharmonicity and Duschinsky rotation. Comparisons between simulated and experimental spectra confirm the assignments of the molecular carrier and electronic states involved but suggest that the experimental vibrational structure has suffered from poor signal-to-noise ratio. An alternative assignment of the vibrational structure to that suggested in the experimental work is presented.

A combined experimental and theoretical studies on FT-IR, FT-Raman and UV-vis spectra of 2-chloro-3-quinolinecarboxaldehyde

NASA Astrophysics Data System (ADS)

Prasad, M. V. S.; Udaya Sri, N.; Veeraiah, V.

2015-09-01

In the present study, the FT-IR and FT-Raman spectra of 2-chloro-3-quinolinecarboxaldehyde (2Cl3QC) have been recorded in the region 4000-400 and 3500-50 cm-1, respectively. The fundamental modes of vibrational frequencies of 2Cl3QC are assigned. Theoretical information on the optimized geometry, harmonic vibrational frequencies, infrared and Raman intensities were obtained by means of density functional theory (DFT) gradient calculations with complete relaxation in the potential energy surface using 6-31G(d,p) basis set. The vibrational frequencies which were determined experimentally from the spectral data are compared with those obtained theoretically from DFT calculations. A close agreement was achieved between the observed and calculated frequencies by refinement of the scale factors. The infrared and Raman spectra were also predicted from the calculated intensities. Thermodynamic properties like entropy, heat capacity, zero point energy, have been calculated for the molecule. The predicted first hyperpolarizability also shows that the molecule might have a reasonably good non-linear optical (NLO) behavior. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. Stability of the molecule arising from hyper conjugative interactions, charge delocalization have been analyzed using natural bond orbitals (NBO) analysis. The results show that charge in electron density (ED) in the π∗ antibonding orbitals and E(2) energies confirms the occurrence of ICT (intra-molecular charge transfer) within the molecule. UV-visible spectrum of the title molecule has also been calculated using TD-DFT/CAM-B3LYP/6-31G(d,p) method. The calculated energy and oscillator strength almost exactly reproduces reported experimental data.

A combined experimental and theoretical studies on FT-IR, FT-Raman and UV-vis spectra of 2-chloro-3-quinolinecarboxaldehyde.

PubMed

Prasad, M V S; Udaya Sri, N; Veeraiah, V

2015-09-05

In the present study, the FT-IR and FT-Raman spectra of 2-chloro-3-quinolinecarboxaldehyde (2Cl3QC) have been recorded in the region 4000-400 and 3500-50 cm(-1), respectively. The fundamental modes of vibrational frequencies of 2Cl3QC are assigned. Theoretical information on the optimized geometry, harmonic vibrational frequencies, infrared and Raman intensities were obtained by means of density functional theory (DFT) gradient calculations with complete relaxation in the potential energy surface using 6-31G(d,p) basis set. The vibrational frequencies which were determined experimentally from the spectral data are compared with those obtained theoretically from DFT calculations. A close agreement was achieved between the observed and calculated frequencies by refinement of the scale factors. The infrared and Raman spectra were also predicted from the calculated intensities. Thermodynamic properties like entropy, heat capacity, zero point energy, have been calculated for the molecule. The predicted first hyperpolarizability also shows that the molecule might have a reasonably good non-linear optical (NLO) behavior. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. Stability of the molecule arising from hyper conjugative interactions, charge delocalization have been analyzed using natural bond orbitals (NBO) analysis. The results show that charge in electron density (ED) in the π(∗) antibonding orbitals and E((2)) energies confirms the occurrence of ICT (intra-molecular charge transfer) within the molecule. UV-visible spectrum of the title molecule has also been calculated using TD-DFT/CAM-B3LYP/6-31G(d,p) method. The calculated energy and oscillator strength almost exactly reproduces reported experimental data. Copyright © 2015 Elsevier B.V. All rights reserved.

On energetic prerequisites of attracting electrons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundholm, Dage

The internal reorganization energy and the zero-point vibrational energy (ZPE) of fractionally charged molecules embedded in molecular materials are discussed. The theory for isolated open quantum systems is taken as the starting point. It is shown that for isolated molecules the internal reorganization-energy function and its slope, i.e., the chemical potential of an open molecular system are monotonically decreasing functions with respect to increasing amount of negative excess charge (q) in the range of q = [0, 1]. Calculations of the ZPE for fractionally charged molecules show that the ZPE may have a minimum for fractional occupation. The calculations showmore » that the internal reorganization energy and changes in the ZPE are of the same order of magnitude with different behavior as a function of the excess charge. The sum of the contributions might favor molecules with fractional occupation of the molecular units and partial delocalization of the excess electrons in solid-state materials also when considering Coulomb repulsion between the excess electrons. The fractional electrons are then coherently distributed on many molecules of the solid-state material forming a condensate of attracting electrons, which is crucial for the superconducting state.« less

First-principles investigation of thermodynamic and kinetic properties in titanium-hydrogen system and B2-nickel-alminum compound: Phase stability, point defect complexes and diffusion

NASA Astrophysics Data System (ADS)

Xu, Qingchuan

The purpose of this thesis is to show the technique of predicting thermodynamic and kinetic properties from first-principles using density functional theory (DFT) calculations, cluster expansion methods and Monte Carlo simulations instead of experiments. Two material systems are selected as examples: one is an interstitial system (Ti-H system) and another is a substitutional compound (B2-NiAl alloy). For Ti-H system, this thesis investigated hydride stability, exploring the role of configurational degrees of freedom, zero-point vibrational energy and coherency strains. The tetragonal gamma-TiH phase was predicted to be unstable relative to hcp alpha-Ti and fcc based delta-TiH2. Zero point vibrational energy makes the gamma phase even less stable. The coherency strains between hydride precipitates and alpha-Ti matrix stabilize gamma-TiH relative to alpha-Ti and delta-TiH2. We also found that hydrogen prefers octahedral sites at low hydrogen concentration and tetrahedral sites at high concentration. For B2-NiAl, this thesis investigated the point defects and various diffusion mechanisms. A low barrier collective hop was discovered that could mediate Al diffusion through the anti-structural-bridge (ASB) mechanism. We also found an alternative hop sequence for the migration of a triple defect and a six-jump-cycle than that proposed previously. Going beyond the mean field approximation, we found that the inclusion of interactions among point defects is crucial to predict the concentration of defect complexes. Accounting for interactions among defects and incorporating all diffusion mechanisms proposed for B2-NiAl in Monte Carlo simulation, we calculated tracer diffusion coefficients. For the first time, the relative importance of various diffusion mechanisms is revealed. The ASB hop is the dominant mechanism for Ni in Ni-rich alloy and for Al diffusion in Al-rich alloys. Other mechanisms also play a role to various extents. We also calculated the self and interdiffusion coefficients for B2-NiAl. We found in Al-rich alloys that the thermodynamic factor of Al is much greater than that of Ni while in Ni-rich alloys they are very similar. This difference in thermodynamic factors results in a much higher self-diffusion coefficient of Al compared to that of Ni in Al-rich alloys and also causes two different interdiffusion coefficients.

Lifetimes and wave functions of ozone metastable vibrational states near the dissociation limit in a full-symmetry approach

NASA Astrophysics Data System (ADS)

Lapierre, David; Alijah, Alexander; Kochanov, Roman; Kokoouline, Viatcheslav; Tyuterev, Vladimir

2016-10-01

Energies and lifetimes (widths) of vibrational states above the lowest dissociation limit of O163 were determined using a previously developed efficient approach, which combines hyperspherical coordinates and a complex absorbing potential. The calculations are based on a recently computed potential energy surface of ozone determined with a spectroscopic accuracy [Tyuterev et al., J. Chem. Phys. 139, 134307 (2013), 10.1063/1.4821638]. The effect of permutational symmetry on rovibrational dynamics and the density of resonance states in O3 is discussed in detail. Correspondence between quantum numbers appropriate for short- and long-range parts of wave functions of the rovibrational continuum is established. It is shown, by symmetry arguments, that the allowed purely vibrational (J =0 ) levels of O163 and O183, both made of bosons with zero nuclear spin, cannot dissociate on the ground-state potential energy surface. Energies and wave functions of bound states of the ozone isotopologue O163 with rotational angular momentum J =0 and 1 up to the dissociation threshold were also computed. For bound levels, good agreement with experimental energies is found: The rms deviation between observed and calculated vibrational energies is 1 cm-1. Rotational constants were determined and used for a simple identification of vibrational modes of calculated levels.

Accurate thermochemistry and spectroscopy of the oxygen-protonated sulfur dioxide isomers.

PubMed

Puzzarini, Cristina

2011-12-28

Despite the promising relevance of protonated sulfur dioxide in astrophysical and atmospheric fields, its thermochemical and spectroscopic characterization is very limited. High-level quantum-chemical calculations have shown that the most stable isomer is the cis oxygen-protonated sulfur dioxide, HOSO(+), while the trans form is about 2 kcal mol(-1) less stable; even less stable (by about 42 kcal mol(-1)) is the S-protonated isomer [V. Lattanzi et al., J. Chem. Phys., 2010, 133, 194305]. The enthalpy of formation for the cis- and trans-HOSO(+) is presented, based on the well tested HEAT protocol [A. Tajti et al., J. Chem. Phys., 2004, 121, 11599]. Systematically extrapolated ab initio energies, accounting for electron correlation through coupled cluster theory, including up to single, double, triple and quadruple excitations, have been corrected for core-electron correlation, anharmonic zero-point vibrational energy, diagonal Born-Oppenheimer and scalar relativistic effects. As a byproduct, proton affinity of sulfur dioxide and atomization energies have also been obtained at the same levels of theory. Vibrational and rotational spectroscopic properties have been investigated by means of composite schemes that allow us to account for truncation of basis set as well as core correlation. Where available, for both thermochemistry and spectroscopy, very good agreement with experimental data has been observed.

Rotational barriers. 1. 1,2-dihaloethanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiberg, K.B.; Murcko, M.A.

1987-06-18

The rotational barrier about the C-C bond of 1,2-dichloroethane has been calculated by using several basis sets (4-31G, 6-31G*, 6-31+G*, and 6-31++G**) and including electron correlation. Corrections for zero-point energy differences, and the differences in enthalpy change from 0 to 298 K, were made by using the calculated geometries and vibrational frequencies. The trans/gauche energy difference was found to be 1.39 kcal/mol as compared to the observed value, 1.1 +/- 0.1 kcal/mol. The intramolecular interactions in the several rotamers are discussed. The trans/gauche energy difference for 1,2-difluoroethane also was calculated (MP3/6-311++G**) and was found to be 0.76 kcal/mol favoring themore » gauche conformer, again in good agreement with the experimental value of 0.57 +/- 0.09 kcal/mol. The trend in trans/gauche energy differences in the series n-butane, 1,2-dichloroethane, 1,2-difluoroethane is noted.« less

Vortex-Induced Vibrations of a Riser with Design Variations

DTIC Science & Technology

2016-06-19

explain the similarities and differences in VIV responses for the two different orientations of the same structure in the same fluid flow field . Figure...length, bending and torsional deformation can be ignored. In comparison to the potential energy in axial strain, bending energy drops off rapidly...with slenderness (diameter/length higher than ~50). Similarly, torsional energy is near zero in bluff, symmetrical and slender structures [Zueck

Computation of deuterium isotope perturbation of 13C NMR chemical shifts of alkanes: a local mode zero-point level approach.

PubMed

Yang, Kin S; Hudson, Bruce

2010-11-25

Replacement of H by D perturbs the (13)C NMR chemical shifts of an alkane molecule. This effect is largest for the carbon to which the D is attached, diminishing rapidly with intervening bonds. The effect is sensitive to stereochemistry and is large enough to be measured reliably. A simple model based on the ground (zero point) vibrational level and treating only the C-H(D) degrees of freedom (local mode approach) is presented. The change in CH bond length with H/D substitution as well as the reduction in the range of the zero-point level probability distribution for the stretch and both bend degrees of freedom are computed. The (13)C NMR chemical shifts are computed with variation in these three degrees of freedom, and the results are averaged with respect to the H and D distribution functions. The resulting differences in the zero-point averaged chemical shifts are compared with experimental values of the H/D shifts for a series of cycloalkanes, norbornane, adamantane, and protoadamantane. Agreement is generally very good. The remaining differences are discussed. The proton spectrum of cyclohexane- is revisited and updated with improved agreement with experiment.

Phase space theory of evaporation in neon clusters: the role of quantum effects.

PubMed

Calvo, F; Parneix, P

2009-12-31

Unimolecular evaporation of neon clusters containing between 14 and 148 atoms is theoretically investigated in the framework of phase space theory. Quantum effects are incorporated in the vibrational densities of states, which include both zero-point and anharmonic contributions, and in the possible tunneling through the centrifugal barrier. The evaporation rates, kinetic energy released, and product angular momentum are calculated as a function of excess energy or temperature in the parent cluster and compared to the classical results. Quantum fluctuations are found to generally increase both the kinetic energy released and the angular momentum of the product, but the effects on the rate constants depend nontrivially on the excess energy. These results are interpreted as due to the very few vibrational states available in the product cluster when described quantum mechanically. Because delocalization also leads to much narrower thermal energy distributions, the variations of evaporation observables as a function of canonical temperature appear much less marked than in the microcanonical ensemble. While quantum effects tend to smooth the caloric curve in the product cluster, the melting phase change clearly keeps a signature on these observables. The microcanonical temperature extracted from fitting the kinetic energy released distribution using an improved Arrhenius form further suggests a backbending in the quantum Ne(13) cluster that is absent in the classical system. Finally, in contrast to delocalization effects, quantum tunneling through the centrifugal barrier does not play any appreciable role on the evaporation kinetics of these rather heavy clusters.

Computational study of Ca, Sr and Ba under pressure

NASA Astrophysics Data System (ADS)

Jona, F.; Marcus, P. M.

2006-05-01

A first-principles procedure for the calculation of equilibrium properties of crystals under hydrostatic pressure is applied to Ca, Sr and Ba. The procedure is based on minimizing the Gibbs free energy G (at zero temperature) with respect to the structure at a given pressure p, and hence does not require the equation of state to fix the pressure. The calculated lattice constants of Ca, Sr and Ba are shown to be generally closer to measured values than previous calculations using other procedures. In particular for Ba, where careful and extensive pressure data are available, the calculated lattice parameters fit measurements to about 1% in three different phases, both cubic and hexagonal. Rigid-lattice transition pressures between phases which come directly from the crossing of G(p) curves are not close to measured transition pressures. One reason is the need to include zero-point energy (ZPE) of vibration in G. The ZPE of cubic phases is calculated with a generalized Debye approximation and applied to Ca and Sr, where it produces significant shifts in transition pressures. An extensive tabulation is given of structural parameters and elastic constants from the literature, including both theoretical and experimental results.

Characterization of the HSiN HNSi system in its electronic ground state

NASA Astrophysics Data System (ADS)

Lind, Maria C.; Pickard, Frank C.; Ingels, Justin B.; Paul, Ankan; Yamaguchi, Yukio; Schaefer, Henry F.

2009-03-01

The electronic ground states (X˜Σ+1) of HSiN, HNSi, and the transition state connecting the two isomers were systematically studied using configuration interaction with single and double (CISD) excitations, coupled cluster with single and double (CCSD) excitations, CCSD with perturbative triple corrections [CCSD(T)], multireference complete active space self-consistent field (CASSCF), and internally contracted multireference configuration interaction (ICMRCI) methods. The correlation-consistent polarized valence (cc-pVXZ), augmented correlation-consistent polarized valence (aug-cc-pVXZ) (X=T,Q,5), correlation-consistent polarized core-valence (cc-pCVYZ), and augmented correlation-consistent polarized core-valence (aug-cc-pCVYZ) (Y=T,Q) basis sets were used. Via focal point analyses, we confirmed the HNSi isomer as the global minimum on the ground state HSiN HNSi zero-point vibrational energy corrected surface and is predicted to lie 64.7kcalmol-1 (22640cm-1, 2.81eV) below the HSiN isomer. The barrier height for the forward isomerization reaction (HSiN→HNSi) is predicted to be 9.7kcalmol-1, while the barrier height for the reverse process (HNSi→HSiN) is determined to be 74.4kcalmol-1. The dipole moments of the HSiN and HNSi isomers are predicted to be 4.36 and 0.26D, respectively. The theoretical vibrational isotopic shifts for the HSiN/DSiN and HNSi/DNSi isotopomers are in strong agreement with the available experimental values. The dissociation energy for HSiN [HSiN(X˜Σ+1)→H(S2)+SiN(XΣ+2)] is predicted to be D0=59.6kcalmol-1, whereas the dissociation energy for HNSi [HNSi(X˜Σ+1)→H(S2)+NSi(XΣ+2)] is predicted to be D0=125.0kcalmol-1 at the CCSD(T)/aug-cc-pCVQZ level of theory. Anharmonic vibrational frequencies computed using second order vibrational perturbation theory are in good agreement with available matrix isolation experimental data for both HSiN and HNSi isomers root mean squared derivation (RMSD=9cm-1).

The Heat of Formation of HNO

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

1995-01-01

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO reversible reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HNO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X double bond H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate (Delta)H(sub f, sup o) value for HNO using state-of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +/- 0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

The Heat of Formation of HNO

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

1995-01-01

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO rev. reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X=H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate(DELTA)H(sup o)(sub f) value for HNO using state of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

Natural bond orbital analysis, electronic structure and vibrational spectral analysis of N-(4-hydroxyl phenyl) acetamide: A density functional theory

NASA Astrophysics Data System (ADS)

Govindasamy, P.; Gunasekaran, S.; Ramkumaar, G. R.

2014-09-01

The Fourier transform infrared (FT-IR) and FT-Raman spectra of N-(4-hydroxy phenyl) acetamide (N4HPA) of painkiller agent were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameter, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using Vibrational energy distribution analysis (VEDA 4) program. The oscillator’s strength calculated by TD-DFT and N4HPA is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The molecular electrostatic potential (MESP) and electron density surfaces of the molecule were constructed. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like entropy, heat capacity and zero vibrational energy have been calculated.

Natural bond orbital analysis, electronic structure and vibrational spectral analysis of N-(4-hydroxyl phenyl) acetamide: a density functional theory.

PubMed

Govindasamy, P; Gunasekaran, S; Ramkumaar, G R

2014-09-15

The Fourier transform infrared (FT-IR) and FT-Raman spectra of N-(4-hydroxy phenyl) acetamide (N4HPA) of painkiller agent were recorded in the region 4000-450 cm(-1) and 4000-50 cm(-1) respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameter, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using Vibrational energy distribution analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and N4HPA is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The molecular electrostatic potential (MESP) and electron density surfaces of the molecule were constructed. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like entropy, heat capacity and zero vibrational energy have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

Structures, energetics, vibrational spectra of NH4+ (H2O)(n=4,6) clusters: Ab initio calculations and first principles molecular dynamics simulations.

PubMed

Karthikeyan, S; Singh, Jiten N; Park, Mina; Kumar, Rajesh; Kim, Kwang S

2008-06-28

Important structural isomers of NH(4) (+)(H(2)O)(n=4,6) have been studied by using density functional theory, Moller-Plesset second order perturbation theory, and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The zero-point energy (ZPE) correction to the complete basis set limit of the CCSD(T) binding energies and free energies is necessary to identify the low energy structures for NH(4) (+)(H(2)O)(n=4,6) because otherwise wrong structures could be assigned for the most probable structures. For NH(4) (+)(H(2)O)(6), the cage-type structure, which is more stable than the previously reported open structure before the ZPE correction, turns out to be less stable after the ZPE correction. In first principles Car-Parrinello molecular dynamics simulations around 100 K, the combined power spectrum of three lowest energy isomers of NH(4) (+)(H(2)O)(4) and two lowest energy isomers of NH(4) (+)(H(2)O)(6) explains each experimental IR spectrum.

Structures, energetics, vibrational spectra of NH4+(H2O)n=4,6 clusters: Ab initio calculations and first principles molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Karthikeyan, S.; Singh, Jiten N.; Park, Mina; Kumar, Rajesh; Kim, Kwang S.

2008-06-01

Important structural isomers of NH4+(H2O)n=4,6 have been studied by using density functional theory, Møller-Plesset second order perturbation theory, and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The zero-point energy (ZPE) correction to the complete basis set limit of the CCSD(T) binding energies and free energies is necessary to identify the low energy structures for NH4+(H2O)n=4,6 because otherwise wrong structures could be assigned for the most probable structures. For NH4+(H2O)6, the cage-type structure, which is more stable than the previously reported open structure before the ZPE correction, turns out to be less stable after the ZPE correction. In first principles Car-Parrinello molecular dynamics simulations around 100 K, the combined power spectrum of three lowest energy isomers of NH4+(H2O)4 and two lowest energy isomers of NH4+(H2O)6 explains each experimental IR spectrum.

The multichannel n-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

NASA Astrophysics Data System (ADS)

Bartlett, Marcus A.; Liang, Tao; Pu, Liang; Schaefer, Henry F.; Allen, Wesley D.

2018-03-01

The n-propyl + O2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol-1 and 2.4 kcal mol-1 below the reactants, respectively. Two competitive β-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol-1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction (ΔDBOC = 1.71 kcal mol-1), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol-1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the n-propyl + O2 potential energy surface provide key benchmarks for future studies of hydrocarbon oxidation.

Vibrational spectroscopy of (SO4(2-)).(H2O)n clusters, n=1-5: harmonic and anharmonic calculations and experiment.

PubMed

Miller, Yifat; Chaban, Galina M; Zhou, Jia; Asmis, Knut R; Neumark, Daniel M; Gerber, R Benny

2007-09-07

The vibrational spectroscopy of (SO4(2-)).(H2O)n is studied by theoretical calculations for n=1-5, and the results are compared with experiments for n=3-5. The calculations use both ab initio MP2 and DFT/B3LYP potential energy surfaces. Both harmonic and anharmonic calculations are reported, the latter with the CC-VSCF method. The main findings are the following: (1) With one exception (H2O bending mode), the anharmonicity of the observed transitions, all in the experimental window of 540-1850 cm(-1), is negligible. The computed anharmonic coupling suggests that intramolecular vibrational redistribution does not play any role for the observed linewidths. (2) Comparison with experiment at the harmonic level of computed fundamental frequencies indicates that MP2 is significantly more accurate than DFT/B3LYP for these systems. (3) Strong anharmonic effects are, however, calculated for numerous transitions of these systems, which are outside the present observation window. These include fundamentals as well as combination modes. (4) Combination modes for the n=1 and n=2 clusters are computed. Several relatively strong combination transitions are predicted. These show strong anharmonic effects. (5) An interesting effect of the zero point energy (ZPE) on structure is found for (SO4(2-)).(H2O)(5): The global minimum of the potential energy corresponds to a C(s) structure, but with incorporation of ZPE the lowest energy structure is C2v, in accordance with experiment. (6) No stable structures were found for (OH-).(HSO4-).(H2O)n, for n

Vibrational spectroscopy of (SO42-).(H2O)n clusters, n=1-5: Harmonic and anharmonic calculations and experiment

NASA Astrophysics Data System (ADS)

Miller, Yifat; Chaban, Galina M.; Zhou, Jia; Asmis, Knut R.; Neumark, Daniel M.; Benny Gerber, R.

2007-09-01

The vibrational spectroscopy of (SO42-)•(H2O)n is studied by theoretical calculations for n =1-5, and the results are compared with experiments for n =3-5. The calculations use both ab initio MP2 and DFT/B3LYP potential energy surfaces. Both harmonic and anharmonic calculations are reported, the latter with the CC-VSCF method. The main findings are the following: (1) With one exception (H2O bending mode), the anharmonicity of the observed transitions, all in the experimental window of 540-1850cm-1, is negligible. The computed anharmonic coupling suggests that intramolecular vibrational redistribution does not play any role for the observed linewidths. (2) Comparison with experiment at the harmonic level of computed fundamental frequencies indicates that MP2 is significantly more accurate than DFT/B3LYP for these systems. (3) Strong anharmonic effects are, however, calculated for numerous transitions of these systems, which are outside the present observation window. These include fundamentals as well as combination modes. (4) Combination modes for the n=1 and n =2 clusters are computed. Several relatively strong combination transitions are predicted. These show strong anharmonic effects. (5) An interesting effect of the zero point energy (ZPE) on structure is found for (SO42-)•(H2O)5: The global minimum of the potential energy corresponds to a Cs structure, but with incorporation of ZPE the lowest energy structure is C2v, in accordance with experiment. (6) No stable structures were found for (OH-)•(HSO4-)•(H2O)n, for n ⩽5.

Lattice vibrations in the Frenkel-Kontorova model. I. Phonon dispersion, number density, and energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meng, Qingping; Wu, Lijun; Welch, David O.

2015-06-17

We studied the lattice vibrations of two inter-penetrating atomic sublattices via the Frenkel-Kontorova (FK) model of a linear chain of harmonically interacting atoms subjected to an on-site potential, using the technique of thermodynamic Green's functions based on quantum field-theoretical methods. General expressions were deduced for the phonon frequency-wave-vector dispersion relations, number density, and energy of the FK model system. In addition, as the application of the theory, we investigated in detail cases of linear chains with various periods of the on-site potential of the FK model. Some unusual but interesting features for different amplitudes of the on-site potential of themore » FK model are discussed. In the commensurate structure, the phonon spectrum always starts at a finite frequency, and the gaps of the spectrum are true ones with a zero density of modes. In the incommensurate structure, the phonon spectrum starts from zero frequency, but at a non-zero wave vector; there are some modes inside these gap regions, but their density is very low. In our approximation, the energy of a higher-order commensurate state of the one-dimensional system at a finite temperature may become indefinitely close to the energy of an incommensurate state. This finding implies that the higher-order incommensurate-commensurate transitions are continuous ones and that the phase transition may exhibit a “devil's staircase” behavior at a finite temperature.« less

Modeling of coupling mechanism of wireless power transfer system and vibration phenomenon of receiver-coil in three-coil system

NASA Astrophysics Data System (ADS)

Liu, Suqi; Tan, Jianping; Wen, Xue

2017-11-01

Wireless power transfer (WPT) via coupled magnetic resonances has become a focus recently, but the mechanisms responsible for such work are uncertain. We found that WPT system is a self-organization system by utilizing self-organization theory to judge. Firstly, the circuit model was established and transfer characteristic of a system was researched by utilizing circuit theories. Thus, with the introduction of entropy variable S, the energy equation of state can be established from the energy of the transmitter side and the energy of the receiver side. According to the energy equation of state, this paper obtains two equations when the reactance of the transmitter side and the receiver side equate to zero respectively. The vibration phenomenon of the receiver-coil in a three-coil WPT system was predicted and explained. Our findings illuminate the unusual self-organization in the WPT system and explain the vibration phenomenon of the receiver-coil in a three-coil WPT system.

Discrete breathers in graphane: Effect of temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baimova, J. A., E-mail: julia.a.baimova@gmail.com; Murzaev, R. T.; Lobzenko, I. P.

The discrete breathers in graphane in thermodynamic equilibrium in the temperature range 50–600 K are studied by molecular dynamics simulation. A discrete breather is a hydrogen atom vibrating along the normal to a sheet of graphane at a high amplitude. As was found earlier, the lifetime of a discrete breather at zero temperature corresponds to several tens of thousands of vibrations. The effect of temperature on the decay time of discrete breathers and the probability of their detachment from a sheet of graphane are studied in this work. It is shown that closely spaced breathers can exchange energy with eachmore » other at zero temperature. The data obtained suggest that thermally activated discrete breathers can be involved in the dehydrogenation of graphane, which is important for hydrogen energetics.« less

Broken symmetries, zero-energy modes, and quantum transport in disordered graphene: from supermetallic to insulating regimes.

PubMed

Cresti, Alessandro; Ortmann, Frank; Louvet, Thibaud; Van Tuan, Dinh; Roche, Stephan

2013-05-10

The role of defect-induced zero-energy modes on charge transport in graphene is investigated using Kubo and Landauer transport calculations. By tuning the density of random distributions of monovacancies either equally populating the two sublattices or exclusively located on a single sublattice, all conduction regimes are covered from direct tunneling through evanescent modes to mesoscopic transport in bulk disordered graphene. Depending on the transport measurement geometry, defect density, and broken sublattice symmetry, the Dirac-point conductivity is either exceptionally robust against disorder (supermetallic state) or suppressed through a gap opening or by algebraic localization of zero-energy modes, whereas weak localization and the Anderson insulating regime are obtained for higher energies. These findings clarify the contribution of zero-energy modes to transport at the Dirac point, hitherto controversial.

Study of the dislocation contribution to the internal friction background of gold

NASA Astrophysics Data System (ADS)

Baur, J.; Benoit, W.

1987-04-01

The dislocation contribution to the internal friction (IF) background is studied in annealed gold samples containing various dilute concentrations of platinum impurities. The measurements are performed in the kHz frequency range in order to determine the loss mechanism responsible for the high IF background observed at these low frequencies. To this end, the IF background was systematically measured as a function of frequency, vibration amplitude, temperature, and impurity concentration. The experimental results show that the high dislocation contribution observed in annealed samples is strain-amplitude independent for amplitudes in the range 10-7 to 2×10-6, but rapidly decreases for amplitudes smaller than 10-7. In particular, the dislocation contribution tends to zero when the strain amplitude tends to zero. Furthermore, this contribution is frequency independent. These observations demonstrate that the dislocation contribution cannot be explained by relaxations. In particular, this contribution cannot be attributed to a viscous damping of the dislocation motion. On the contrary, the experiments show that the IF background due to dislocations must be explained by hysteretic and athermal motions of dislocations interacting with point defects. However, these hysteretic motions are not due to breakaway of dislocations from pinning points distributed along their length. The experimental results can be explained by the presence of point defects close to the dislocations, but not on them. The mechanical energy loss is attributed to hysteretic motions of dislocations between potential minima created by point defects.

A direct potential fitting RKR method: Semiclassical vs. quantal comparisons

NASA Astrophysics Data System (ADS)

Tellinghuisen, Joel

2016-12-01

Quantal and semiclassical (SC) eigenvalues are compared for three diatomic molecular potential curves: the X state of CO, the X state of Rb2, and the A state of I2. The comparisons show higher levels of agreement than generally recognized, when the SC calculations incorporate a quantum defect correction to the vibrational quantum number, in keeping with the Kaiser modification. One particular aspect of this is better agreement between quantal and SC estimates of the zero-point vibrational energy, supporting the need for the Y00 correction in this context. The pursuit of a direct-potential-fitting (DPF) RKR method is motivated by the notion that some of the limitations of RKR potentials may be innate, from their generation by an exact inversion of approximate quantities: the vibrational energy Gυ and rotational constant Bυ from least-squares analysis of spectroscopic data. In contrast, the DPF RKR method resembles the quantal DPF methods now increasingly used to analyze diatomic spectral data, but with the eigenvalues obtained from SC phase integrals. Application of this method to the analysis of 9500 assigned lines in the I2A ← X spectrum fails to alter the quantal-SC disparities found for the A-state RKR curve from a previous analysis. On the other hand, the SC method can be much faster than the quantal method in exploratory work with different potential functions, where it is convenient to use finite-difference methods to evaluate the partial derivatives required in nonlinear fitting.

Large entropy derived from low-frequency vibrations and its implications for hydrogen storage

NASA Astrophysics Data System (ADS)

Wang, Xiaoxia; Chen, Hongshan

2018-02-01

Adsorption and desorption are driven by the energy and entropy competition, but the entropy effect is often ignored in hydrogen storage and the optimal adsorption strength for the ambient storage is controversial in the literature. This letter investigated the adsorption states of the H2 molecule on M-B12C6N6 (M = Li, Na, Mg, Ca, and Sc) and analyzed the correlation among the zero point energy (ZPE), the entropy change, and the adsorption energy and their effects on the delivery capacities. The ZPE has large correction to the adsorption energy due to the light mass of hydrogen. The computations show that the potential energies along the spherical surface centered at the alkali metals are very flat and it leads to large entropy (˜70 J/mol.K) of the adsorbed H2 molecules. The entropy change can compensate the enthalpy change effectively, and the ambient storage can be realized with relatively weak adsorption of ΔH = -12 kJ/mol. The results are encouraging and instructive for the design of hydrogen storage materials.

Relative electronic and free energies of octane's unique conformations

NASA Astrophysics Data System (ADS)

Kirschner, Karl N.; Heiden, Wolfgang; Reith, Dirk

2017-06-01

This study reports the geometries and electronic energies of n-octane's unique conformations using perturbation methods that best mimic CCSD(T) results. In total, the fully optimised minima of n-butane (2 conformations), n-pentane (4 conformations), n-hexane (12 conformations) and n-octane (96 conformations) were investigated at several different theory levels and basis sets. We find that DF-MP2.5/aug-cc-pVTZ is in very good agreement with the more expensive CCSD(T) results. At this level, we can clearly confirm the 96 stable minima which were previously found using a reparameterised density functional theory (DFT). Excellent agreement was found between their DFT results and our DF-MP2.5 perturbation results. Subsequent Gibbs free energy calculations, using scaled MP2/aug-cc-pVTZ zero-point vibrational energy and frequencies, indicate a significant temperature dependency of the relative energies, with a change in the predicted global minimum. The results of this work will be important for future computational investigations of fuel-related octane reactions and for optimisation of molecular force fields (e.g. lipids).

Post-transition state dynamics and product energy partitioning following thermal excitation of the F∙∙∙HCH 2 CN transition state: Disagreement with experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratihar, Subha; Ma, Xinyou; Xie, Jing

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH 3CN → HF + CH 2CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. In accord with experiment and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F-HCH 2CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST for the simulation. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation.more » The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH 2CN and then trapping in the CH 2CN-HF post-reaction potential energy well of ~10 kcal/mol with respect to the HF + CH 2CN products. In contrast to this IRC, five different trajectory types were observed, with the majority involving direct dissociation and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH 2CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. From the simulations and with an anharmonic zero-point energy constraint, the percentage partitioning of the product energy to relative translation, HF rotation, HF vibration, CH 2CN rotation and CH 2CN vibration is 5, 11, 60, 7, and 16%, respectively. In contrast the experimental energy partitioning percentages to HF rotation and vibration are 6 and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH 3CN → HF + CH 2CN are similar to those for these other reactions. A detailed discussion is given of possible origins of the difference between the simulation and experimental energy partitioning dynamics for the F + CH 3CN → HF + CH 2CN reaction. The F + CH 3CN reaction also forms the CH 3C(F)N intermediate, in which the F-atom adds to the C≡N bond. However, this intermediate and the F---CH 3CN and CH 3CN-F van der Waals complexes are not expected to affect the F + CH 3CN → HF + CH 2CN product energy partitioning.« less

Vibration isolation using six degree-of-freedom quasi-zero stiffness magnetic levitation

NASA Astrophysics Data System (ADS)

Zhu, Tao; Cazzolato, Benjamin; Robertson, William S. P.; Zander, Anthony

2015-12-01

In laboratories and high-tech manufacturing applications, passive vibration isolators are often used to isolate vibration sensitive equipment from ground-borne vibrations. However, in traditional passive isolation devices, where the payload weight is supported by elastic structures with finite stiffness, a design trade-off between the load capacity and the vibration isolation performance is unavoidable. Low stiffness springs are often required to achieve vibration isolation, whilst high stiffness is desired for supporting payload weight. In this paper, a novel design of a six degree of freedom (six-dof) vibration isolator is presented, as well as the control algorithms necessary for stabilising the passively unstable maglev system. The system applies magnetic levitation as the payload support mechanism, which realises inherent quasi-zero stiffness levitation in the vertical direction, and zero stiffness in the other five dofs. While providing near zero stiffness in multiple dofs, the design is also able to generate static magnetic forces to support the payload weight. This negates the trade-off between load capacity and vibration isolation that often exists in traditional isolator designs. The paper firstly presents the novel design concept of the isolator and associated theories, followed by the mechanical and control system designs. Experimental results are then presented to demonstrate the vibration isolation performance of the proposed system in all six directions.

Vibrational renormalisation of the electronic band gap in hexagonal and cubic ice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engel, Edgar A., E-mail: eae32@cam.ac.uk; Needs, Richard J.; Monserrat, Bartomeu

2015-12-28

Electron-phonon coupling in hexagonal and cubic water ice is studied using first-principles quantum mechanical methods. We consider 29 distinct hexagonal and cubic ice proton-orderings with up to 192 molecules in the simulation cell to account for proton-disorder. We find quantum zero-point vibrational corrections to the minimum electronic band gaps ranging from −1.5 to −1.7 eV, which leads to improved agreement between calculated and experimental band gaps. Anharmonic nuclear vibrations play a negligible role in determining the gaps. Deuterated ice has a smaller band-gap correction at zero-temperature of −1.2 to −1.4 eV. Vibrations reduce the differences between the electronic band gapsmore » of different proton-orderings from around 0.17 eV to less than 0.05 eV, so that the electronic band gaps of hexagonal and cubic ice are almost independent of the proton-ordering when quantum nuclear vibrations are taken into account. The comparatively small reduction in the band gap over the temperature range 0 − 240 K of around 0.1 eV does not depend on the proton ordering, or whether the ice is protiated or deuterated, or hexagonal, or cubic. We explain this in terms of the atomistic origin of the strong electron-phonon coupling in ice.« less

Quantitative characterization of the (D2O)3 torsional manifold by terahertz laser spectroscopy and theoretical analysis

NASA Astrophysics Data System (ADS)

Viant, Mark R.; Brown, Mac G.; Cruzan, Jeff D.; Saykally, Richard J.; Geleijns, Michel; van der Avoird, Ad

1999-03-01

We report the measurement of two new perpendicular (D2O)3 torsional bands by terahertz laser vibration-rotation-tunneling (VRT) spectroscopy of a planar pulsed supersonic expansion. The first (28.0 cm-1) band corresponds to the k=±2l←0 transition, and is the lowest frequency vibrational spectrum observed for a water cluster. The second (81.8 cm-1) band originates in the first excited torsional state, and has been assigned as k=3u←±1l. An effective three-dimensional Hamiltonian is derived to describe the rotational structure of each torsional state. Degenerate torsional levels with k=±1 and k=±2 exhibit a Coriolis splitting linear in K implying the presence of vibrational angular momentum, and a second-order splitting from off-diagonal coupling between degenerate sublevels with +|k| and -|k|. With this effective Hamiltonian we fit a total of 554 rovibrational transitions in five different bands connecting the lowest nine torsional states, with a rms residual of 1.36 MHz. The data set comprises the two new VRT bands together with the 41.1 cm-1 parallel band, the 89.6 cm-1 parallel band, and the 98.1 cm-1 perpendicular band. This analysis provides a comprehensive characterization of the torsional energy levels in (D2O)3 up to 100 cm-1 above the zero-point energy, and confirms the torsional assignments for all five (D2O)3 VRT bands observed to date. Moreover, it vindicates the adiabatic separation of the trimer torsional and hydrogen bond stretch/bend vibrational modes which underlies the torsional model.

Coherent vibrational climbing in carboxyhemoglobin

PubMed Central

Ventalon, Cathie; Fraser, James M.; Vos, Marten H.; Alexandrou, Antigoni; Martin, Jean-Louis; Joffre, Manuel

2004-01-01

We demonstrate vibrational climbing in the CO stretch of carboxyhemoglobin pumped by midinfrared chirped ultrashort pulses. By use of spectrally resolved pump-probe measurements, we directly observed the induced absorption lines caused by excited vibrational populations up to v = 6. In some cases, we also observed stimulated emission, providing direct evidence of vibrational population inversion. This study provides important spectroscopic parameters on the CO stretch in the strong-field regime, such as transition frequencies and dephasing times up to the v = 6to v = 7 vibrational transition. We measured equally spaced vibrational transitions, in agreement with the energy levels of a Morse potential up to v = 6. It is interesting that the integral of the differential absorption spectra was observed to deviate far from zero, in contrast to what one would expect from a simple one-dimensional Morse model assuming a linear dependence of dipole moment with bond length. PMID:15319472

Mode-specific tunneling using the Qim path: theory and an application to full-dimensional malonaldehyde.

PubMed

Wang, Yimin; Bowman, Joel M

2013-10-21

We present a theory of mode-specific tunneling that makes use of the general tunneling path along the imaginary-frequency normal mode of the saddle point, Qim, and the associated relaxed potential, V(Qim) [Y. Wang and J. M. Bowman, J. Chem. Phys. 129, 121103 (2008)]. The novel aspect of the theory is the projection of the normal modes of a minimum onto the Qim path and the determination of turning points on V(Qim). From that projection, the change in tunneling upon mode excitation can be calculated. If the projection is zero, no enhancement of tunneling is predicted. In that case vibrationally adiabatic (VA) theory could apply. However, if the projection is large then VA theory is not applicable. The approach is applied to mode-specific tunneling in full-dimensional malonaldehyde, using an accurate full-dimensional potential energy surface. Results are in semi-quantitative agreement with experiment for modes that show large enhancement of the tunneling, relative to the ground state tunneling splitting. For the six out-of-plane modes, which have zero projection on the planar Qim path, VA theory does apply, and results from that theory agree qualitatively and even semi-quantitatively with experiment. We also verify the failure of simple VA theory for modes that show large enhancement of tunneling.

Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment

NASA Astrophysics Data System (ADS)

Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J. A.; Setser, Donald W.; Hase, William L.

2017-10-01

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH3CN → HF + CH2CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH2CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH2CN and then trapping in the CH2CN⋯HF post-reaction potential energy well of ˜10 kcal/mol with respect to the HF + CH2CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH2CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH2CN rotation, and CH2CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH3CN → HF + CH2CN resemble those for other reactions. A detailed discussion is given of possible origins of the difference between the simulation and experimental energy partitioning dynamics for F + CH3CN → HF + CH2CN. The F + CH3CN reaction also forms the CH3C(F)N intermediate, in which the F-atom adds to the C≡N bond. However, this intermediate and F⋯CH3CN and CH3CN⋯F van der Waals complexes are not expected to affect the F + CH3CN → HF + CH2CN product energy partitioning.

Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment.

PubMed

Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J A; Setser, Donald W; Hase, William L

2017-10-14

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH 3 CN → HF + CH 2 CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH 2 CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH 2 CN and then trapping in the CH 2 CN⋯HF post-reaction potential energy well of ∼10 kcal/mol with respect to the HF + CH 2 CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH 2 CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH 2 CN rotation, and CH 2 CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH 3 CN → HF + CH 2 CN resemble those for other reactions. A detailed discussion is given of possible origins of the difference between the simulation and experimental energy partitioning dynamics for F + CH 3 CN → HF + CH 2 CN. The F + CH 3 CN reaction also forms the CH 3 C(F)N intermediate, in which the F-atom adds to the C≡N bond. However, this intermediate and F⋯CH 3 CN and CH 3 CN⋯F van der Waals complexes are not expected to affect the F + CH 3 CN → HF + CH 2 CN product energy partitioning.

Direct measurement of the energy thresholds to conformational isomerization in tryptamine: experiment and theory.

PubMed

Clarkson, Jasper R; Dian, Brian C; Moriggi, Loïck; DeFusco, Albert; McCarthy, Valerie; Jordan, Kenneth D; Zwier, Timothy S

2005-06-01

The methods of stimulated emission pumping-hole filling spectroscopy (SEP-HFS) and stimulated emission pumping population transfer spectroscopy (SEP-PTS) were applied to the conformation-specific study of conformational isomerization in tryptamine [TRA, 3-(2-aminoethyl)indole]. These experimental methods employ stimulated emission pumping to selectively excite a fraction of the population of a single conformation of TRA to well-defined ground-state vibrational levels. This produces single conformations with well-defined internal energy, tunable over a range of energies from near the zero-point level to well above the lowest barriers to conformational isomerization. When the SEP step overcomes a barrier to isomerization, a fraction of the excited population isomerizes to form that product. By carrying out SEP excitation early in a supersonic expansion, these product molecules are subsequently cooled to their zero-point vibrational levels, where they can be detected downstream with a third tunable laser that probes the ground-state population of a particular product conformer via a unique ultraviolet transition using laser-induced fluorescence. The population transfer spectra (recorded by tuning the SEP dump laser while holding the pump and probe lasers fixed) exhibit sharp onsets that directly determine the energy thresholds for conformational isomerization in a given reactant-product conformer pair. In the absence of tunneling effects, the first observed transition in a given X-Y PTS constitutes an upper bound to the energy barrier to conformational isomerization, while the last transition not observed constitutes a lower bound. The bounds for isomerizing conformer A of tryptamine to B(688-748 cm(-1)), C(1)(860-1000 cm(-1)), C(2)(1219-1316 cm(-1)), D(1219-1282 cm(-1)), E(1219-1316 cm(-1)), and F(688-748 cm(-1)) are determined. In addition, thresholds for isomerizing from B to A(<1562 cm(-1)), B to F(562-688 cm(-1)), and out of C(2) to B(<747 cm(-1)) are also determined. The A-->B and B-->A transitions are used to place bounds on the relative energies of minima B relative to A, with B lying at least 126 cm(-1) above A. The corresponding barriers have been computed using both density functional and second-order many-body perturbation theory methods in order to establish the level of theory needed to reproduce experimental results. While most of the computed barriers match experiment well, the barriers for the A-F and B-F transitions are too high by almost a factor of 2. Possible reasons for this discrepancy are discussed.

Monitoring Bridge Dynamic Deformation in Vibration by Digital Photography

NASA Astrophysics Data System (ADS)

Yu, Chengxin; Zhang, Guojian; Liu, Xiaodong; Fan, Li; Hai, Hua

2018-01-01

This study adopts digital photography to monitor bridge dynamic deformation in vibration. Digital photography in this study is based on PST-TBPM (photographing scale transformation-time baseline parallax method). Firstly, we monitor the bridge in static as a zero image. Then, we continuously monitor the bridge in vibration as the successive images. Based on the reference points on each image, PST-TBPM is used to calculate the images to obtain the dynamic deformation values of these deformation points. Results show that the average measurement accuracies are 0.685 pixels (0.51mm) and 0.635 pixels (0.47mm) in X and Z direction, respectively. The maximal deformations in X and Z direction of the bridge are 4.53 pixels and 5.21 pixels, respectively. PST-TBPM is valid in solving the problem that the photographing direction is not perpendicular to the bridge. Digital photography in this study can be used to assess bridge health through monitoring the dynamic deformation of a bridge in vibration. The deformation trend curves also can warn the possible dangers over time.

Vibrational effects in x-ray absorption and resonant inelastic x-ray scattering using a semiclassical scheme

NASA Astrophysics Data System (ADS)

Ljungberg, Mathias P.

2017-12-01

A method is presented for describing vibrational effects in x-ray absorption spectroscopy and resonant inelastic x-ray scattering (RIXS) using a combination of the classical Franck-Condon (FC) approximation and classical trajectories run on the core-excited state. The formulation of RIXS is an extension of the semiclassical Kramers-Heisenberg formalism of Ljungberg et al. [Phys. Rev. B 82, 245115 (2010), 10.1103/PhysRevB.82.245115] to the resonant case, retaining approximately the same computational cost. To overcome difficulties with connecting the absorption and emission processes in RIXS, the classical FC approximation is used for the absorption, which is seen to work well provided that a zero-point-energy correction is included. In the case of core-excited states with dissociative character, the method is capable of closely reproducing the main features for one-dimensional test systems, compared to the quantum-mechanical formulation. Due to the good accuracy combined with the relatively low computational cost, the method has great potential of being used for complex systems with many degrees of freedom, such as liquids and surface adsorbates.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Torcellini, Paul A.; Bonnema, Eric; Goldwasser, David

Building energy consumption can only be measured at the site or at the point of utility interconnection with a building. Often, to evaluate the total energy impact, this site-based energy consumption is translated into source energy, that is, the energy at the point of fuel extraction. Consistent with this approach, the U.S. Department of Energy's (DOE) definition of zero energy buildings uses source energy as the metric to account for energy losses from the extraction, transformation, and delivery of energy. Other organizations, as well, use source energy to characterize the energy impacts. Four methods of making the conversion from sitemore » energy to source energy were investigated in the context of the DOE definition of zero energy buildings. These methods were evaluated based on three guiding principles--improve energy efficiency, reduce and stabilize power demand, and use power from nonrenewable energy sources as efficiently as possible. This study examines relative trends between strategies as they are implemented on very low-energy buildings to achieve zero energy. A typical office building was modeled and variations to this model performed. The photovoltaic output that was required to create a zero energy building was calculated. Trends were examined with these variations to study the impacts of the calculation method on the building's ability to achieve zero energy status. The paper will highlight the different methods and give conclusions on the advantages and disadvantages of the methods studied.« less

Finite frequency current noise in the Holstein model

NASA Astrophysics Data System (ADS)

Stadler, P.; Rastelli, G.; Belzig, W.

2018-05-01

We investigate the effects of local vibrational excitations in the nonsymmetrized current noise S (ω ) of a nanojunction. For this purpose, we analyze a simple model—the Holstein model—in which the junction is described by a single electronic level that is coupled to two metallic leads and to a single vibrational mode. Using the Keldysh Green's function technique, we calculate the nonsymmetrized current noise to the leading order in the charge-vibration interaction. For the noise associated to the latter, we identify distinct terms corresponding to the mean-field noise and the vertex correction. The mean-field result can be further divided into an elastic correction to the noise and in an inelastic correction, the second one being related to energy exchange with the vibration. To illustrate the general behavior of the noise induced by the charge-vibration interaction, we consider two limit cases. In the first case, we assume a strong coupling of the dot to the leads with an energy-independent transmission, whereas in the second case we assume a weak tunneling coupling between the dot and the leads such that the transport occurs through a sharp resonant level. We find that the noise associated to the vibration-charge interaction shows a complex pattern as a function of the frequency ω and of the transmission function or of the dot's energy level. Several transitions from enhancement to suppression of the noise occurs in different regions, which are determined, in particular, by the vibrational frequency. Remarkably, in the regime of an energy-independent transmission, the zero-order elastic noise vanishes at perfect transmission and at positive frequency, whereas the noise related to the charge-vibration interaction remains finite, enabling the analysis of the pure vibrational-induced current noise.

Collisions of excited Na atoms with H/sub 2/ molecules. I. Ab initio potential energy surfaces and qualitative discussion of the quenching process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Botschwina, P.; Meyer, W.; Hertel, I.V.

Potential energy surfaces have been calculated for the four lowest electronic states of Na (3 /sup 2/S, 3 /sup 2/P)+H/sub 2/(/sup 1/..sigma../sup +//sub g/) by means of the RHF--SCF and PNO--CEPA methods. For the so-called quenching process of Na (3 /sup 2/P) by H/sub 2/ at low initial translational energies (E--VRT energy transfer) the energetically most favorable path occurs in C/sub 2v/ symmetry, since: at intermediate Na--H/sub 2/ separation: the A /sup 2/B/sub 2/ potential energy surface is attractive. From the CEPA calculations, the crossing point of minimal energy between the X /sup 2/A/sub 1/ and A /sup 2/B/sub 2/more » surfaces is obtained at R/sub c/ = 3.57 a.u. and r/sub c/ = 2.17 a.u. with an energy difference to the asymptotic limit (R = infinity, r = r/sub e/) of -0.06 eV. It is thus classically accessible without any initial translational energy, but at low initial translational energies (approx.0.1 eV) quenching will be efficient only for arrangements of collision partners close to C/sub 2v/ symmetry. There is little indication of an avoiding crossing with an ionic intermediate correlating asymptotically with Na/sup +/ and H/sub 2//sup -/ as was assumed in previous discussions of the quenching process. The dependence of the total quenching cross sections on the initial translational energy is discussed by means of the ''absorbing sphere'' model, taking the initial zero-point vibrational energy of the hydrogen molecule into account. New experimental data of the product channel distribution in H/sub 2/ for center-of-mass forward scattering are presented. The final vibrational states v' = 3, 2, 1, and 0 of H/sub 2/ are populated to about 26%, 61%, 13%, and 0%, respectively. The observed distributions in H/sub 2/ (and D/sub 2/) may be rationalized by simple dynamic considerations on the basis of the calculated surfaces.« less

Uncertainty of the potential curve minimum for diatomic molecules extrapolated from Dunham type coefficients

NASA Astrophysics Data System (ADS)

Ilieva, T.; Iliev, I.; Pashov, A.

2016-12-01

In the traditional description of electronic states of diatomic molecules by means of molecular constants or Dunham coefficients, one of the important fitting parameters is the value of the zero point energy - the minimum of the potential curve or the energy of the lowest vibrational-rotational level - E00 . Their values are almost always the result of an extrapolation and it may be difficult to estimate their uncertainties, because they are connected not only with the uncertainty of the experimental data, but also with the distribution of experimentally observed energy levels and the particular realization of set of Dunham coefficients. This paper presents a comprehensive analysis based on Monte Carlo simulations, which aims to demonstrate the influence of all these factors on the uncertainty of the extrapolated minimum of the potential energy curve U (Re) and the value of E00 . The very good extrapolation properties of the Dunham coefficients are quantitatively confirmed and it is shown that for a proper estimate of the uncertainties, the ambiguity in the composition of the Dunham coefficients should be taken into account.

Interaction of monovalent cations with acetonitrile

NASA Astrophysics Data System (ADS)

Černušák, Ivan; Aranyosiová, Monika; Vollárová, Ol'ga; Velič, Dušan; Kirdajová, Ol'ga; Benko, Ján

Solvation of monovalent cations (Me+) of alkali metals=Na+, K+, Rb+, and Cs+, coinage metals=Cu+, Ag+, Au+, and p-block elements Ga+, In+, and Tl+ with acetonitrile was studied by means of ab initio calculations and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The intermolecular interactions in the complexes Me+···CH3CN were investigated using the coupled clusters theory including single, double, and noniterative triple substitutions (CCSD(T)) in conjunction with the Pol and Pol-dk basis sets. The binding energies of these donor-acceptor complexes were estimated; taking into account the basis set superposition error, zero-point vibrations, correlation contribution, and scalar relativistic corrections. The theoretical ΔG0298 K values based on CCSD(T)/Pol and/or CCSD(T)/Pol-dk binding energies correlated well with experimental transfer Gibbs energies (from water to acetonitrile) for the series of cations. In the case of Au monocation, relativistic correction turned out to be extremely important. Composition of the complex of Ag+ and Na+ with acetonitrile was determined by using SIMS supporting both theoretical and experimental transfer Gibbs energies.

Uncertainty relations, zero point energy and the linear canonical group

NASA Technical Reports Server (NTRS)

Sudarshan, E. C. G.

1993-01-01

The close relationship between the zero point energy, the uncertainty relations, coherent states, squeezed states, and correlated states for one mode is investigated. This group-theoretic perspective enables the parametrization and identification of their multimode generalization. In particular the generalized Schroedinger-Robertson uncertainty relations are analyzed. An elementary method of determining the canonical structure of the generalized correlated states is presented.

Rotating Casimir systems: Magnetic-field-enhanced perpetual motion, possible realization in doped nanotubes, and laws of thermodynamics

NASA Astrophysics Data System (ADS)

Chernodub, M. N.

2013-01-01

Recently, we have demonstrated that for a certain class of Casimir-type systems (“devices”) the energy of zero-point vacuum fluctuations reaches its global minimum when the device rotates about a certain axis rather than remains static. This rotational vacuum effect may lead to the emergence of permanently rotating objects provided the negative rotational energy of zero-point fluctuations cancels the positive rotational energy of the device itself. In this paper, we show that for massless electrically charged particles the rotational vacuum effect should be drastically (astronomically) enhanced in the presence of a magnetic field. As an illustration, we show that in a background of experimentally available magnetic fields the zero-point energy of massless excitations in rotating torus-shaped doped carbon nanotubes may indeed overwhelm the classical energy of rotation for certain angular frequencies so that the permanently rotating state is energetically favored. The suggested “zero-point-driven” devices—which have no internally moving parts—correspond to a perpetuum mobile of a new, fourth kind: They do not produce any work despite the fact that their equilibrium (ground) state corresponds to a permanent rotation even in the presence of an external environment. We show that our proposal is consistent with the laws of thermodynamics.

Polyad quantum numbers and multiple resonances in anharmonic vibrational studies of polyatomic molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krasnoshchekov, Sergey V.; Stepanov, Nikolay F.

2013-11-14

In the theory of anharmonic vibrations of a polyatomic molecule, mixing the zero-order vibrational states due to cubic, quartic and higher-order terms in the potential energy expansion leads to the appearance of more-or-less isolated blocks of states (also called polyads), connected through multiple resonances. Such polyads of states can be characterized by a common secondary integer quantum number. This polyad quantum number is defined as a linear combination of the zero-order vibrational quantum numbers, attributed to normal modes, multiplied by non-negative integer polyad coefficients, which are subject to definition for any particular molecule. According to Kellman's method [J. Chem. Phys.more » 93, 6630 (1990)], the corresponding formalism can be conveniently described using vector algebra. In the present work, a systematic consideration of polyad quantum numbers is given in the framework of the canonical Van Vleck perturbation theory (CVPT) and its numerical-analytic operator implementation for reducing the Hamiltonian to the quasi-diagonal form, earlier developed by the authors. It is shown that CVPT provides a convenient method for the systematic identification of essential resonances and the definition of a polyad quantum number. The method presented is generally suitable for molecules of significant size and complexity, as illustrated by several examples of molecules up to six atoms. The polyad quantum number technique is very useful for assembling comprehensive basis sets for the matrix representation of the Hamiltonian after removal of all non-resonance terms by CVPT. In addition, the classification of anharmonic energy levels according to their polyad quantum numbers provides an additional means for the interpretation of observed vibrational spectra.« less

Representing and selecting vibrational angular momentum states for quasiclassical trajectory chemical dynamics simulations.

PubMed

Lourderaj, Upakarasamy; Martínez-Núñez, Emilio; Hase, William L

2007-10-18

Linear molecules with degenerate bending modes have states, which may be represented by the quantum numbers N and L. The former gives the total energy for these modes and the latter identifies their vibrational angular momentum jz. In this work, the classical mechanical analog of the N,L-quantum states is reviewed, and an algorithm is presented for selecting initial conditions for these states in quasiclassical trajectory chemical dynamics simulations. The algorithm is illustrated by choosing initial conditions for the N = 3 and L = 3 and 1 states of CO2. Applications of this algorithm are considered for initial conditions without and with zero-point energy (zpe) included in the vibrational angular momentum states and the C-O stretching modes. The O-atom motions in the x,y-plane are determined for these states from classical trajectories in Cartesian coordinates and are compared with the motion predicted by the normal-mode model. They are only in agreement for the N = L = 3 state without vibrational angular momentum zpe. For the remaining states, the Cartesian O-atom motions are considerably different from the elliptical motion predicted by the normal-mode model. This arises from bend-stretch coupling, including centrifugal distortion, in the Cartesian trajectories, which results in tubular instead of elliptical motion. Including zpe in the C-O stretch modes introduces considerable complexity into the O-atom motions for the vibrational angular momentum states. The short-time O-atom motions for these trajectories are highly irregular and do not appear to have any identifiable characteristics. However, the O-atom motions for trajectories integrated for substantially longer period of times acquire unique properties. With C-O stretch zpe included, the long-time O-atom motion becomes tubular for trajectories integrated to approximately 14 ps for the L = 3 states and to approximately 44 ps for the L = 1 states.

Zero-point fluctuations in naphthalene and their effect on charge transport parameters.

PubMed

Kwiatkowski, Joe J; Frost, Jarvist M; Kirkpatrick, James; Nelson, Jenny

2008-09-25

We calculate the effect of vibronic coupling on the charge transport parameters in crystalline naphthalene, between 0 and 400 K. We find that nuclear fluctuations can cause large changes in both the energy of a charge on a molecule and on the electronic coupling between molecules. As a result, nuclear fluctuations cause wide distributions of both energies and couplings. We show that these distributions have a small temperature dependence and that, even at high temperatures, vibronic coupling is dominated by the effect of zero-point fluctuations. Because of the importance of zero-point fluctuations, we find that the distributions of energies and couplings have substantial width, even at 0 K. Furthermore, vibronic coupling with high energy modes may be significant, even though these modes are never thermally activated. Our results have implications for the temperature dependence of charge mobilities in organic semiconductors.

On the contribution of intramolecular zero point energy to the equation of state of solid H2

NASA Technical Reports Server (NTRS)

Chandrasekharan, V.; Etters, R. D.

1978-01-01

Experimental evidence shows that the internal zero-point energy of the H2 molecule exhibits a relatively strong pressure dependence in the solid as well as changing considerably upon condensation. It is shown that these effects contribute about 6% to the total sublimation energy and to the pressure in the solid state. Methods to modify the ab initio isolated pair potential to account for these environmental effects are discussed.

Coupled-cluster and explicitly correlated perturbation-theory calculations of the uracil anion.

PubMed

Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej

2007-02-28

A valence-type anion of the canonical tautomer of uracil has been characterized using explicitly correlated second-order Moller-Plesset perturbation theory (RI-MP2-R12) in conjunction with conventional coupled-cluster theory with single, double, and perturbative triple excitations. At this level of electron-correlation treatment and after inclusion of a zero-point vibrational energy correction, determined in the harmonic approximation at the RI-MP2 level of theory, the valence anion is adiabatically stable with respect to the neutral molecule by 40 meV. The anion is characterized by a vertical detachment energy of 0.60 eV. To obtain accurate estimates of the vertical and adiabatic electron binding energies, a scheme was applied in which electronic energy contributions from various levels of theory were added, each of them extrapolated to the corresponding basis-set limit. The MP2 basis-set limits were also evaluated using an explicitly correlated approach, and the results of these calculations are in agreement with the extrapolated values. A remarkable feature of the valence anionic state is that the adiabatic electron binding energy is positive but smaller than the adiabatic electron binding energy of the dipole-bound state.

Multi-directional electromagnetic vibration energy harvester using circular Halbach array

NASA Astrophysics Data System (ADS)

Qiu, Jing; Liu, Xin; Hu, Zhenwen; Chang, Qijie; Gao, Yuan; Yang, Jin; Wen, Jing; Tang, Xiaosheng; Hu, Wei

2017-05-01

In this paper, a multi-directional electromagnetic vibration energy harvester (EVEH) using the circular Halbach array (HA) is presented based on the Faraday's law of electromagnetic induction. The circular HA is a specific arrangement of permanent magnets which could concentrate the magnetic field inside the circular array by a certain rule, while reduce the magnetic field outside the circular array to almost zero at the same time. The HA could break through the limitation of the related published vibration energy harvesters that could work in only one single direction. Thus, it could optimize the collecting efficiency. The experimental results show that the presented harvester could generate considerable electric output power in all vibrating directions. An optimal output power is 9.32 mW at a resonant frequency of 15.40 Hz with an acceleration of 0.5 g (with g=9.8 m/s2) across a 700-turn coil in the vibrating direction of 90°, which is 1.53 times than the minimum optimal one in the direction of 45°. The EVEH using the circular HA could work in all directions and generate considerable electric output power, which validates the feasibility of the EVEH that works in all directions and is beneficial for improving the practical application.

Temperature Dependence of Wavelength Selectable Zero-Phonon Emission from Single Defects in Hexagonal Boron Nitride.

PubMed

Jungwirth, Nicholas R; Calderon, Brian; Ji, Yanxin; Spencer, Michael G; Flatté, Michael E; Fuchs, Gregory D

2016-10-12

We investigate the distribution and temperature-dependent optical properties of sharp, zero-phonon emission from defect-based single photon sources in multilayer hexagonal boron nitride (h-BN) flakes. We observe sharp emission lines from optically active defects distributed across an energy range that exceeds 500 meV. Spectrally resolved photon-correlation measurements verify single photon emission, even when multiple emission lines are simultaneously excited within the same h-BN flake. We also present a detailed study of the temperature-dependent line width, spectral energy shift, and intensity for two different zero-phonon lines centered at 575 and 682 nm, which reveals a nearly identical temperature dependence despite a large difference in transition energy. Our temperature-dependent results are well described by a lattice vibration model that considers piezoelectric coupling to in-plane phonons. Finally, polarization spectroscopy measurements suggest that whereas the 575 nm emission line is directly excited by 532 nm excitation, the 682 nm line is excited indirectly.

Full-Dimensional Quantum Calculations of Vibrational Levels of NH4(+) and Isotopomers on An Accurate Ab Initio Potential Energy Surface.

PubMed

Yu, Hua-Gen; Han, Huixian; Guo, Hua

2016-04-14

Vibrational energy levels of the ammonium cation (NH4(+)) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4(+) and ND4(+) exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. The low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm(-1).

Water Electrolyzers and the Zero-Point Energy

NASA Astrophysics Data System (ADS)

King, M. B.

The gas emitted from popular water electrolyzer projects manifests unusual energetic anomalies, which include vaporizing tungsten when used in a welding torch and running internal combustion engines on small quantities of the gas. Some claim to run generators in closed loop fashion solely on the gas from the electrolyzer, which is powered solely from the generator. Most investigators believe the energy is from burning hydrogen. A hypothesis is proposed that the dominant energy is not coming from hydrogen, but rather it is coming from charged water gas clusters, which activate and coherently trap zero-point energy.

Internal proton transfer and H2 rotations in the H5(+) cluster: a marked influence on its thermal equilibrium state.

PubMed

de Tudela, Ricardo Pérez; Barragán, Patricia; Prosmiti, Rita; Villarreal, Pablo; Delgado-Barrio, Gerardo

2011-03-31

Classical and path integral Monte Carlo (CMC, PIMC) "on the fly" calculations are carried out to investigate anharmonic quantum effects on the thermal equilibrium structure of the H5(+) cluster. The idea to follow in our computations is based on using a combination of the above-mentioned nuclear classical and quantum statistical methods, and first-principles density functional (DFT) electronic structure calculations. The interaction energies are computed within the DFT framework using the B3(H) hybrid functional, specially designed for hydrogen-only systems. The global minimum of the potential is predicted to be a nonplanar configuration of C(2v) symmetry, while the next three low-lying stationary points on the surface correspond to extremely low-energy barriers for the internal proton transfer and to the rotation of the H2 molecules, around the C2 axis of H5(+), connecting the symmetric C(2v) minima in the planar and nonplanar orientations. On the basis of full-dimensional converged PIMC calculations, results on the quantum vibrational zero-point energy (ZPE) and state of H5(+) are reported at a low temperature of 10 K, and the influence of the above-mentioned topological features of the surface on its probability distributions is clearly demonstrated.

Theory and Normal Mode Analysis of Change in Protein Vibrational Dynamics on Ligand Binding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mortisugu, Kei; Njunda, Brigitte; Smith, Jeremy C

2009-12-01

The change of protein vibrations on ligand binding is of functional and thermodynamic importance. Here, this process is characterized using a simple analytical 'ball-and-spring' model and all-atom normal-mode analysis (NMA) of the binding of the cancer drug, methotrexate (MTX) to its target, dihydrofolate reductase (DHFR). The analytical model predicts that the coupling between protein vibrations and ligand external motion generates entropy-rich, low-frequency vibrations in the complex. This is consistent with the atomistic NMA which reveals vibrational softening in forming the DHFR-MTX complex, a result also in qualitative agreement with neutron-scattering experiments. Energy minimization of the atomistic bound-state (B) structure whilemore » gradually decreasing the ligand interaction to zero allows the generation of a hypothetical 'intermediate' (I) state, without the ligand force field but with a structure similar to that of B. In going from I to B, it is found that the vibrational entropies of both the protein and MTX decrease while the complex structure becomes enthalpically stabilized. However, the relatively weak DHFR:MTX interaction energy results in the net entropy gain arising from coupling between the protein and MTX external motion being larger than the loss of vibrational entropy on complex formation. This, together with the I structure being more flexible than the unbound structure, results in the observed vibrational softening on ligand binding.« less

Semiclassical wave packet treatment of scattering resonances: application to the delta zero-point energy effect in recombination reactions.

PubMed

Vetoshkin, Evgeny; Babikov, Dmitri

2007-09-28

For the first time Feshbach-type resonances important in recombination reactions are characterized using the semiclassical wave packet method. This approximation allows us to determine the energies, lifetimes, and wave functions of the resonances and also to observe a very interesting correlation between them. Most important is that this approach permits description of a quantum delta-zero-point energy effect in recombination reactions and reproduces the anomalous rates of ozone formation.

Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N2 Collisions.

PubMed

Kim, Hyunsik; Paul, Amit K; Pratihar, Subha; Hase, William L

2016-07-14

Chemical dynamics simulations were performed to investigate collisional energy transfer from highly vibrationally excited azulene (Az*) in a N2 bath. The intermolecular potential between Az and N2, used for the simulations, was determined from MP2/6-31+G* ab initio calculations. Az* is prepared with an 87.5 kcal/mol excitation energy by using quantum microcanonical sampling, including its 95.7 kcal/mol zero-point energy. The average energy of Az* versus time, obtained from the simulations, shows different rates of Az* deactivation depending on the N2 bath density. Using the N2 bath density and Lennard-Jones collision number, the average energy transfer per collision ⟨ΔEc⟩ was obtained for Az* as it is collisionally relaxed. By comparing ⟨ΔEc⟩ versus the bath density, the single collision limiting density was found for energy transfer. The resulting ⟨ΔEc⟩, for an 87.5 kcal/mol excitation energy, is 0.30 ± 0.01 and 0.32 ± 0.01 kcal/mol for harmonic and anharmonic Az potentials, respectively. For comparison, the experimental value is 0.57 ± 0.11 kcal/mol. During Az* relaxation there is no appreciable energy transfer to Az translation and rotation, and the energy transfer is to the N2 bath.

Two-component, ab initio potential energy surface for CO2—H2O, extension to the hydrate clathrate, CO2@(H2O)20, and VSCF/VCI vibrational analyses of both

NASA Astrophysics Data System (ADS)

Wang, Qingfeng Kee; Bowman, Joel M.

2017-10-01

We report an ab initio, full-dimensional, potential energy surface (PES) for CO2—H2O, in which two-body interaction energies are fit using a basis of permutationally invariant polynomials and combined with accurate potentials for the non-interacting monomers. This approach which we have termed "plug and play" is extended here to improve the precision of the 2-body fit in the long range. This is done by combining two separate fits. One is a fit to 47 593 2-body energies in the region of strong interaction and approaching the long range, and the second one is a fit to 6244 2-body energies in the long range. The two fits have a region of overlap which permits a smooth switch from one to the other. All energies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ level of theory. Properties of the full PES, i.e., stationary points, harmonic frequencies of the global minimum, etc., are shown to be in excellent agreement with direct CCSD(T)-F12b/aug-cc-pVTZ results. Diffusion Monte Carlo calculations of the dimer zero-point energy (ZPE) are performed, and a dissociation energy, D0, of 787 cm-1 is obtained using that ZPE, De, and the rigorous ZPEs of the monomers. Using a benchmark De, D0 is 758 cm-1. Vibrational self-consistent field (VSCF)/virtual state configuration interaction (VCI) MULTIMODE calculations of intramolecular fundamentals are reported and are in good agreement with available experimental results. Finally, the full dimer PES is combined with an existing ab initio water potential to develop a potential for the CO2 hydrate clathrate CO2(H2O)20(512 water cage). A full normal-mode analysis of this hydrate clathrate is reported as are local-monomer VSCF/VCI calculations of the fundamentals of CO2.

Two-component, ab initio potential energy surface for CO2-H2O, extension to the hydrate clathrate, CO2@(H2O)20, and VSCF/VCI vibrational analyses of both.

PubMed

Wang, Qingfeng Kee; Bowman, Joel M

2017-10-28

We report an ab initio, full-dimensional, potential energy surface (PES) for CO 2 -H 2 O, in which two-body interaction energies are fit using a basis of permutationally invariant polynomials and combined with accurate potentials for the non-interacting monomers. This approach which we have termed "plug and play" is extended here to improve the precision of the 2-body fit in the long range. This is done by combining two separate fits. One is a fit to 47 593 2-body energies in the region of strong interaction and approaching the long range, and the second one is a fit to 6244 2-body energies in the long range. The two fits have a region of overlap which permits a smooth switch from one to the other. All energies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ level of theory. Properties of the full PES, i.e., stationary points, harmonic frequencies of the global minimum, etc., are shown to be in excellent agreement with direct CCSD(T)-F12b/aug-cc-pVTZ results. Diffusion Monte Carlo calculations of the dimer zero-point energy (ZPE) are performed, and a dissociation energy, D 0 , of 787 cm -1 is obtained using that ZPE, D e , and the rigorous ZPEs of the monomers. Using a benchmark D e , D 0 is 758 cm -1 . Vibrational self-consistent field (VSCF)/virtual state configuration interaction (VCI) MULTIMODE calculations of intramolecular fundamentals are reported and are in good agreement with available experimental results. Finally, the full dimer PES is combined with an existing ab initio water potential to develop a potential for the CO 2 hydrate clathrate CO 2 (H 2 O) 20 (5 12 water cage). A full normal-mode analysis of this hydrate clathrate is reported as are local-monomer VSCF/VCI calculations of the fundamentals of CO 2 .

A benchmark theoretical study of the electronic ground state and of the singlet-triplet split of benzene and linear acenes

NASA Astrophysics Data System (ADS)

Hajgató, B.; Szieberth, D.; Geerlings, P.; De Proft, F.; Deleuze, M. S.

2009-12-01

A benchmark theoretical study of the electronic ground state and of the vertical and adiabatic singlet-triplet (ST) excitation energies of benzene (n =1) and n-acenes (C4n+2H2n+4) ranging from naphthalene (n =2) to heptacene (n =7) is presented, on the ground of single- and multireference calculations based on restricted or unrestricted zero-order wave functions. High-level and large scale treatments of electronic correlation in the ground state are found to be necessary for compensating giant but unphysical symmetry-breaking effects in unrestricted single-reference treatments. The composition of multiconfigurational wave functions, the topologies of natural orbitals in symmetry-unrestricted CASSCF calculations, the T1 diagnostics of coupled cluster theory, and further energy-based criteria demonstrate that all investigated systems exhibit a A1g singlet closed-shell electronic ground state. Singlet-triplet (S0-T1) energy gaps can therefore be very accurately determined by applying the principles of a focal point analysis onto the results of a series of single-point and symmetry-restricted calculations employing correlation consistent cc-pVXZ basis sets (X=D, T, Q, 5) and single-reference methods [HF, MP2, MP3, MP4SDQ, CCSD, CCSD(T)] of improving quality. According to our best estimates, which amount to a dual extrapolation of energy differences to the level of coupled cluster theory including single, double, and perturbative estimates of connected triple excitations [CCSD(T)] in the limit of an asymptotically complete basis set (cc-pV∞Z), the S0-T1 vertical excitation energies of benzene (n =1) and n-acenes (n =2-7) amount to 100.79, 76.28, 56.97, 40.69, 31.51, 22.96, and 18.16 kcal/mol, respectively. Values of 87.02, 62.87, 46.22, 32.23, 24.19, 16.79, and 12.56 kcal/mol are correspondingly obtained at the CCSD(T)/cc-pV∞Z level for the S0-T1 adiabatic excitation energies, upon including B3LYP/cc-PVTZ corrections for zero-point vibrational energies. In line with the absence of Peierls distortions, extrapolations of results indicate a vanishingly small S0-T1 energy gap of 0 to ˜4 kcal/mol (˜0.17 eV) in the limit of an infinitely large polyacene.

Energy of the quasi-free electron in supercritical krypton near the critical point.

PubMed

Li, Luxi; Evans, C M; Findley, G L

2005-12-01

Field ionization measurements of high-n CH(3)I and C(2)H(5)I Rydberg states doped into krypton are presented as a function of krypton number density along the critical isotherm. These data exhibit a decrease in the krypton-induced shift of the dopant ionization energy near the critical point. This change in shift is modeled to within +/-0.2% of experiment using a theory that accounts for the polarization of krypton by the dopant ion, the polarization of krypton by the quasi-free electron that arises from field ionization of the dopant, and the zero point kinetic energy of the free electron. The overall decrease in the shift of the dopant ionization energy near the critical point of krypton, which is a factor of 2 larger than that observed in argon, is dominated by the increase in the zero point kinetic energy of the quasi-free electron.

Self-tuning pressure-feedback control by pole placement for vibration reduction of excavator with independent metering fluid power system

NASA Astrophysics Data System (ADS)

Ding, Ruqi; Xu, Bing; Zhang, Junhui; Cheng, Min

2017-08-01

Independent metering control systems are promising fluid power technologies compared with traditional valve controlled systems. By breaking the mechanical coupling between the inlet and outlet, the meter-out valve can open as large as possible to reduce energy consumptions. However, the lack of damping in outlet causes stronger vibrations. To address the problem, the paper designs a hybrid control method combining dynamic pressure-feedback and active damping control. The innovation resides in the optimization of damping by introducing pressure feedback to make trade-offs between high stability and fast response. To achieve this goal, the dynamic response pertaining to the control parameters consisting of feedback gain and cut-off frequency, are analyzed via pole-zero locations. Accordingly, these parameters are tuned online in terms of guaranteed dominant pole placement such that the optimal damping can be accurately captured under a considerable variation of operating conditions. The experiment is deployed in a mini-excavator. The results pertaining to different control parameters confirm the theoretical expectations via pole-zero locations. By using proposed self-tuning controller, the vibrations are almost eliminated after only one overshoot for different operation conditions. The overshoots are also reduced with less decrease of the response time. In addition, the energy-saving capability of independent metering system is still not affected by the improvement of controllability.

Thermodynamic Stability of Ice II and Its Hydrogen-Disordered Counterpart: Role of Zero-Point Energy.

PubMed

Nakamura, Tatsuya; Matsumoto, Masakazu; Yagasaki, Takuma; Tanaka, Hideki

2016-03-03

We investigate why no hydrogen-disordered form of ice II has been found in nature despite the fact that most of hydrogen-ordered ices have hydrogen-disordered counterparts. The thermodynamic stability of a set of hydrogen-ordered ice II variants relative to ice II is evaluated theoretically. It is found that ice II is more stable than the disordered variants so generated as to satisfy the simple ice rule due to the lower zero-point energy as well as the pair interaction energy. The residual entropy of the disordered ice II phase gradually compensates the unfavorable free energy with increasing temperature. The crossover, however, occurs at a high temperature well above the melting point of ice III. Consequently, the hydrogen-disordered phase does not exist in nature. The thermodynamic stability of partially hydrogen-disordered ices is also scrutinized by examining the free-energy components of several variants obtained by systematic inversion of OH directions in ice II. The potential energy of one variant is lower than that of the ice II structure, but its Gibbs free energy is slightly higher than that of ice II due to the zero-point energy. The slight difference in the thermodynamic stability leaves the possibility of the partial hydrogen-disorder in real ice II.

The structure and energetics of the HCN → HNC transition state

NASA Astrophysics Data System (ADS)

Lee, Timothy J.; Rendell, Alistair P.

1991-03-01

The optimum geometries and quadratic force constants of HCN, HNC and the transition state connecting them have been determined at the single and double excitation coupled-cluster (CCSD) and CCSD(T) levels of theory. Energy differences were evaluated using the CCSD and CCSD(T) methods in conjunction with large atomic natural orbital basis sets containing g-type basis functions on the heavy atoms and f-type functions on hydrogen. The most reliable structure obtained for the transition state has bond distances of 1.194, 1.188 and 1.389 Å for rCN, rCH and rNH, respectively. Including a correction for zero-point vibrational energies, the transition state is predicted to be 44.6 ± 1.0 kcal/mol above the HCN isomer, while HNC is predicted to be 14.4 ± 1.0 kcal/mol above HCN. The latter value is in excellent agreement with the most recent experimental determination (14.8 ± 2.0 kcal/mol).

Reshaping the phonon energy landscape of nanocrystals inside a terahertz plasmonic nanocavity.

PubMed

Jin, Xin; Cerea, Andrea; Messina, Gabriele C; Rovere, Andrea; Piccoli, Riccardo; De Donato, Francesco; Palazon, Francisco; Perucchi, Andrea; Di Pietro, Paola; Morandotti, Roberto; Lupi, Stefano; De Angelis, Francesco; Prato, Mirko; Toma, Andrea; Razzari, Luca

2018-02-22

Phonons (quanta of collective vibrations) are a major source of energy dissipation and drive some of the most relevant properties of materials. In nanotechnology, phonons severely affect light emission and charge transport of nanodevices. While the phonon response is conventionally considered an inherent property of a nanomaterial, here we show that the dipole-active phonon resonance of semiconducting (CdS) nanocrystals can be drastically reshaped inside a terahertz plasmonic nanocavity, via the phonon strong coupling with the cavity vacuum electric field. Such quantum zero-point field can indeed reach extreme values in a plasmonic nanocavity, thanks to a mode volume well below λ 3 /10 7 . Through Raman measurements, we find that the nanocrystals within a nanocavity exhibit two new "hybridized" phonon peaks, whose spectral separation increases with the number of nanocrystals. Our findings open exciting perspectives for engineering the optical phonon response of functional nanomaterials and for implementing a novel platform for nanoscale quantum optomechanics.

The Strength of Hydrogen Bonds between Fluoro-Organics and Alcohols, a Theoretical Study.

PubMed

Rosenberg, Robert E

2018-05-10

Fluorinated organic compounds are ubiquitous in the pharmaceutical and agricultural industries. To better discern the mode of action of these compounds, it is critical to understand the strengths of hydrogen bonds involving fluorine. There are only a few published examples of the strengths of these bonds. This study provides a high level ab initio study of inter- and intramolecular hydrogen bonds between RF and R'OH, where R and R' are aryl, vinyl, alkyl, and cycloalkyl. Intermolecular binding energies average near 5 kcal/mol, while intramolecular binding energies average about 3 kcal/mol. Inclusion of zero-point energies and applying a counterpoise correction lessen the difference. In both series, modest increases in binding energies are seen with increased acidity of R'OH and increased electron donation of R in RF. In the intramolecular compounds, binding energy increases with the rigidity of the F-(C) n -OH ring. Inclusion of free energy corrections at 298 K results in exoergic binding energies for the intramolecular compounds and endoergic binding energies for the intermolecular compounds. Parameters such as bond lengths, vibrational frequencies, and atomic populations are consistent with formation of a hydrogen bond and with slightly stronger binding in the intermolecular cases over the intramolecular cases. However, these parameters correlated poorly with binding energies.

Zero photon dissociation of CS2+ in intense ultrashort laser pulses

NASA Astrophysics Data System (ADS)

Severt, Travis; Betsch, K. J.; Zohrabi, M.; Ablikim, U.; Jochim, Bethany; Carnes, K. D.; Esry, B. D.; Ben-Itzhak, I.

2013-05-01

We measured the dissociation of a CS2+ molecular ion beam in intense laser pulses (<50 fs, <1015 W/cm2), focusing on the zero photon dissociation (ZPD) and above threshold dissociation (ATD) mechanisms. The ZPD mechanism leads to dissociation with the net absorption of zero photons in a strong field. The present work extends the idea of ZPD to more complex molecules than the H2+ discussed in literature. Preliminary data suggests that ZPD is larger than ATD for CS2+ --> C+ + S+. We speculate that a pump-dump process occurs whereby the vibrational wavepacket in the electronic ground state of CS2+ is pumped into the electronic first excited state's continuum by a single photon during the laser pulse. Once this continuum vibrational wavepacket passes the potential barrier in the ground electronic potential, the emission of a second photon is stimulated by the same laser pulse, most likely when the wavepacket moves through the internuclear distance where the two electronic states are in resonance with the driving field. A comparison is made to ZPD and ATD in the isovalent CO2+ species. Curiously, ATD is the favored mechanism in CO2+. The underlying molecular structure and dynamics determining this preference will be discussed. Supported by Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy.

Generalized energy detector for weak random signals via vibrational resonance

NASA Astrophysics Data System (ADS)

Ren, Yuhao; Pan, Yan; Duan, Fabing

2018-03-01

In this paper, the generalized energy (GE) detector is investigated for detecting weak random signals via vibrational resonance (VR). By artificially injecting the high-frequency sinusoidal interferences into an array of GE statistics formed for the detector, we show that the normalized asymptotic efficacy can be maximized when the interference intensity takes an appropriate non-zero value. It is demonstrated that the normalized asymptotic efficacy of the dead-zone-limiter detector, aided by the VR mechanism, outperforms that of the GE detector without the help of high-frequency interferences. Moreover, the maximum normalized asymptotic efficacy of dead-zone-limiter detectors can approach a quarter of the second-order Fisher information for a wide range of non-Gaussian noise types.

Torsional, Vibrational and Vibration-Torsional Levels in the S_{1} and Ground Cationic D_{0}^{+} States of Para-Fluorotoluene

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William Duncan; Whalley, Laura E.; Claydon, Andrew; Carter, Joseph H.; Wright, Timothy G.

2017-06-01

The S_{1} electronic state and ground state of the cation of para-fluorotoluene (pFT) have been investigated using resonance-enhanced multiphoton ionization (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy. Here we focus on the low wavenumber region where a number of "pure" torsional, fundamental vibrational and vibration-torsional levels are expected; assignments of observed transitions are discussed, which are compared to results of published work on toluene (methylbenzene) from the Lawrance group. The similarity in the activity observed in the excitation spectrum of the two molecules is striking. A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). J. R. Gascooke, E. A. Virgo, and W. D. Lawrance J. Chem. Phys., 143, 044313 (2015).

Location of protons in N-H···N hydrogen-bonded systems: a theoretical study on intramolecular pyridine-dihydropyridine and pyridine-pyridinium pairs.

PubMed

Mori, Yukie; Takano, Keiko

2012-08-21

Two-dimensional potential energy surfaces (PESs) were calculated for the degenerate intramolecular proton transfer (PT) in two N-H···N hydrogen-bonded systems, (Z)-2-(2-pyridylmethylidene)-1,2-dihydropyridine (1) and monoprotonated di(2-pyridyl) ether (2), at the MP2/cc-pVDZ level of theory. The calculated PES had two minima in both cases. The energy barrier in 1 was higher than the zero-point energy (ZPE) level, while that in 2 was close to the ZPE. Vibrational wavefunctions were obtained by solving time-independent Schrödinger equations with the calculated PESs. The maximum points of the probability density were shifted from the energy minima towards the region where the covalent N-H bond was elongated and the N···N distance shortened. The effects of a polar solvent on the PES were investigated with the continuum or cluster models in such a way that the solute-solvent electrostatic interactions could be taken into account under non-equilibrated conditions. A solvated contact ion-pair was modelled by a cluster consisting of one cation 2, one chloride ion and 26 molecules of acetonitrile. The calculation with this model suggested that the bridging proton is localised in the deeper well due to the significant asymmetry of the PES and the high potential barrier.

The influence of micro-vibration on space-borne Fourier transform spectrometers

NASA Astrophysics Data System (ADS)

Bai, Shaojun; Hou, Lizhou; Ke, Junyu

2014-11-01

The space-borne Fourier Transform Spectrometers (FTS) are widely used for atmospheric studies and planetary explorations. An adapted version of the classical Michelson interferometer have succeeded in several space missions, which utilized a rotating arm carrying a pair of cube corner retro-reflectors to produce a variable optical path difference (OPD), and a metrology laser source to generate the trigger signals. One characteristic of this kind of FTS is that it is highly sensitive to micro-vibration disturbances. However, a variety of mechanical disturbances are present as the satellite is in orbit, such as flying wheels, pointing mechanisms and cryocoolers. Therefore, this paper investigates the influence of micro-vibration on the space-borne FTS. Firstly, the interferogram of metrology laser under harmonic disturbances is analyzed. The results show that the zero crossings of interferogram shift periodically, and it gives rise to ghost lines in the retrieved spectra. The amplitudes of ghost lines increase rapidly with the increasing of micro-vibration levels. As to the system that employs the constant OPD sampling strategy, the effect of zero-crossing shifting is reduced significantly. Nevertheless, the time delays between the reference signal and the main signal acquisition are inevitable because of the electronic circuit. Thus, the effect of time delays on the interferogram and eventually on the spectra is simulated. The analysis suggests that the amplitudes of ghost line in spectra increase with the increasing of time delay intervals.

A DFT study for the structural and electronic properties of Zn m Se n nanoclusters

NASA Astrophysics Data System (ADS)

Yadav, Phool Singh; Pandey, Dheeraj Kumar

2012-09-01

An ab initio study has been performed for the stability, structural and electronic properties of 19 small zinc selenide Zn m Se n ( m + n = 2-4) nanoclusters. Out of these nanoclusters, one nanocluster is found to be unstable due to its imaginary vibrational frequency. A B3LYP-DFT/6-311G(3df) method is used in the optimization of the geometries of the nanoclusters. We have calculated the zero point energy (ZPE), which is ignored by the other workers. The binding energies (BE), HOMO-LUMO gaps and bond lengths have been obtained for all the optimized nanoclusters. For the same value of ` m' and ` n', we designate the most stable structure the one, which has maximum final binding energy (FBE) per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), dipole moments and charge on atoms have been investigated for the most stable nanoclusters. For the same value of ` m' and ` n', the nanocluster containing maximum number of Se atoms is found to be most stable.

Diffusion dynamics of the Li+ ion on a model surface of amorphous carbon: a direct molecular orbital dynamics study.

PubMed

Tachikawa, Hiroto; Shimizu, Akira

2005-07-14

Diffusion processes of the Li+ ion on a model surface of amorphous carbon (Li+C96H24 system) have been investigated by means of the direct molecular orbital (MO) dynamics method at the semiempirical AM1 level. The total energy and energy gradient on the full-dimensional AM1 potential energy surface were calculated at each time step in the dynamics calculation. The optimized structure, where Li+ is located in the center of the cluster, was used as the initial structure at time zero. The dynamics calculation was carried out in the temperature range 100-1000 K. The calculations showed that the Li+ ion vibrates around the equilibrium point below 200 K, while the Li+ ion moves on the surface above 250 K. At intermediate temperatures (300 K < T < 400 K), the ion moves on the surface and falls in the edge regions of the cluster. At higher temperatures (600 K < T), the Li+ ion transfers freely on the surface and edge regions. The diffusion pathway of the Li+ ion was discussed on the basis of theoretical results.

Performance of an Optimally Tuned Range-Separated Hybrid Functional for 0-0 Electronic Excitation Energies.

PubMed

Jacquemin, Denis; Moore, Barry; Planchat, Aurélien; Adamo, Carlo; Autschbach, Jochen

2014-04-08

Using a set of 40 conjugated molecules, we assess the performance of an "optimally tuned" range-separated hybrid functional in reproducing the experimental 0-0 energies. The selected protocol accounts for the impact of solvation using a corrected linear-response continuum approach and vibrational corrections through calculations of the zero-point energies of both ground and excited-states and provides basis set converged data thanks to the systematic use of diffuse-containing atomic basis sets at all computational steps. It turns out that an optimally tuned long-range corrected hybrid form of the Perdew-Burke-Ernzerhof functional, LC-PBE*, delivers both the smallest mean absolute error (0.20 eV) and standard deviation (0.15 eV) of all tested approaches, while the obtained correlation (0.93) is large but remains slightly smaller than its M06-2X counterpart (0.95). In addition, the efficiency of two other recently developed exchange-correlation functionals, namely SOGGA11-X and ωB97X-D, has been determined in order to allow more complete comparisons with previously published data.

Ab initio study of structural, electronic, optical, and vibrational properties of Zn x S y ( x + y = 2 to 5) nanoclusters

NASA Astrophysics Data System (ADS)

Yadav, P. S.; Pandey, D. K.; Agrawal, S.; Agrawal, B. K.

2010-03-01

An ab initio study of the stability, structural, electronic. and optical properties has been performed for 46 zinc sulfide nanoclusters Zn x S y ( x + y = n = 2 to 5). Five out of them are seen to be unstable as their vibrational frequencies are found to be imaginary. A B3LYP-DFT/6-311G(3df) method is employed to optimize the geometries and a TDDFT method is used for the study of the optical properties. The binding energies (BE), HOMO-LUMO gaps and the bond lengths have been obtained for all the clusters. For the ZnS2, ZnS3, and ZnS4 nanoclusters, our stable structures are seen to be different from those obtained earlier by using the effective core potentials. We have also considered the zero point energy (ZPE) corrections ignored by the earlier workers. For a fixed value of n, we designate the most stable structure the one, which has maximum final binding energy per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), charges on the atoms, dipole moments, optical properties, vibrational frequencies, infrared intensities, relative infrared intensities, and Raman scattering activities have been investigated for the most stable structures. The nanoclusters containing large number of S atoms for each n is found to be most stable. The HOMO-LUMO gap decreases from n = 2-3 and then increases above n = 3. The IP and EA both fluctuate with the cluster size n. The optical absorption is quite weak in visible region but strong in the ultraviolet region in most of the nanoclusters except a few. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every nanocluster and may be used to characterize a specific nanocluster. The growth of most stable nanoclusters may be possible in the experiments.

Cooperative triple-proton/hydrogen atom relay in 7-azaindole(CH3OH)2 in the gas phase: remarkable change in the reaction mechanism from vibrational-mode specific to statistical fashion with increasing internal energy.

PubMed

Sakota, Kenji; Inoue, Naomi; Komoto, Yusuke; Sekiya, Hiroshi

2007-05-31

The 7-azaindole-methanol 1:2 cluster [7AI(CH(3)OH)2] undergoes excited-state triple-proton/hydrogen atom transfer (ESTPT/HT) along the hydrogen-bonded network in the gas phase. The measurements of the resonance-enhanced multiphoton ionization (REMPI) spectra of 7AI(CH(3)OH)2-d(n) (n = 0-3), where subscript n indicates the number of deuterium, and the fluorescence excitation spectrum of 7AI(CH(3)OH)2-d(0) allowed us to investigate the ESTPT/HT dynamics. By comparing the intensity ratios of the vibronic bands between 7AI(CH(3)OH)2-d(0) and 7AI(CH(3)OH)2-d(3) in REMPI spectra, we obtained the lower limit of an acceleration factor (f(a)(low)) of 7AI(CH(3)OH)2-d(0), which is the ratio of the reaction rate for the excitation of a vibronic state to that of the zero-point state in S(1). The f(a)(low) values are 2.7 +/- 0.83 and 4.0 +/- 1.2 for an in-phase intermolecular stretching vibration (sigma(1)) and its overtone (2sigma(1)) observed at 181 cm(-1) and 359 cm(-1) in the excitation spectrum, respectively, while that of the vibration (nu(2)/sigma(1) or nu(3)/sigma(1)) at 228 cm(-1) is 1.1 +/- 0.83. Thus, vibrational-mode-specific ESTPT/HT occurs in the low-energy region (600 cm(-1)). The excitation of an intramolecular ring mode (nu(intra)) of 7AI at 744 cm(-1) substantially enhances the reaction rate (f(a)(low) = 4.4 +/- 0.98), but the increase of f(a)(low) is not prominent for the excitation of v(intra) + sigma(1) at 926 cm(-1) (f(a)(low) = 5.0 +/- 1.6), although the sigma(1) mode is excited. These results suggest that the ESTPT/HT reaction in 7AI(CH(3)OH)2-d(0) directly proceeds from the photoexcited states with the internal energy less than approximately 600 cm(-1), but it occurs from the isoenergetically vibrational-energy redistributed states when the internal energy is large. This shows a remarkable feature of ESTPT/HT in 7AI(CH(3)OH)2; the nature of the reaction mechanism changes from vibrational-mode specific to statistical fashion with increasing the internal energy. The hydrogen-bonded network in 7AI(CH(3)OH)2-d(0) is represented by a directed graph. This shows that ESTPT/HT is one of the simplest examples of cooperative phenomena.

Full-dimensional quantum calculations of vibrational levels of NH 4 + and isotopomers on an accurate ab initio potential energy surface

DOE PAGES

Hua -Gen Yu; Han, Huixian; Guo, Hua

2016-03-29

Vibrational energy levels of the ammonium cation (NH 4 +) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH 4 + and ND 4 + exhibit a polyad structure, characterized by a collective quantum number P = 2(v 1 + v 3) + v 2 + v 4. As a result, the low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data ismore » better than 1 cm –1.« less

An assessment of mean-field mixed semiclassical approaches: Equilibrium populations and algorithm stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bellonzi, Nicole; Jain, Amber; Subotnik, Joseph E.

2016-04-21

We study several recent mean-field semiclassical dynamics methods, focusing on the ability to recover detailed balance for long time (equilibrium) populations. We focus especially on Miller and Cotton’s [J. Phys. Chem. A 117, 7190 (2013)] suggestion to include both zero point electronic energy and windowing on top of Ehrenfest dynamics. We investigate three regimes: harmonic surfaces with weak electronic coupling, harmonic surfaces with strong electronic coupling, and anharmonic surfaces with weak electronic coupling. In most cases, recent additions to Ehrenfest dynamics are a strong improvement upon mean-field theory. However, for methods that include zero point electronic energy, we show thatmore » anharmonic potential energy surfaces often lead to numerical instabilities, as caused by negative populations and forces. We also show that, though the effect of negative forces can appear hidden in harmonic systems, the resulting equilibrium limits do remain dependent on any windowing and zero point energy parameters.« less

Structure, stability, thermodynamic properties, and infrared spectra of the protonated water octamer H(+)(H2O)8.

PubMed

Karthikeyan, S; Park, Mina; Shin, Ilgyou; Kim, Kwang S

2008-10-16

We investigated various two-dimensional (2D) and three-dimensional (3D) structures of H (+)(H 2O) 8, using density functional theory (DFT), Moller-Plesset second-order perturbation theory (MP2), and coupled cluster theory with single, double, and perturbative triple excitations (CCSD(T)). The 3D structure is more stable than the 2D structure at all levels of theory on the Born-Oppenheimer surface. With the zero-point energy (ZPE) correction, the predicted structure varies depending on the level of theory. The DFT employing Becke's three parameters with Lee-Yang-Parr functionals (B3LYP) favors the 2D structure. At the complete basis set (CBS) limit, the MP2 calculation favors the 3D structure by 0.29 kcal/mol, and the CCSD(T) calculation favors the 3D structure by 0.27 kcal/mol. It is thus expected that both 2D and 3D structures are nearly isoenergetic near 0 K. At 100 K, all the calculations show that the 2D structure is much more stable in free binding energy than the 3D structure. The DFT and MP2 vibrational spectra of the 2D structure are consistent with the experimental spectra. First-principles Car-Parrinello molecular dynamics (CPMD) simulations show that the 2D Zundel-type vibrational spectra are in good agreement with the experiment.

Lattice vibrations in the Frenkel-Kontorova model. I. Phonon dispersion, number density, and energy

NASA Astrophysics Data System (ADS)

Meng, Qingping; Wu, Lijun; Welch, David O.; Zhu, Yimei

2015-06-01

We studied the lattice vibrations of two interpenetrating atomic sublattices via the Frenkel-Kontorova (FK) model of a linear chain of harmonically interacting atoms subjected to an on-site potential using the technique of thermodynamic Green's functions based on quantum field-theoretical methods. General expressions were deduced for the phonon frequency-wave-vector dispersion relations, number density, and energy of the FK model system. As the application of the theory, we investigated in detail cases of linear chains with various periods of the on-site potential of the FK model. Some unusual but interesting features for different amplitudes of the on-site potential of the FK model are discussed. In the commensurate structure, the phonon spectrum always starts at a finite frequency, and the gaps of the spectrum are true ones with a zero density of modes. In the incommensurate structure, the phonon spectrum starts from zero frequency, but at a nonzero wave vector; there are some modes inside these gap regions, but their density is very low. In our approximation, the energy of a higher-order commensurate state of the one-dimensional system at a finite temperature may become indefinitely close to the energy of an incommensurate state. This finding implies that the higher-order incommensurate-commensurate transitions are continuous ones and that the phase transition may exhibit a "devil's staircase" behavior at a finite temperature.

Modified relaxation dynamics and coherent energy exchange in coupled vibration-cavity polaritons

PubMed Central

Dunkelberger, A. D.; Spann, B. T.; Fears, K. P.; Simpkins, B. S.; Owrutsky, J. C.

2016-01-01

Coupling vibrational transitions to resonant optical modes creates vibrational polaritons shifted from the uncoupled molecular resonances and provides a convenient way to modify the energetics of molecular vibrations. This approach is a viable method to explore controlling chemical reactivity. In this work, we report pump–probe infrared spectroscopy of the cavity-coupled C–O stretching band of W(CO)6 and the direct measurement of the lifetime of a vibration-cavity polariton. The upper polariton relaxes 10 times more quickly than the uncoupled vibrational mode. Tuning the polariton energy changes the polariton transient spectra and relaxation times. We also observe quantum beats, so-called vacuum Rabi oscillations, between the upper and lower vibration-cavity polaritons. In addition to establishing that coupling to an optical cavity modifies the energy-transfer dynamics of the coupled molecules, this work points out the possibility of systematic and predictive modification of the excited-state kinetics of vibration-cavity polariton systems. PMID:27874010

Infrared-induced conformational isomerization and vibrational relaxation dynamics in melatonin and 5-methoxy-N-acetyl tryptophan methyl amide

NASA Astrophysics Data System (ADS)

Dian, Brian C.; Florio, Gina M.; Clarkson, Jasper R.; Longarte, Asier; Zwier, Timothy S.

2004-05-01

The conformational isomerization dynamics of melatonin and 5-methoxy N-acetyltryptophan methyl amide (5-methoxy NATMA) have been studied using the methods of IR-UV hole-filling spectroscopy and IR-induced population transfer spectroscopy. Using these techniques, single conformers of melatonin were excited via a well-defined NH stretch fundamental with an IR pump laser. This excess energy was used to drive conformational isomerization. By carrying out the infrared excitation early in a supersonic expansion, the excited molecules were re-cooled into their zero-point levels, partially re-filling the hole created in the ground state population of the excited conformer, and creating gains in population of the other conformers. These changes in population were detected using laser-induced fluorescence downstream in the expansion via an UV probe laser. The isomerization quantum yields for melatonin show some conformation specificity but no hint of vibrational mode specificity. In 5-methoxy NATMA, no isomerization was observed out of the single conformational well populated in the expansion in the absence of the infrared excitation. In order to study the dependence of the isomerization on the cooling rate, the experimental arrangement was modified so that faster cooling conditions could be studied. In this arrangement, the pump and probe lasers were overlapped in space in the high density region of the expansion, and the time dependence of the zero-point level populations of the conformers was probed following selective excitation of a single conformation. The analysis needed to extract isomerization quantum yields from the timing scans was developed and applied to the melatonin timing scans. Comparison between the frequency and time domain isomerization quantum yields under identical experimental conditions produced similar results. Under fast cooling conditions, the product quantum yields were shifted from their values under standard conditions. The results for melatonin are compared with those for N-acetyl tryptophan methyl amide.

Bearing damage assessment using Jensen-Rényi Divergence based on EEMD

NASA Astrophysics Data System (ADS)

Singh, Jaskaran; Darpe, A. K.; Singh, S. P.

2017-03-01

An Ensemble Empirical Mode Decomposition (EEMD) and Jensen Rényi divergence (JRD) based methodology is proposed for the degradation assessment of rolling element bearings using vibration data. The EEMD decomposes vibration signals into a set of intrinsic mode functions (IMFs). A systematic methodology to select IMFs that are sensitive and closely related to the fault is proposed in the paper. The change in probability distribution of the energies of the sensitive IMFs is measured through JRD which acts as a damage identification parameter. Evaluation of JRD with sensitive IMFs makes it largely unaffected by change/fluctuations in operating conditions. Further, an algorithm based on Chebyshev's inequality is applied to JRD to identify exact points of change in bearing health and remove outliers. The identified change points are investigated for fault classification as possible locations where specific defect initiation could have taken place. For fault classification, two new parameters are proposed: 'α value' and Probable Fault Index, which together classify the fault. To standardize the degradation process, a Confidence Value parameter is proposed to quantify the bearing degradation value in a range of zero to unity. A simulation study is first carried out to demonstrate the robustness of the proposed JRD parameter under variable operating conditions of load and speed. The proposed methodology is then validated on experimental data (seeded defect data and accelerated bearing life test data). The first validation on two different vibration datasets (inner/outer) obtained from seeded defect experiments demonstrate the effectiveness of JRD parameter in detecting a change in health state as the severity of fault changes. The second validation is on two accelerated life tests. The results demonstrate the proposed approach as a potential tool for bearing performance degradation assessment.

Insights into the phase diagram of bismuth ferrite from quasiharmonic free-energy calculations

NASA Astrophysics Data System (ADS)

Cazorla, Claudio; Iñiguez, Jorge

2013-12-01

We have used first-principles methods to investigate the phase diagram of multiferroic bismuth ferrite (BiFeO3 or BFO), revealing the energetic and vibrational features that control the occurrence of various relevant structures. More precisely, we have studied the relative stability of four low-energy BFO polymorphs by computing their free energies within the quasiharmonic approximation, introducing a practical scheme that allows us to account for the main effects of spin disorder. As expected, we find that the ferroelectric ground state of the material (with R3c space group) transforms into an orthorhombic paraelectric phase (Pnma) upon heating. We show that this transition is not significantly affected by magnetic disorder, and that the occurrence of the Pnma structure relies on its being vibrationally (although not elastically) softer than the R3c phase. We also investigate a representative member of the family of nanotwinned polymorphs recently predicted for BFO [S. Prosandeev et al., Adv. Funct. Mater. 23, 234 (2013), 10.1002/adfm.201201467] and discuss their possible stabilization at the boundaries separating the R3c and Pnma regions in the corresponding pressure-temperature phase diagram. Finally, we elucidate the intriguing case of the so-called supertetragonal phases of BFO: Our results explain why such structures have never been observed in the bulk material, despite their being stable polymorphs of very low energy. Quantitative comparison with experiment is provided whenever possible, and the relative importance of various physical effects (zero-point motion, spin fluctuations, thermal expansion) and technical features (employed exchange-correlation energy density functional) is discussed. Our work attests the validity and usefulness of the quasiharmonic scheme to investigate the phase diagram of this complex oxide, and prospective applications are discussed.

Comment on ‘The paradoxical zero reflection at zero energy’

NASA Astrophysics Data System (ADS)

van Dijk, W.; Nogami, Y.

2017-05-01

We point out that the anomalous threshold effect in one dimension occurs when the reflection probability at zero energy R(0) has some other value than unity, rather than R(0)=0 or R(0)\\ll 1 as implied by Ahmed et al in their paper entitled ‘The paradoxical zero reflection at zero energy’ (2017 Eur. J. Phys. 38 025401).

Changes in the zero-point energy of the protons as the source of the binding energy of water to A-phase DNA.

PubMed

Reiter, G F; Senesi, R; Mayers, J

2010-10-01

The measured changes in the zero-point kinetic energy of the protons are entirely responsible for the binding energy of water molecules to A phase DNA at the concentration of 6  water molecules/base pair. The changes in kinetic energy can be expected to be a significant contribution to the energy balance in intracellular biological processes and the properties of nano-confined water. The shape of the momentum distribution in the dehydrated A phase is consistent with coherent delocalization of some of the protons in a double well potential, with a separation of the wells of 0.2 Å.

Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy.

PubMed

Goncharov, Vasiliy; Kaledin, Leonid A; Heaven, Michael C

2006-10-07

The pulsed field ionization-zero kinetic energy photoelectron technique has been used to observe the low-lying energy levels of UO+. Rotationally resolved spectra were recorded for the ground state and the first nine electronically excited states. Extensive vibrational progressions were characterized. Omega+ assignments were unambiguously determined from the first rotational lines identified in each vibronic band. Term energies, vibrational frequencies, and anharmonicity constants for low-lying energy levels of UO+ are reported. In addition, accurate values for the ionization energies for UO [48,643.8(2) cm(-1)] and U [49,957.6(2) cm(-1)] were determined. The pattern of low-lying electronic states for UO+ indicates that they originate from the U3+(5f3)O2- configuration, where the uranium ion-centered interactions between the 5f electrons are significantly stronger than interactions with the intramolecular electric field. The latter lifts the degeneracy of U3+ ion-core states, but the atomic angular momentum quantum numbers remain reasonably well defined.

Neural networks vs Gaussian process regression for representing potential energy surfaces: A comparative study of fit quality and vibrational spectrum accuracy

NASA Astrophysics Data System (ADS)

Kamath, Aditya; Vargas-Hernández, Rodrigo A.; Krems, Roman V.; Carrington, Tucker; Manzhos, Sergei

2018-06-01

For molecules with more than three atoms, it is difficult to fit or interpolate a potential energy surface (PES) from a small number of (usually ab initio) energies at points. Many methods have been proposed in recent decades, each claiming a set of advantages. Unfortunately, there are few comparative studies. In this paper, we compare neural networks (NNs) with Gaussian process (GP) regression. We re-fit an accurate PES of formaldehyde and compare PES errors on the entire point set used to solve the vibrational Schrödinger equation, i.e., the only error that matters in quantum dynamics calculations. We also compare the vibrational spectra computed on the underlying reference PES and the NN and GP potential surfaces. The NN and GP surfaces are constructed with exactly the same points, and the corresponding spectra are computed with the same points and the same basis. The GP fitting error is lower, and the GP spectrum is more accurate. The best NN fits to 625/1250/2500 symmetry unique potential energy points have global PES root mean square errors (RMSEs) of 6.53/2.54/0.86 cm-1, whereas the best GP surfaces have RMSE values of 3.87/1.13/0.62 cm-1, respectively. When fitting 625 symmetry unique points, the error in the first 100 vibrational levels is only 0.06 cm-1 with the best GP fit, whereas the spectrum on the best NN PES has an error of 0.22 cm-1, with respect to the spectrum computed on the reference PES. This error is reduced to about 0.01 cm-1 when fitting 2500 points with either the NN or GP. We also find that the GP surface produces a relatively accurate spectrum when obtained based on as few as 313 points.

Noncolocated Structural Vibration Suppression Using Zero Annihilation Periodic Control

NASA Technical Reports Server (NTRS)

Bayard, David S.; Boussalis, Dhemetrios

1993-01-01

The Zero Annihilation Periodic (ZAP) controller is applied to the problem of vibration control of a noncolocated flexible structure. It is shown that even though the transfer function is nonminimum-phase, a plant inverse controller can be designed which elicits a deadbeat closed-loop response.

Torsional, Vibrational and Vibration-Torsional Levels in the S_{1} and Ground Cationic D_{0}^{+} States of Para-Xylene

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William Duncan; Groner, Peter; Wright, Timothy G.

2017-06-01

Insight gained from examining the "pure" torsional, vibrational and vibration-torsional (vibtor) levels of the single rotor molecules: toluene (methylbenzene) and para-fluorotoluene (pFT), is applied to the double rotor para-xylene (p-dimethylbenzene) molecule . Resonance-enhanced multiphoton ionization (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy are employed in order to investigate the S_{1} and ground cationic states of para-xylene. Observed transitions are assigned in the full molecular symmetry group (G_{72}) for the first time. J. R. Gascooke, E. A. Virgo, and W. D. Lawrance, J. Chem. Phys., 143, 044313 (2015). A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). A. M. Gardner, W. D. Tuttle, P. Groner and T. G. Wright, J. Chem. Phys., (2017, in press).

Algebraic Theory of Crystal Vibrations: Localization Properties of Wave Functions in Two-Dimensional Lattices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dietz, Barbara; Iachello, Francesco; Macek, Michal

The localization properties of the wave functions of vibrations in two-dimensional (2D) crystals are studied numerically for square and hexagonal lattices within the framework of an algebraic model. The wave functions of 2D lattices have remarkable localization properties, especially at the van Hove singularities (vHs). Finite-size sheets with a hexagonal lattice (graphene-like materials), in addition, exhibit at zero energy a localization of the wave functions at zigzag edges, so-called edge states. The striped structure of the wave functions at a vHs is particularly noteworthy. We have investigated its stability and that of the edge states with respect to perturbations inmore » the lattice structure, and the effect of the boundary shape on the localization properties. We find that the stripes disappear instantaneously at the vHs in a square lattice when turning on the perturbation, whereas they broaden but persist at the vHss in a hexagonal lattice. For one of them, they eventually merge into edge states with increasing coupling, which, in contrast to the zero-energy edge states, are localized at armchair edges. The results are corroborated based on participation ratios, obtained under various conditions.« less

Is localized infrared spectroscopy now possible in the electron microscope?

PubMed

Rez, Peter

2014-06-01

The recently developed in-column monochromators make it possible to record energy-c spectra with resolutions better than 30 meV from nanometer-sized regions. It should therefore in principle be possible to detect localized vibrational excitations. The scattering geometry in the electron microscope means that bond stretching in the specimen plane or longitudinal optic phonons dominate the scattering. Most promising for initial studies are vibrations with energies between 300 and 400 meV from hydrogen bonded to other atoms. Estimates of the scattering cross-sections on the basis of a simple model show that they are about the same as inner shell scattering cross-sections. Cross-sections also increase with charge transfer between the atoms, and theory incorporating realistic charge distributions shows that signal/noise is the only limitation to high-resolution imaging. Given the magnitude of the scattering cross-sections, minimizing the tail of the zero-loss peak is just as important as achieving a small-width at half-maximum. Improvements in both resolution and controlling the zero-loss tail will be necessary before it is practical to detect optic phonons in solids between 40 and 60 meV.

Algebraic Theory of Crystal Vibrations: Localization Properties of Wave Functions in Two-Dimensional Lattices

DOE PAGES

Dietz, Barbara; Iachello, Francesco; Macek, Michal

2017-08-07

The localization properties of the wave functions of vibrations in two-dimensional (2D) crystals are studied numerically for square and hexagonal lattices within the framework of an algebraic model. The wave functions of 2D lattices have remarkable localization properties, especially at the van Hove singularities (vHs). Finite-size sheets with a hexagonal lattice (graphene-like materials), in addition, exhibit at zero energy a localization of the wave functions at zigzag edges, so-called edge states. The striped structure of the wave functions at a vHs is particularly noteworthy. We have investigated its stability and that of the edge states with respect to perturbations inmore » the lattice structure, and the effect of the boundary shape on the localization properties. We find that the stripes disappear instantaneously at the vHs in a square lattice when turning on the perturbation, whereas they broaden but persist at the vHss in a hexagonal lattice. For one of them, they eventually merge into edge states with increasing coupling, which, in contrast to the zero-energy edge states, are localized at armchair edges. The results are corroborated based on participation ratios, obtained under various conditions.« less

Ab initio anharmonic vibrational frequency predictions for linear proton-bound complexes OC-H(+)-CO and N(2)-H(+)-N(2).

PubMed

Terrill, Kasia; Nesbitt, David J

2010-08-01

Ab initio anharmonic transition frequencies are calculated for strongly coupled (i) asymmetric and (ii) symmetric proton stretching modes in the X-H(+)-X linear ionic hydrogen bonded complexes for OCHCO(+) and N(2)HN(2)(+). The optimized potential surface is calculated in these two coordinates for each molecular ion at CCSD(T)/aug-cc-pVnZ (n = 2-4) levels and extrapolated to the complete-basis-set limit (CBS). Slices through both 2D surfaces reveal a relatively soft potential in the asymmetric proton stretching coordinate at near equilibrium geometries, which rapidly becomes a double minimum potential with increasing symmetric proton acceptor center of mass separation. Eigenvalues are obtained by solution of the 2D Schrödinger equation with potential/kinetic energy coupling explicity taken into account, converged in a distributed Gaussian basis set as a function of grid density. The asymmetric proton stretch fundamental frequency for N(2)HN(2)(+) is predicted at 848 cm(-1), with strong negative anharmonicity in the progression characteristic of a shallow "particle in a box" potential. The corresponding proton stretch fundamental for OCHCO(+) is anomalously low at 386 cm(-1), but with a strong alternation in the vibrational spacing due to the presence of a shallow D(infinityh) transition state barrier (Delta = 398 cm(-1)) between the two equivalent minimum geometries. Calculation of a 2D dipole moment surface and transition matrix elements reveals surprisingly strong combination and difference bands with appreciable intensity throughout the 300-1500 cm(-1) region. Corrected for zero point (DeltaZPE) and thermal vibrational excitation (DeltaE(vib)) at 300 K, the single and double dissociation energies in these complexes are in excellent agreement with thermochemical gas phase ion data.

An Active Micro Vibration Isolator with Zero-Power Controlled Magnetic Suspension Technology

NASA Astrophysics Data System (ADS)

Hoque, Md. Emdadul; Takasaki, Masaya; Ishino, Yuji; Suzuki, Hirohisa; Mizuno, Takeshi

In this paper, a three-degree-of-freedom vibration isolation system using active zero-power controlled magnetic suspension is presented in order to isolate vibrations transmitted from the ground and to attenuate the effect of direct disturbances on the table. The zero-compliance of the isolator for direct disturbances was realized by connecting a conventional mechanical spring in series with a negative spring produced by an active magnetic suspension mechanism. In this work, each degree-of-freedom-of-motion of the vibration isolator is treated analytically and it is shown that the developed system is capable to generate infinite stiffness in each mode. Experimental studies have been conducted as well to measure the effectiveness of the isolator under both types of disturbances. Further improvements for the developed system as well as the control techniques are also discussed.

High-Level, First-Principles, Full-Dimensional Quantum Calculation of the Ro-vibrational Spectrum of the Simplest Criegee Intermediate (CH2OO).

PubMed

Li, Jun; Carter, Stuart; Bowman, Joel M; Dawes, Richard; Xie, Daiqian; Guo, Hua

2014-07-03

The ro-vibrational spectrum of the simplest Criegee intermediate (CH2OO) has been determined quantum mechanically based on nine-dimensional potential energy and dipole surfaces for its ground electronic state. The potential energy surface is fitted to more than 50 000 high-level ab initio points with a root-mean-square error of 25 cm(-1), using a recently proposed permutation invariant polynomial neural network method. The calculated rotational constants, vibrational frequencies, and spectral intensities of CH2OO are in excellent agreement with experiment. The potential energy surface provides a valuable platform for studying highly excited vibrational and unimolecular reaction dynamics of this important molecule.

Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

NASA Astrophysics Data System (ADS)

Lu, Xiu Hui; Yu, Hai Bin; Wu, Wei Rong; Xu, Yue Hua

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second-order Møller-Plesset (MP2)/6-31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero-point energy (ZPE) and CCSD(T)/6-31G* single-point calculations. From the PES obtained with the CCSD(T)//MP2/6-31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four-membered ring intermediate, INT2, which is a barrier-free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four-membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier-free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier-free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol.

New Ways of Treating Data for Diatomic Molecule 'shelf' and Double-Minimum States

NASA Astrophysics Data System (ADS)

Le Roy, Robert J.; Tao, Jason; Khanna, Shirin; Pashov, Asen; Tellinghuisen, Joel

2017-06-01

Electronic states whose potential energy functions have 'shelf' or double-minimum shapes have always presented special challenges because, as functions of vibrational quantum number, the vibrational energies/spacings and inertial rotational constants either have an abrupt change of character with discontinuous slope, or past a given point, become completely chaotic. The present work shows that a `traditional' methodology developed for deep `regular' single-well potentials can also provide accurate `parameter-fit' descriptions of the v-dependence of the vibrational energies and rotational constants of shelf-state potentials that allow a conventional RKR calculation of their Potential energy functions. It is also shown that a merging of Pashov's uniquely flexible 'spline point-wise' potential function representation with Le Roy's `Morse/Long-Range' (MLR) analytic functional form which automatically incorporates the correct theoretically known long-range form, yields an analytic function that incorporates most of the advantages of both approaches. An illustrative application of this method to data to a double-minimum state of Na_2 will be described.

Stable long-time semiclassical description of zero-point energy in high-dimensional molecular systems.

PubMed

Garashchuk, Sophya; Rassolov, Vitaly A

2008-07-14

Semiclassical implementation of the quantum trajectory formalism [J. Chem. Phys. 120, 1181 (2004)] is further developed to give a stable long-time description of zero-point energy in anharmonic systems of high dimensionality. The method is based on a numerically cheap linearized quantum force approach; stabilizing terms compensating for the linearization errors are added into the time-evolution equations for the classical and nonclassical components of the momentum operator. The wave function normalization and energy are rigorously conserved. Numerical tests are performed for model systems of up to 40 degrees of freedom.

Zero field reversal probability in thermally assisted magnetization reversal

NASA Astrophysics Data System (ADS)

Prasetya, E. B.; Utari; Purnama, B.

2017-11-01

This paper discussed about zero field reversal probability in thermally assisted magnetization reversal (TAMR). Appearance of reversal probability in zero field investigated through micromagnetic simulation by solving stochastic Landau-Lifshitz-Gibert (LLG). The perpendicularly anisotropy magnetic dot of 50×50×20 nm3 is considered as single cell magnetic storage of magnetic random acces memory (MRAM). Thermally assisted magnetization reversal was performed by cooling writing process from near/almost Curie point to room temperature on 20 times runs for different randomly magnetized state. The results show that the probability reversal under zero magnetic field decreased with the increase of the energy barrier. The zero-field probability switching of 55% attained for energy barrier of 60 k B T and the reversal probability become zero noted at energy barrier of 2348 k B T. The higest zero-field switching probability of 55% attained for energy barrier of 60 k B T which corespond to magnetif field of 150 Oe for switching.

A theoretical study of hydrogen complexes of the XH-pi type between propyne and HF, HCL or HCN.

PubMed

Tavares, Alessandra M; da Silva, Washington L V; Lopes, Kelson C; Ventura, Elizete; Araújo, Regiane C M U; do Monte, Silmar A; da Silva, João Bosco P; Ramos, Mozart N

2006-05-15

The present manuscript reports a systematic investigation of the basis set dependence of some properties of hydrogen-bonded (pi type) complexes formed by propyne and a HX molecule, where X=F, Cl and CN. The calculations have been performed at Hartree-Fock, MP2 and B3LYP levels. Geometries, H-bond energies and vibrational have been considered. The more pronounced effects on the structural parameters of the isolated molecules, as a result of complexation, are verified on RCtriple bondC and HX bond lengths. As compared to double-zeta (6-31G**), triple-zeta (6-311G**) basis set leads to an increase of RCtriple bondC bond distance, at all three computational levels. In the case where diffuse functions are added to both hydrogen and 'heavy' atoms, the effect is more pronounced. The propyne-HX structural parameters are quite similar to the corresponding parameters of acetylene-HX complexes, at all levels. The largest difference is obtained for hydrogen bond distance, RH, with a smaller value for propyne-HX complex, indicating a stronger bond. Concerning the electronic properties, the results yield the following ordering for H-bond energies, DeltaE: propynecdots, three dots, centeredHF>propynecdots, three dots, centeredHCl>propynecdots, three dots, centeredHCN. It is also important to point out that the inclusion of BSSE and zero-point energies (ZPE) corrections cause significant changes on DeltaE. The smaller effect of ZPE is obtained for propynecdots, three dots, centeredHCN at HF/6-311++G** level, while the greatest difference is obtained at MP2/6-31G** level for propynecdots, three dots, centeredHF system. Concerning the IR vibrational it was obtained that larger shift can be associated with stronger hydrogen bonds. The more pronounced effect on the normal modes of the isolated molecule after the complexation is obtained for HX stretching frequency, which is shifted downward.

A theoretical study of hydrogen complexes of the X sbnd H-π type between propyne and HF, HCL or HCN

NASA Astrophysics Data System (ADS)

Tavares, Alessandra M.; da Silva, Washington L. V.; Lopes, Kelson C.; Ventura, Elizete; Araújo, Regiane C. M. U.; do Monte, Silmar A.; da Silva, João Bosco P.; Ramos, Mozart N.

2006-05-01

The present manuscript reports a systematic investigation of the basis set dependence of some properties of hydrogen-bonded (π type) complexes formed by propyne and a HX molecule, where X = F, Cl and CN. The calculations have been performed at Hartree-Fock, MP2 and B3LYP levels. Geometries, H-bond energies and vibrational have been considered. The more pronounced effects on the structural parameters of the isolated molecules, as a result of complexation, are verified on RC tbnd C and HX bond lengths. As compared to double-ζ (6-31G **), triple-ζ (6-311G **) basis set leads to an increase of RC tbnd C bond distance, at all three computational levels. In the case where diffuse functions are added to both hydrogen and 'heavy' atoms, the effect is more pronounced. The propyne-HX structural parameters are quite similar to the corresponding parameters of acetylene-HX complexes, at all levels. The largest difference is obtained for hydrogen bond distance, RH, with a smaller value for propyne-HX complex, indicating a stronger bond. Concerning the electronic properties, the results yield the following ordering for H-bond energies, Δ E: propyne⋯HF > propyne⋯HCl > propyne⋯HCN. It is also important to point out that the inclusion of BSSE and zero-point energies (ZPE) corrections cause significant changes on Δ E. The smaller effect of ZPE is obtained for propyne⋯HCN at HF/6-311++G ** level, while the greatest difference is obtained at MP2/6-31G ** level for propyne⋯HF system. Concerning the IR vibrational it was obtained that larger shift can be associated with stronger hydrogen bonds. The more pronounced effect on the normal modes of the isolated molecule after the complexation is obtained for H sbnd X stretching frequency, which is shifted downward.

Proton affinity and enthalpy of formation of formaldehyde

NASA Astrophysics Data System (ADS)

Czakó, Gábor; Nagy, Balázs; Tasi, Gyula; Somogyi, Árpád; Šimunek, Ján; Noga, Jozef; Braams, Bastiaan J.; Bowman, Joel M.; Császár; , Attila G.

The proton affinity and the enthalpy of formation of the prototypical carbonyl, formaldehyde, have been determined by the first-principles composite focal-point analysis (FPA) approach. The electronic structure computations employed the all-electron coupled-cluster method with up to single, double, triple, quadruple, and even pentuple excitations. In these computations the aug-cc-p(C)VXZ [X = 2(D), 3(T), 4(Q), 5, and 6] correlation-consistent Gaussian basis sets for C and O were used in conjunction with the corresponding aug-cc-pVXZ (X = 2-6) sets for H. The basis set limit values have been confirmed via explicitly correlated computations. Our FPA study supersedes previous computational work for the proton affinity and to some extent the enthalpy of formation of formaldehyde by accounting for (a) electron correlation beyond the "gold standard" CCSD(T) level; (b) the non-additivity of core electron correlation effects; (c) scalar relativity; (d) diagonal Born-Oppenheimer corrections computed at a correlated level; (e) anharmonicity of zero-point vibrational energies, based on global potential energy surfaces and variational vibrational computations; and (f) thermal corrections to enthalpies by direct summation over rovibrational energy levels. Our final proton affinities at 298.15 (0.0) K are ΔpaHo (H2CO) = 711.02 (704.98) ± 0.39 kJ mol-1. Our final enthalpies of formation at 298.15 (0.0) K are ΔfHo (H2CO) = -109.23 (-105.42) ± 0.33 kJ mol-1. The latter values are based on the enthalpy of the H2 + CO → H2CO reaction but supported by two further reaction schemes, H2O + C → H2CO and 2H + C + O → H2CO. These values, especially ΔpaHo (H2CO), have better accuracy and considerably lower uncertainty than the best previous recommendations and thus should be employed in future studies.

Structural, electronic and vibrational properties of small GaxNy (x+y = 2 5) nanoclusters: a B3LYP-DFT study

NASA Astrophysics Data System (ADS)

Yadav, P. S.; Yadav, R. K.; Agrawal, B. K.

2007-02-01

An ab initio study of the stability, structural and electronic properties has been made for 49 gallium nitride nanoclusters, GaxNy (x+y = 2-5). Among the various configurations corresponding to a fixed x+y = n value, the configuration possessing the maximum value of binding energy (BE) is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize the geometries of the nanoclusters fully. The binding energies (BEs), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps and the bond lengths have been obtained for all the clusters. We have considered the zero-point energy (ZPE) corrections ignored by the earlier workers. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have been investigated for the most stable structures. The configurations containing the N atoms in majority are seen to be the most stable structures. The strong N-N bond has an important role in stabilizing the clusters. For clusters containing one Ga atom and all the others as N atoms, the BE increases monotonically with the number of the N atoms. The HOMO-LUMO gap and IP fluctuate with the cluster size n, having larger values for the clusters containing odd number of N atoms. On the other hand, the EA decreases with the cluster size up to n = 3, and shows slow fluctuations thereafter for the larger clusters. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA) because of the lower energies of the most stable ground state of the cationic (anionic) clusters. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the experimental data wherever available. The growth of these most stable structures should be possible in experiments.

Strength analysis of piezoceramic materials for structural considerations in energy harvesting for UAVs

NASA Astrophysics Data System (ADS)

Anton, S. R.; Erturk, A.; Inman, D. J.

2010-04-01

Vibration energy harvesting has received considerable attention in the research community over the past decade. Typical vibration harvesting systems are designed to be added on to existing host structures and capture ambient vibration energy. An interesting application of vibration energy harvesting exists in unmanned aerial vehicles (UAVs), where a multifunctional approach, as opposed to the traditional method, is needed due to weight and aerodynamic considerations. The authors propose a multifunctional design for energy harvesting in UAVs where the piezoelectric harvesting device is integrated into the wing of a UAV and provides energy harvesting, energy storage, and load bearing capability. The brittle piezoceramic layer of the harvester is a critical member in load bearing applications; therefore, it is the goal of this research to investigate the bending strength of various common piezoceramic materials. Three-point bend tests are carried out on several piezoelectric ceramics including monolithic piezoceramics PZT-5A and PZT-5H, single crystal piezoelectric PMN-PZT, and commercially packaged QuickPack devices. Bending strength results are reported and can be used as a design tool in the development of piezoelectric vibration energy harvesting systems in which the active device is subjected to bending loads.

Skill Analysis of the Wrist Release in the Golf Swings Utilizing Shaft Elasticity

NASA Astrophysics Data System (ADS)

Suzuki, Soichiro; Hoshino, Yohei; Kobayashi, Yukinori

This study analyzes the skill component of the wrist release in the golf swing by employing a three-dimensional dynamic model considering vibration of the club shaft. It is observed that professional and expert golfers relax their wrists in the swing motion as a "natural" or "late" release. Thus, the relationship between the timing of the wrist release and the shaft vibration is examined in this study. First, it is demonstrated that "natural release" at the zero-crossing point of the bending vibration of the shaft efficiently increases the head speed at impact. In the next step, the "late hitting" condition is imposed upon the model. It is demonstrated that "late hitting" could further improve the efficiency of the swing motion. Finally, the skill component in the wrist release for the long drive is experimentally verified by measuring the movement of the wrist and the dynamic deformation of the shaft during the downswing.

The GaOH-HGaO potential energy hypersurface and the necessity of correlating the 3d electrons

NASA Astrophysics Data System (ADS)

Richards, Claude A., Jr.; Yamaguchi, Yukio; Kim, Seung-Joon; Schaefer, Henry F., III

1996-06-01

The ground state potential energy hypersurface of the GaOH-HGaO system has been investigated using high level ab initio molecular electronic structure theory. The geometries and physical properties of two equilibrium structures, one isomerization transition state and one inversion transition state were determined at the self-consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double excitations (CCSD), and CCSD with perturbative triple excitations [CCSD(T)] levels of theory with four sets of basis functions. It has been found that freezing the 3d electrons of the Ga atom in the correlation procedures is not appropriate for this system. For the energy difference ΔE (GaOH-HGaO) the freezing of the 3d electrons results in an error of 25 kcal/mol! The dipole moments, harmonic vibrational frequencies, and infrared (IR) intensities are predicted for the four stationary points. At the highest level of theory employed in this study, CCSD(T) using triple zeta plus double polarization with higher angular momentum and diffuse functions [TZ2P(f,d)+diff] basis set, the bent GaOH was found to be 41.9 kcal/mol more stable than the linear HGaO species; with the zero-point vibrational energy (ZPVE) correction, the energy separation becomes 40.4 kcal/mol. The classical barrier height for the exothermic isomerization (1,2 hydrogen shift) reaction HGaO→GaOH is determined to be 44.5 kcal/mol and the barrier height with the ZPVE correction 42.3 kcal/mol. The classical barrier to linearity for the bent GaOH molecule is determined to be 1.7 kcal/mol and the barrier height with the ZPVE correction to be 1.2 kcal/mol. The predicted dipole moments of GaOH and HGaO are 1.41 and 4.45 Debye, respectively. The effects of electron correlation reduce the dipole moment of HGaO by the sizable amount of 1.2 Debye. The two equilibrium species may be suitable for microwave spectroscopic investigation. Furthermore, they may also be detectable by IR techniques due to the relatively large intensities of their vibrational modes. The geometrical and energetic features are compared with those of the valence isoelectronic HXO-XOH systems, where X is a group IIIA atom and the HXO+-XOH+ systems, where X is a group IVA atom.

Investigating the significance of zero-point motion in small molecular clusters of sulphuric acid and water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stinson, Jake L.; Kathmann, Shawn M.; Ford, Ian J.

2014-01-14

The nucleation of particles from trace gases in the atmosphere is an important source of cloud condensation nuclei (CCN), and these are vital for the formation of clouds in view of the high supersaturations required for homogeneous water droplet nucleation. The methods of quantum chemistry have increasingly been employed to model nucleation due to their high accuracy and efficiency in calculating configurational energies; and nucleation rates can be obtained from the associated free energies of particle formation. However, even in such advanced approaches, it is typically assumed that the nuclei have a classical nature, which is questionable for some systems.more » The importance of zero-point motion (also known as quantum nuclear dynamics) in modelling small clusters of sulphuric acid and water is tested here using the path integral molecular dynamics (PIMD) method at the density functional theory (DFT) level of theory. We observe a small zero-point effect on the the equilibrium structures of certain clusters. One configuration is found to display a bimodal behaviour at 300 K in contrast to the stable ionised state suggested from a zero temperature classical geometry optimisation. The general effect of zero-point motion is to promote the extent of proton transfer with respect to classical behaviour. We thank Prof. Angelos Michaelides and his group in University College London (UCL) for practical advice and helpful discussions. This work benefited from interactions with the Thomas Young Centre through seminar and discussions involving the PIMD method. SMK was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. JLS and IJF were supported by the IMPACT scheme at UCL and by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. We are grateful for use of the UCL Legion High Performance Computing Facility and the resources of the National Energy Research Scientific Computing Center (NERSC), which is supported by the U.S. Department of Energy, Office of Science of the under Contract No. DE-AC02-05CH11231.« less

Quantum dynamics of small H2 and D2 clusters in the large cage of structure II clathrate hydrate: Energetics, occupancy, and vibrationally averaged cluster structures

NASA Astrophysics Data System (ADS)

Sebastianelli, Francesco; Xu, Minzhong; Bačić, Zlatko

2008-12-01

We report diffusion Monte Carlo (DMC) calculations of the quantum translation-rotation (T-R) dynamics of one to five para-H2 (p-H2) and ortho-D2 (o-D2) molecules inside the large hexakaidecahedral (51264) cage of the structure II clathrate hydrate, which was taken to be rigid. These calculations provide a quantitative description of the size evolution of the ground-state properties, energetics, and the vibrationally averaged geometries, of small (p-H2)n and (o-D2)n clusters, n=1-5, in nanoconfinement. The zero-point energy (ZPE) of the T-R motions rises steeply with the cluster size, reaching 74% of the potential well depth for the caged (p-H2)4. At low temperatures, the rapid increase of the cluster ZPE as a function of n is the main factor that limits the occupancy of the large cage to at most four H2 or D2 molecules, in agreement with experiments. Our DMC results concerning the vibrationally averaged spatial distribution of four D2 molecules, their mean distance from the cage center, the D2-D2 separation, and the specific orientation and localization of the tetrahedral (D2)4 cluster relative to the framework of the large cage, agree very well with the low-temperature neutron diffraction experiments involving the large cage with the quadruple D2 occupancy.

Quantum dynamics of small H2 and D2 clusters in the large cage of structure II clathrate hydrate: energetics, occupancy, and vibrationally averaged cluster structures.

PubMed

Sebastianelli, Francesco; Xu, Minzhong; Bacić, Zlatko

2008-12-28

We report diffusion Monte Carlo (DMC) calculations of the quantum translation-rotation (T-R) dynamics of one to five para-H(2) (p-H(2)) and ortho-D(2) (o-D(2)) molecules inside the large hexakaidecahedral (5(12)6(4)) cage of the structure II clathrate hydrate, which was taken to be rigid. These calculations provide a quantitative description of the size evolution of the ground-state properties, energetics, and the vibrationally averaged geometries, of small (p-H(2))(n) and (o-D(2))(n) clusters, n=1-5, in nanoconfinement. The zero-point energy (ZPE) of the T-R motions rises steeply with the cluster size, reaching 74% of the potential well depth for the caged (p-H(2))(4). At low temperatures, the rapid increase of the cluster ZPE as a function of n is the main factor that limits the occupancy of the large cage to at most four H(2) or D(2) molecules, in agreement with experiments. Our DMC results concerning the vibrationally averaged spatial distribution of four D(2) molecules, their mean distance from the cage center, the D(2)-D(2) separation, and the specific orientation and localization of the tetrahedral (D(2))(4) cluster relative to the framework of the large cage, agree very well with the low-temperature neutron diffraction experiments involving the large cage with the quadruple D(2) occupancy.

Measurements of the electric field of zero-point optical phonons in GaAs quantum wells support the Urbach rule for zero-temperature lifetime broadening.

PubMed

Bhattacharya, Rupak; Mondal, Richarj; Khatua, Pradip; Rudra, Alok; Kapon, Eli; Malzer, Stefan; Döhler, Gottfried; Pal, Bipul; Bansal, Bhavtosh

2015-01-30

We study a specific type of lifetime broadening resulting in the well-known exponential "Urbach tail" density of states within the energy gap of an insulator. After establishing the frequency and temperature dependence of the Urbach edge in GaAs quantum wells, we show that the broadening due to the zero-point optical phonons is the fundamental limit to the Urbach slope in high-quality samples. In rough analogy with Welton's heuristic interpretation of the Lamb shift, the zero-temperature contribution to the Urbach slope can be thought of as arising from the electric field of the zero-point longitudinal-optical phonons. The value of this electric field is experimentally measured to be 3  kV cm-1, in excellent agreement with the theoretical estimate.

Input Shaping to Reduce Solar Array Structural Vibrations

NASA Technical Reports Server (NTRS)

Doherty, Michael J.; Tolson, Robert J.

1998-01-01

Structural vibrations induced by actuators can be minimized using input shaping. Input shaping is a feedforward method in which actuator commands are convolved with shaping functions to yield a shaped set of commands. These commands are designed to perform the maneuver while minimizing the residual structural vibration. In this report, input shaping is extended to stepper motor actuators. As a demonstration, an input-shaping technique based on pole-zero cancellation was used to modify the Solar Array Drive Assembly (SADA) actuator commands for the Lewis satellite. A series of impulses were calculated as the ideal SADA output for vibration control. These impulses were then discretized for use by the SADA stepper motor actuator and simulated actuator outputs were used to calculate the structural response. The effectiveness of input shaping is limited by the accuracy of the knowledge of the modal frequencies. Assuming perfect knowledge resulted in significant vibration reduction. Errors of 10% in the modal frequencies caused notably higher levels of vibration. Controller robustness was improved by incorporating additional zeros in the shaping function. The additional zeros did not require increased performance from the actuator. Despite the identification errors, the resulting feedforward controller reduced residual vibrations to the level of the exactly modeled input shaper and well below the baseline cases. These results could be easily applied to many other vibration-sensitive applications involving stepper motor actuators.

Gas phase hydrolysis of formaldehyde to form methanediol: impact of formic acid catalysis.

PubMed

Hazra, Montu K; Francisco, Joseph S; Sinha, Amitabha

2013-11-21

We find that formic acid (FA) is very effective at facilitating diol formation through its ability to reduce the barrier for the formaldehyde (HCHO) hydrolysis reaction. The rate limiting step in the mechanism involves the isomerization of a prereactive collision complex formed through either the HCHO···H2O + FA and/or HCHO + FA···H2O pathways. The present study finds that the effective barrier height, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state (TS) and the HCHO···H2O + FA and HCHO + FA···H2O starting reagents, are respectively only ∼1 and ∼4 kcal/mol. These barriers are substantially lower than the ∼17 kcal/mol barrier associated with the corresponding step in the hydrolysis of HCHO catalyzed by a single water molecule (HCHO + H2O + H2O). The significantly lower barrier heights for the formic acid catalyzed pathway reveal a new important role that organic acids play in the gas phase hydrolysis of atmospheric carbonyl compounds.

First-Principles Study of the Li-Mg-N-H System: Compound Structures and Hydrogen Storage Properties

NASA Astrophysics Data System (ADS)

Michel, Kyle; Ozolins, Vidvuds

2009-03-01

The Li-Mg-N-H system is studied with the addition of the Li4Mg(NH)3, MgNH, and Li4NH compounds using first-principles density-functional theory (DFT) calculations. A structure for the mixed imide Li4Mg(NH)3 is proposed, belonging to the Imm2 space group. A new structure for Li2Mg(NH)2 is given that has Pca21 symmetry; this compound has been previously reported as having Iba2 symmetry. The stability of the Li4Mg-imide is studied with respect to its decomposition reactions. The static, zero-point (ZPE), and vibrational energies of all relevant compounds belonging to this system are reported along with their predicted lowest-energy structures. Dehydrogenation reactions are presented that involve these phases and which are found to be spontaneously occurring within 400 K of room temperature. It is predicted that mixing LiH, LiNH2, and Li2Mg(NH)2 at 505 K will form Li4Mg(NH)3 with the release of 2.04 wt. % H2.

Titan's Ionic Species: Theoretical Treatment of N2H+ and Related Ions

NASA Astrophysics Data System (ADS)

Brites, V.; Hochlaf, M.

2009-06-01

We use different ab initio methods to compute the three-dimensional potential energy surface (3D-PES) of the ground state of N2H+. This includes the standard coupled cluster, the complete active space self-consistent field, the internally contacted multi reference configuration interaction, and the newly developed CCSD(T)-F12 methods. For the description of H and N atoms, several basis sets are tested. Then, we incorporate the 3D-PES analytical representations into variational calculations of the rovibrational spectrum of N2H+(X˜1Σ+) up to 7200 cm-1 above the zero point vibrational energy. Our data show that the CCSD(T)-F12/aug-cc-pVTZ approach represents a compromise for good description of the PES and computation cost. This technique is recommended for full dimensional PES generation of atmospheric and astrophysical relevant polyatomic systems. We applied this method to derive the rovibrational spectra of N2H+(X˜1Σ+) and of N2H++(X˜2Σ+). Finally, we discuss the existence of the N2H++(X˜2Σ+) in Titan's atmosphere.

Quasiparticle Lifetime Broadening in Resonant X-ray Scattering of NH4NO3.

PubMed

Vinson, John; Jach, Terrence; Müller, Matthias; Unterumsberger, Rainer; Beckhoff, Burkhard

2016-07-15

It has been previously shown that two effects cause dramatic changes in the x-ray absorption and emission spectra from the N K edge of the insulating crystal ammonium nitrate. First, vibrational disorder causes major changes in the absorption spectrum, originating not only from the thermal population of phonons, but, significantly, from zero-point motion as well. Second, the anomalously large broadening ( ~ 4 eV) of the emission originating from nitrate σ states is due to unusually short lifetimes of quasiparticles in an otherwise extremely narrow band. In this work we investigate the coupling of these effects to core and valence excitons that are created as the initial x-ray excitation energy is progressively reduced toward the N edge. Using a GW /Bethe-Salpeter approach, we show the extent to which this anomalous broadening is captured by the GW approximation. The data and calculations demonstrate the importance that the complex self-energies (finite lifetimes) of valence bands have on the interpretation of emission spectra. We produce a scheme to explain why extreme lifetimes should appear in σ states of other similar compounds.

Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

PubMed

Zhang, Jiaxu; Xie, Jing; Hase, William L

2015-12-17

Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F(-) + CH3I proton transfer are compared with those reported previously (J. Phys. Chem. A 2013, 117, 7162-7178) for the isoelectronic OH(-) + CH3I reaction.

Ubiquity of quantum zero-point fluctuations in dislocation glide

NASA Astrophysics Data System (ADS)

Landeiro Dos Reis, Marie; Choudhury, Anshuman; Proville, Laurent

2017-03-01

Modeling the dislocation glide through atomic scale simulations in Al, Cu, and Ni and in solid solution alloys Al(Mg) and Cu(Ag), we show that in the course of the plastic deformation the variation of the crystal zero-point energy (ZPE) and the dislocation potential energy barriers are of opposite sign. The multiplicity of situations where we have observed the same trend allows us to conclude that quantum fluctuations, giving rise to the crystal ZPE, make easier the dislocation glide in most materials, even those constituted of atoms heavier than H and He.

Full-dimensional quantum calculations of ground-state tunneling splitting of malonaldehyde using an accurate ab initio potential energy surface

NASA Astrophysics Data System (ADS)

Wang, Yimin; Braams, Bastiaan J.; Bowman, Joel M.; Carter, Stuart; Tew, David P.

2008-06-01

Quantum calculations of the ground vibrational state tunneling splitting of H-atom and D-atom transfer in malonaldehyde are performed on a full-dimensional ab initio potential energy surface (PES). The PES is a fit to 11 147 near basis-set-limit frozen-core CCSD(T) electronic energies. This surface properly describes the invariance of the potential with respect to all permutations of identical atoms. The saddle-point barrier for the H-atom transfer on the PES is 4.1 kcal/mol, in excellent agreement with the reported ab initio value. Model one-dimensional and ``exact'' full-dimensional calculations of the splitting for H- and D-atom transfer are done using this PES. The tunneling splittings in full dimensionality are calculated using the unbiased ``fixed-node'' diffusion Monte Carlo (DMC) method in Cartesian and saddle-point normal coordinates. The ground-state tunneling splitting is found to be 21.6 cm-1 in Cartesian coordinates and 22.6 cm-1 in normal coordinates, with an uncertainty of 2-3 cm-1. This splitting is also calculated based on a model which makes use of the exact single-well zero-point energy (ZPE) obtained with the MULTIMODE code and DMC ZPE and this calculation gives a tunneling splitting of 21-22 cm-1. The corresponding computed splittings for the D-atom transfer are 3.0, 3.1, and 2-3 cm-1. These calculated tunneling splittings agree with each other to within less than the standard uncertainties obtained with the DMC method used, which are between 2 and 3 cm-1, and agree well with the experimental values of 21.6 and 2.9 cm-1 for the H and D transfer, respectively.

Full-dimensional quantum calculations of ground-state tunneling splitting of malonaldehyde using an accurate ab initio potential energy surface.

PubMed

Wang, Yimin; Braams, Bastiaan J; Bowman, Joel M; Carter, Stuart; Tew, David P

2008-06-14

Quantum calculations of the ground vibrational state tunneling splitting of H-atom and D-atom transfer in malonaldehyde are performed on a full-dimensional ab initio potential energy surface (PES). The PES is a fit to 11 147 near basis-set-limit frozen-core CCSD(T) electronic energies. This surface properly describes the invariance of the potential with respect to all permutations of identical atoms. The saddle-point barrier for the H-atom transfer on the PES is 4.1 kcalmol, in excellent agreement with the reported ab initio value. Model one-dimensional and "exact" full-dimensional calculations of the splitting for H- and D-atom transfer are done using this PES. The tunneling splittings in full dimensionality are calculated using the unbiased "fixed-node" diffusion Monte Carlo (DMC) method in Cartesian and saddle-point normal coordinates. The ground-state tunneling splitting is found to be 21.6 cm(-1) in Cartesian coordinates and 22.6 cm(-1) in normal coordinates, with an uncertainty of 2-3 cm(-1). This splitting is also calculated based on a model which makes use of the exact single-well zero-point energy (ZPE) obtained with the MULTIMODE code and DMC ZPE and this calculation gives a tunneling splitting of 21-22 cm(-1). The corresponding computed splittings for the D-atom transfer are 3.0, 3.1, and 2-3 cm(-1). These calculated tunneling splittings agree with each other to within less than the standard uncertainties obtained with the DMC method used, which are between 2 and 3 cm(-1), and agree well with the experimental values of 21.6 and 2.9 cm(-1) for the H and D transfer, respectively.

Modified Nose-Hoover thermostat for solid state for constant temperature molecular dynamics simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Wen-Hwa, E-mail: whchen@pme.nthu.edu.tw; National Applied Research Laboratories, Taipei 10622, Taiwan, ROC; Wu, Chun-Hung

2011-07-10

Nose-Hoover (NH) thermostat methods incorporated with molecular dynamics (MD) simulation have been widely used to simulate the instantaneous system temperature and feedback energy in a canonical ensemble. The method simply relates the kinetic energy to the system temperature via the particles' momenta based on the ideal gas law. However, when used in a tightly bound system such as solids, the method may suffer from deriving a lower system temperature and potentially inducing early breaking of atomic bonds at relatively high temperature due to the neglect of the effect of the potential energy of atoms based on solid state physics. Inmore » this paper, a modified NH thermostat method is proposed for solid system. The method takes into account the contribution of phonons by virtue of the vibrational energy of lattice and the zero-point energy, derived based on the Debye theory. Proof of the equivalence of the method and the canonical ensemble is first made. The modified NH thermostat is tested on different gold nanocrystals to characterize their melting point and constant volume specific heat, and also their size and temperature dependence. Results show that the modified NH method can give much more comparable results to both the literature experimental and theoretical data than the standard NH. Most importantly, the present model is the only one, among the six thermostat algorithms under comparison, that can accurately reproduce the experimental data and also the T{sup 3}-law at temperature below the Debye temperature, where the specific heat of a solid at constant volume is proportional to the cube of temperature.« less

Theoretical investigation of the relative stability of Na{sup +}He{sub n} (n = 2–24) clusters: Many-body versus delocalization effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Issaoui, Noureddine, E-mail: issaoui-noureddine@yahoo.fr; Abdessalem, Kawther; Ghalla, Houcine

2014-11-07

The solvation of the Na{sup +} ion in helium clusters has been studied theoretically using optimization methods. A many-body empirical potential was developed to account for Na{sup +}–He and polarization interactions, and the most stable structures of Na{sup +}He{sub n} clusters were determined using the basin-hopping method. Vibrational delocalization was accounted for using zero-point energy corrections at the harmonic or anharmonic levels, the latter being evaluated from quantum Monte Carlo simulations for spinless particles. From the static perspective, many-body effects are found to play a minor role, and the structures obtained reflect homogeneous covering up to n = 10, followedmore » by polyicosahedral packing above this size, the cluster obtained at n = 12 appearing particularly stable. The cationic impurity binds the closest helium atoms sufficiently to negate vibrational delocalization at small sizes. However, this snowball effect is obliterated earlier than shell completion, the nuclear wavefunctions of {sup 4}He{sub n}Na{sup +} with n = 5–7, and n > 10 already exhibiting multiple inherent structures. The decrease in the snowball size due to many-body effects is consistent with recent mass spectrometry measurements.« less

A Comparison of Density Functional Theory with Ab initio Approaches for Systems Involving First Transition Row Metals

NASA Technical Reports Server (NTRS)

Ricca, Alessandra; Bauschlicher, Charles W.; Langhoff, Stephen R. (Technical Monitor)

1994-01-01

Density functional theory (DFT) is found to give a better description of the geometries and vibrational frequencies of FeL and FeL(sup +) systems than second order Moller Plesset perturbation theory (MP2). Namely, the DFT correctly predicts the shift in the CO vibrational frequency between free CO and the Sigma(sup -) state of FeCO and yields a good result for the Fe-C distance in the quartet states of FeCH4(+) 4 These are properties where the MP2 results are unsatisfactory. Thus DFT appears to be an excellent approach for optimizing the geometries and computing the zero-point energies of systems containing first transition row atoms. Because the DFT approach is biased in favor of the 3d(exp 7) occupation, whereas the more traditional approaches are biased in favor of the 3d(exp 6) occupation, differences are found in the relative ordering of states. It is shown that if the dissociation is computed to the most appropriate atomic asymptote and corrected to the ground state asymptote using the experimental separations, the DFT results are in good agreement with high levels of theory. The energetics at the DFT level are much superior to the MP2 and in most cases in good agreement with high levels of theory.

Condition monitoring of a prototype turbine. Description of the system and main results

NASA Astrophysics Data System (ADS)

Valero, C.; Egusquiza, E.; Presas, A.; Valentin, D.; Egusquiza, M.; Bossio, M.

2017-04-01

The fast change in new renewable energy is affecting directly the required operating range of hydropower plants. According to the present demand of electricity, it is necessary to generate different levels of power. Because of its ease to regulate and its huge storage capacity of energy, hydropower is the unique energy source that can adapt to the demand. Today, the required operating range of turbine units is expected to extend from part load to overload. These extreme operations points can cause several pressure pulsations, cavitation and vibrations in different parts of the machine. To determine the effects on the machine, vibration measurements are necessary in actual machines. Vibrations can be used for machinery protection and to identify problems in the machine (diagnosis). In this paper, some results obtained in a hydropower plant are presented. The variation of global levels and vibratory signatures has been analysed as function as gross head, transducer location and operating points.

Watching Electrons at Conical Intersections and Funnels

NASA Astrophysics Data System (ADS)

Jonas, David M.; Smith, Eric R.; Peters, William K.; Kitney, Katherine A.

2009-06-01

The electronic motion at conical intersections and funnels is probed after polarized excitation of aligned electronic wavepackets. The pulses have bandwidth sufficient to observe vibrations mainly through their effect on the electrons. Vibrational symmetry can be identified by the polarization anisotropy of vibrational quantum beats. The polarized transients show signatures of electronic wavepacket motion (due to the energy gaps) and of electron transfer between orbitals (due to the couplings) driven by the conical intersection. For a conical intersection in a four-fold symmetric symmetry silicon naphthalocyanine molecule, electronic motions on a 100 fs timescale are driven by couplings of 1 meV. In the lower symmetry free-base naphthalocyanine, the conical intersection may be missed or missing (conical funnel), and the motions are nearly as rapid, but electronic equilibration is incomplete for red-edge excitation. These experiments probe non-adiabatic electronic dynamics with near-zero nuclear momentum - the electronic motions are determined by the principal slopes of the conical intersection and the width of the vibrational wavepacket.

Gravity and Zero Point Energy

NASA Astrophysics Data System (ADS)

Massie, U. W.

When Planck introduced the 1/2 hv term to his 1911 black body equation he showed that there is a residual energy remaining at zero degree K after all thermal energy ceased. Other investigators, including Lamb, Casimir, and Dirac added to this information. Today zero point energy (ZPE) is accepted as an established condition. The purpose of this paper is to demonstrate that the density of the ZPE is given by the gravity constant (G) and the characteristics of its particles are revealed by the cosmic microwave background (CMB). Eddies of ZPE particles created by flow around mass bodies reduce the pressure normal to the eddy flow and are responsible for the force of gravity. Helium atoms resonate with ZPE particles at low temperature to produce superfluid helium. High velocity micro vortices of ZPE particles about a basic particle or particles are responsible for electromagnetic forces. The speed of light is the speed of the wave front in the ZPE and its value is a function of the temperature and density of the ZPE.

Simulation analysis of space remote sensing image quality degradation induced by satellite platform vibration

NASA Astrophysics Data System (ADS)

Yang, Feng; Zhang, Xiaofang; Huang, Yu; Hao, Weiwei; Guo, Baiwei

2012-11-01

Satellite platform vibration causes the image quality to be degraded, it is necessary to study its influence on image quality. The forms of Satellite platform vibration consist of linear vibration, sinusoidal vibration and random vibration. Based on Matlab & Zemax, the simulation system has been developed for simulating impact caused by satellite platform vibration on image quality. Dynamic Data Exchange is used for the communication between Matlab and Zemax. The data of sinusoidal vibration are produced by sinusoidal curve with specific amplitude and frequency. The data of random vibration are obtained by combining sinusoidal signals with 10Hz, 100Hz and 200Hz's frequency, 100, 12, 1.9's amplitude and white noise with zero mean value. Satellite platform vibration data which produced by Matlab are added to the optical system, and its point spread function can be obtained by Zemax. Blurred image can be gained by making the convolution of PSF and the original image. The definition of the original image and the blurred image are evaluated by using average gradient values of image gray. The impact caused by the sine and random vibration of six DOFs on the image quality are respectively simulated. The simulation result reveal that the decenter of X-, Y-, Z- direction and the tilt of Z-direction have a little effect on image quality, while the tilt of X-, Y- direction make image quality seriously degraded. Thus, it can be concluded that correcting the error of satellite platform vibration by FSM is a viable and effective way.

Zero-point term and quantum effects in the Johnson noise of resistors: a critical appraisal

NASA Astrophysics Data System (ADS)

Kish, Laszlo B.; Niklasson, Gunnar A.; Granqvist, Claes G.

2016-05-01

There is a longstanding debate about the zero-point term in the Johnson noise voltage of a resistor. This term originates from a quantum-theoretical treatment of the fluctuation-dissipation theorem (FDT). Is the zero-point term really there, or is it only an experimental artifact, due to the uncertainty principle, for phase-sensitive amplifiers? Could it be removed by renormalization of theories? We discuss some historical measurement schemes that do not lead to the effect predicted by the FDT, and we analyse new features that emerge when the consequences of the zero-point term are measured via the mean energy and force in a capacitor shunting the resistor. If these measurements verify the existence of a zero-point term in the noise, then two types of perpetual motion machines can be constructed. Further investigation with the same approach shows that, in the quantum limit, the Johnson-Nyquist formula is also invalid under general conditions even though it is valid for a resistor-antenna system. Therefore we conclude that in a satisfactory quantum theory of the Johnson noise, the FDT must, as a minimum, include also the measurement system used to evaluate the observed quantities. Issues concerning the zero-point term may also have implications for phenomena in advanced nanotechnology.

Structural, electronic and vibrational properties of GexCy (x+y=2-5) nanoclusters: A B3LYP-DFT study

NASA Astrophysics Data System (ADS)

Goswami, Sohini; Saha, Sushmita; Yadav, R. K.

2015-11-01

An ab-initio study of the stability, structural and electronic properties has been made for 84 germanium carbide nanoclusters, GexCy (x+y=2-5). The configuration possessing the maximum value of final binding energy (FBE), among the various configurations corresponding to a fixed x+y=n value, is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize fully the geometries of the nanoclusters. The binding energies (BE), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps have been obtained for all the clusters and the bond lengths have been reported for the most stable clusters. We have considered the zero point energy (ZPE) corrections. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have also been investigated for the most stable structures. The configurations containing the carbon atoms in majority are seen to be the most stable structures. The strong C-C bond has important role in stabilizing the clusters. For the clusters containing one germanium atom and all the other as carbon atoms, the BE increases monotonically with the number of the carbon atoms. The HOMO-LUMO gap, IPs and EAs fluctuates with increase in the number of atoms. The nanoclusters containing even number of carbon atoms have large HOMO-LUMO gaps and IPs, whereas the nanoclusters containing even number of carbon atoms have small EAs. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA). The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the experimental data wherever available. The growth of these most stable structures should be possible in the experiments.

Structure, stability, thermodynamic properties, and IR spectra of the protonated water decamer H+(H2O)10.

PubMed

Karthikeyan, S; Kim, Kwang S

2009-08-13

Protonated water clusters H+(H2O)n favor two-dimensional (2D) structures for n < or = 7 at low temperatures. At 0 K, the 2D and three-dimensional (3D) structures for n = 8 are almost isoenergetic, and the 3D structures for n > 9 tend to be more stable. However, for n = 9, the netlike structures are likely to be more stable above 150 K. In this regard, we investigate the case of n = 10 to find which structure is more stable between the 3D structure and the netlike structure around 150 and 250 K. We use density functional theory, Møller-Plesset second-order perturbation theory, and coupled cluster theory with single, double, and perturbative triple excitations (CCSD(T)). At the complete basis set limit for the CCSD(T) level of theory, three isomers of 3D cage structure are much more stable in zero point energy corrected binding energy and in free binding energies at 150 K than the lowest energy netlike structures, while the netlike structure would be more stable around approximately 250 K. The predicted vibrational spectra are in good agreement with the experiment. One of the three isomers explains the experimental IR observation of an acceptor (A) type peak of a dangling hydrogen atom.

Solution and diffusion of hydrogen isotopes in tungsten-rhenium alloy

NASA Astrophysics Data System (ADS)

Ren, Fei; Yin, Wen; Yu, Quanzhi; Jia, Xuejun; Zhao, Zongfang; Wang, Baotian

2017-08-01

Rhenium is one of the main transmutation elements forming in tungsten under neutron irradiation. Therefore, it is essential to understand the influence of rhenium impurity on hydrogen isotopes retention in tungsten. First-principle calculations were used to study the properties of hydrogen solution and diffusion in perfect tungsten-rhenium lattice. The interstitial hydrogen still prefers the tetrahedral site in presence of rhenium, and rhenium atom cannot act directly as a trapping site of hydrogen. The presence of rhenium in tungsten raises the solution energy and the real normal modes of vibration on the ground state and the transition state, compared to hydrogen in pure tungsten. Without zero point energy corrections, the presence of rhenium decreases slightly the migration barrier. It is found that although the solution energy would tend to increase slightly with the rising of the concentration of rhenium, but which does not influence noticeably the solution energy of hydrogen in tungsten-rhenium alloy. The solubility and diffusion coefficient of hydrogen in perfect tungsten and tungsten-rhenium alloy have been estimated, according to Sievert's law and harmonic transition state theory. The results show the solubility of hydrogen in tungsten agrees well the experimental data, and the presence of Re would decrease the solubility and increase the diffusivity for the perfect crystals.

A hybrid indoor ambient light and vibration energy harvester for wireless sensor nodes.

PubMed

Yu, Hua; Yue, Qiuqin; Zhou, Jielin; Wang, Wei

2014-05-19

To take advantage of applications where both light and vibration energy are available, a hybrid indoor ambient light and vibration energy harvesting scheme is proposed in this paper. This scheme uses only one power conditioning circuit to condition the combined output power harvested from both energy sources so as to reduce the power dissipation. In order to more accurately predict the instantaneous power harvested from the solar panel, an improved five-parameter model for small-scale solar panel applying in low light illumination is presented. The output voltage is increased by using the MEMS piezoelectric cantilever arrays architecture. It overcomes the disadvantage of traditional MEMS vibration energy harvester with low voltage output. The implementation of the maximum power point tracking (MPPT) for indoor ambient light is implemented using analog discrete components, which improves the whole harvester efficiency significantly compared to the digital signal processor. The output power of the vibration energy harvester is improved by using the impedance matching technique. An efficient mechanism of energy accumulation and bleed-off is also discussed. Experiment results obtained from an amorphous-silicon (a-Si) solar panel of 4.8 × 2.0 cm2 and a fabricated piezoelectric MEMS generator of 11 × 12.4 mm2 show that the hybrid energy harvester achieves a maximum efficiency around 76.7%.

Zero-point Energy is Needed in Molecular Dynamics Calculations to Access the Saddle Point for H+HCN→H2CN* and cis/trans-HCNH* on a New Potential Energy Surface.

PubMed

Wang, Xiaohong; Bowman, Joel M

2013-02-12

We calculate the probabilities for the association reactions H+HCN→H2CN* and cis/trans-HCNH*, using quasiclassical trajectory (QCT) and classical trajectory (CT) calculations, on a new global ab initio potential energy surface (PES) for H2CN including the reaction channels. The surface is a linear least-squares fit of roughly 60 000 CCSD(T)-F12b/aug-cc-pVDZ electronic energies, using a permutationally invariant basis with Morse-type variables. The reaction probabilities are obtained at a variety of collision energies and impact parameters. Large differences in the threshold energies in the two types of dynamics calculations are traced to the absence of zero-point energy in the CT calculations. We argue that the QCT threshold energy is the realistic one. In addition, trajectories find a direct pathway to trans-HCNH, even though there is no obvious transition state (TS) for this pathway. Instead the saddle point (SP) for the addition to cis-HCNH is evidently also the TS for direct formation of trans-HCNH.

Diffuse Vibrational Signature of a Single Proton Embedded in the Oxalate Scaffold, HO2CCO2(-).

PubMed

Wolke, Conrad T; DeBlase, Andrew F; Leavitt, Christopher M; McCoy, Anne B; Johnson, Mark A

2015-12-31

To understand how the D2d oxalate scaffold (C2O4)(2-) distorts upon capture of a proton, we report the vibrational spectra of the cryogenically cooled HO2CCO2(-) anion and its deuterated isotopologue DO2CCO2(-). The transitions associated with the skeletal vibrations and OH bending modes are sharp and are well described by inclusion of cubic terms in the normal mode expansion of the potential surface through an extended Fermi resonance analysis. The ground state structure features a five-membered ring with an asymmetric intramolecular proton bond. The spectral signatures of the hydrogen stretches, on the contrary, are surprisingly diffuse, and this behavior is not anticipated by the extended Fermi scheme. We trace the diffuse bands to very strong couplings between the high-frequency OH-stretch and the low-frequency COH bends as well as heavy particle skeletal deformations. A simple vibrationally adiabatic model recovers this breadth of oscillator strength as a 0 K analogue of the motional broadening commonly used to explain the diffuse spectra of H-bonded systems at elevated temperatures, but where these displacements arise from the configurations present at the vibrational zero-point level.

Dynamics and control of high precision magnetically levitated vibration isolation systems

NASA Technical Reports Server (NTRS)

Youcef-Toumi, K.; Yeh, T-J.

1992-01-01

Vibration control of flexible structures has received a great deal of interest in recent years. Several authors have investigated this topic in the areas of robot manipulators, space structures, and flexible rotors. Key issues associated with the dynamics and control of vibration isolation systems are addressed. Among other important issues to consider in the control of such systems, the location and number of actuators and sensors are essential to effectively control and suppress vibration. We first address the selection of proper actuator and sensor locations leading to a controllable and observable system. The Rayleigh-Ritz modal analysis method is used to develop a lumped-parameter model of a flexible vibration isolation table top. This model is then used to investigate the system's controllability and observability including the coupling effects introduced by the magnetic bearing. This analysis results in necessary and sufficient conditions for proper selection of actuator and sensor locations. These locations are also important for both controller system's complexity and stability of point of views. A favorable pole-zero plot of the open loop transfer functions is presented. Necessary and sufficient conditions for reducing the controller complexity are derived. The results are illustrated by examples using approximate mode shape functions.

Microscopic description of fission in odd-mass uranium and plutonium nuclei with the Gogny energy density functional

NASA Astrophysics Data System (ADS)

Rodrıguez-Guzmán, R.; Robledo, L. M.

2017-12-01

The parametrization D1M of the Gogny energy density functional is used to study fission in the odd-mass Uranium and Plutonium isotopes with A=233, \\ldots , 249 within the framework of the Hartree-Fock-Bogoliubov (HFB) Equal Filling Approximation (EFA). Ground state quantum numbers and deformations, pairing energies, one-neutron separation energies, barrier heights and fission isomer excitation energies are given. Fission paths, collective masses and zero point rotational and vibrational quantum corrections are used to compute the systematic of the spontaneous fission half-lives t_{SF}, the masses and charges of the fission fragments as well as their intrinsic shapes. Although there exits a strong variance of the predicted fission rates with respect to the details involved in their computation, it is shown that both the specialization energy and the pairing quenching effects, taken into account fully variationally within the HFB-EFA blocking scheme, lead to larger spontaneous fission half-lives in odd-mass U and Pu nuclei as compared with the corresponding even-even neighbors. It is shown that modifications of a few percent in the strengths of the neutron and proton pairing fields can have a significant impact on the collective masses leading to uncertainties of several orders of magnitude in the predicted t_{SF} values. Alpha-decay lifetimes have also been computed using a parametrization of the Viola-Seaborg formula.

Towards a comprehensive model for the electronic and vibrational structure of the Creutz-Taube ion.

PubMed

Reimers, Jeffrey R; Wallace, Brett B; Hush, Noel S

2008-01-13

Since the synthesis of the Creutz-Taube ion, the nature of its charge localization has been of immense scientific interest, this molecule providing a model system for the understanding of the operation of biological photosynthetic and electron-transfer processes. However, recent work has shown that its nature remains an open question. Many systems of this type, including photosynthetic reaction centres, are of current research interest, and thereby the Creutz-Taube ion provides an important chemical paradigm: the key point of interest is the details of how such molecules behave. We lay the groundwork for the construction of a comprehensive model for its chemical and spectroscopic properties. Advances are described in some of the required areas including: simulation of electronic absorption spectra; quantitative depiction of the large interaction of the ion's electronic description with solvent motions; and the physics of Ru-NH3 spectator-mode vibrations. We show that details of the solvent electron-phonon coupling are critical in the interpretation of the spectator-mode vibrations, as these strongly mix with solvent motions when 0.75<2J/lambda<1. In this regime, a double-well potential exists which does not support localized zero-point vibration, and many observed properties of the Creutz-Taube ion are shown to be consistent with the hypothesis that the ion has this character.

An ab initio global potential-energy surface for NH2(A(2)A') and vibrational spectrum of the Renner-Teller A(2)A'-X(2)A" system.

PubMed

Zhou, Shulan; Li, Zheng; Xie, Daiqian; Lin, Shi Ying; Guo, Hua

2009-05-14

A global potential-energy surface for the first excited electronic state of NH(2)(A(2)A(')) has been constructed by three-dimensional cubic spline interpolation of more than 20,000 ab initio points, which were calculated at the multireference configuration-interaction level with the Davidson correction using the augmented correlation-consistent polarized valence quadruple-zeta basis set. The (J=0) vibrational energy levels for the ground (X(2)A(")) and excited (A(2)A(')) electronic states of NH(2) were calculated on our potential-energy surfaces with the diagonal Renner-Teller terms. The results show a good agreement with the experimental vibrational frequencies of NH(2) and its isotopomers.

Potential energy surface and vibrational band origins of the triatomic lithium cation

NASA Astrophysics Data System (ADS)

Searles, Debra J.; Dunne, Simon J.; von Nagy-Felsobuki, Ellak I.

The 104 point CISD Li +3 potential energy surface and its analytical representation is reported. The calculations predict the minimum energy geometry to be an equilateral triangle of side RLiLi = 3.0 Å and of energy - 22.20506 E h. A fifth-order Morse—Dunham type analytical force field is used in the Carney—Porter normal co-ordinate vibrational Hamiltonian, the corresponding eigenvalue problem being solved variationally using a 560 configurational finite-element basis set. The predicted assignment of the vibrational band origins is in accord with that reported for H +3. Moreover, for 6Li +3 and 7Li +3 the lowest i.r. accessible band origin is the overlineν0,1,±1 predicted to be at 243.6 and 226.0 cm -1 respectively.

Sensing Atomic Motion from the Zero Point to Room Temperature with Ultrafast Atom Interferometry.

PubMed

Johnson, K G; Neyenhuis, B; Mizrahi, J; Wong-Campos, J D; Monroe, C

2015-11-20

We sense the motion of a trapped atomic ion using a sequence of state-dependent ultrafast momentum kicks. We use this atom interferometer to characterize a nearly pure quantum state with n=1 phonon and accurately measure thermal states ranging from near the zero-point energy to n[over ¯]~10^{4}, with the possibility of extending at least 100 times higher in energy. The complete energy range of this method spans from the ground state to far outside of the Lamb-Dicke regime, where atomic motion is greater than the optical wavelength. Apart from thermometry, these interferometric techniques are useful for characterizing ultrafast entangling gates between multiple trapped ions.

Computational and Matrix Isolation Studies of (2- and 3-Furyl)methylene

DTIC Science & Technology

1994-01-01

ynal, (Appendix 3) Simple HF calculations using the 6-31 G basis set + ZPE (zero point energy correction applied) predict 2.2 to be more stable in both...QCISD(T)/6-31 1 G** + ZPE predict the triplet to more stable by 2.9 Kcal/mol. However, calculations using MP4SDTQ/6-31 1 G + ZPE predict the singlet to...calculated frequencies were scaled by a factor of 0.9. 53 Table 2.30 Calculated ZPE for 2-Oxabicyclo(3.1.0]hexa-3,5-diene.a Zero Point Energy 49.9 (KcaVmol

Nonlinear dynamics and health monitoring of 6-DOF breathing cracked Jeffcott rotor

NASA Astrophysics Data System (ADS)

Zhao, Jie; DeSmidt, Hans; Yao, Wei

2015-04-01

Jeffcott rotor is employed to study the nonlinear vibration characteristics of breathing cracked rotor system and explore the possibility of further damage identification. This paper is an extension work of prior study based on 4 degree-of-freedom Jeffcott rotor system. With consideration of disk tilting and gyroscopic effect, 6-dof EOM is derived and the crack model is established using SERR (strain energy release rate) in facture mechanics. Same as the prior work, the damaged stiffness matrix is updated by computing the instant crack closure line through Zero Stress Intensity Factor method. The breathing crack area is taken as a variable to analyze the breathing behavior in terms of eccentricity phase and shaft speed. Furthermore, the coupled vibration among lateral, torsional and longitudinal d.o.f is studied under torsional/axial excitation. The final part demonstrates the possibility of using vibration signal of damaged system for the crack diagnosis and health monitoring.

The emergence of gravity as a retro-causal post-inflation macro-quantum-coherent holographic vacuum Higgs-Goldstone field

NASA Astrophysics Data System (ADS)

Sarfatti, Jack; Levit, Creon

2009-06-01

We present a model for the origin of gravity, dark energy and dark matter: Dark energy and dark matter are residual pre-inflation false vacuum random zero point energy (w = - 1) of large-scale negative, and short-scale positive pressure, respectively, corresponding to the "zero point" (incoherent) component of a superfluid (supersolid) ground state. Gravity, in contrast, arises from the 2nd order topological defects in the post-inflation virtual "condensate" (coherent) component. We predict, as a consequence, that the LHC will never detect exotic real on-mass-shell particles that can explain dark matter ΩMDM approx 0.23. We also point out that the future holographic dark energy de Sitter horizon is a total absorber (in the sense of retro-causal Wheeler-Feynman action-at-a-distance electrodynamics) because it is an infinite redshift surface for static detectors. Therefore, the advanced Hawking-Unruh thermal radiation from the future de Sitter horizon is a candidate for the negative pressure dark vacuum energy.

Damping mathematical modelling and dynamic responses for FRP laminated composite plates with polymer matrix

NASA Astrophysics Data System (ADS)

Liu, Qimao

2018-02-01

This paper proposes an assumption that the fibre is elastic material and polymer matrix is viscoelastic material so that the energy dissipation depends only on the polymer matrix in dynamic response process. The damping force vectors in frequency and time domains, of FRP (Fibre-Reinforced Polymer matrix) laminated composite plates, are derived based on this assumption. The governing equations of FRP laminated composite plates are formulated in both frequency and time domains. The direct inversion method and direct time integration method for nonviscously damped systems are employed to solve the governing equations and achieve the dynamic responses in frequency and time domains, respectively. The computational procedure is given in detail. Finally, dynamic responses (frequency responses with nonzero and zero initial conditions, free vibration, forced vibrations with nonzero and zero initial conditions) of a FRP laminated composite plate are computed using the proposed methodology. The proposed methodology in this paper is easy to be inserted into the commercial finite element analysis software. The proposed assumption, based on the theory of material mechanics, needs to be further proved by experiment technique in the future.

Homogeneous and heterogeneous noncovalent dimers of formaldehyde and thioformaldehyde: structures, energetics, and vibrational frequencies.

PubMed

Van Dornshuld, Eric; Holy, Christina M; Tschumper, Gregory S

2014-05-08

This work provides the first characterization of five stationary points of the homogeneous thioformaldehyde dimer, (CH2S)2, and seven stationary points of the heterogeneous formaldehyde/thioformaldehyde dimer, CH2O/CH2S, with correlated ab initio electronic structure methods. Full geometry optimizations and corresponding harmonic vibrational frequencies were computed with second-order Møller-Plesset perturbation theory (MP2) and 13 different density functionals in conjunction with triple-ζ basis sets augmented with diffuse and multiple sets of polarization functions. The MP2 results indicate that the three stationary points of (CH2S)2 and four of CH2O/CH2S are minima, in contrast to two stationary points of the formaldehyde dimer, (CH2O)2. Single-point energies were also computed using the explicitly correlated MP2-F12 and CCSD(T)-F12 methods and basis sets as large as heavy-aug-cc-pVTZ. The (CH2O)2 and CH2O/CH2S MP2 and MP2-F12 binding energies deviated from the CCSD(T)-F12 binding energies by no more than 0.2 and 0.4 kcal mol(-1), respectively. The (CH2O)2 and CH2O/CH2S global minimum is the same at every level of theory. However, the MP2 methods overbind (CH2S)2 by as much as 1.1 kcal mol(-1), effectively altering the energetic ordering of the thioformaldehyde dimer minima relative to the CCSD(T)-F12 energies. The CCSD(T)-F12 binding energies of the (CH2O)2 and CH2O/CH2S stationary points are quite similar, with the former ranging from around -2.4 to -4.6 kcal mol(-1) and the latter from about -1.1 to -4.4 kcal mol(-1). Corresponding (CH2S)2 stationary points have appreciably smaller CCSD(T)-F12 binding energies ranging from ca. -1.1 to -3.4 kcal mol(-1). The vibrational frequency shifts upon dimerization are also reported for each minimum on the MP2 potential energy surfaces.

New mechanism for autocatalytic decomposition of H2CO3 in the vapor phase.

PubMed

Ghoshal, Sourav; Hazra, Montu K

2014-04-03

In this article, we present high level ab initio calculations investigating the energetics of a new autocatalytic decomposition mechanism for carbonic acid (H2CO3) in the vapor phase. The calculation have been performed at the MP2 level of theory in conjunction with aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(3df,3pd) basis sets as well as at the CCSD(T)/aug-cc-pVTZ level. The present study suggests that this new decomposition mechanism is effectively a near-barrierless process at room temperature and makes vapor phase of H2CO3 unstable even in the absence of water molecules. Our calculation at the MP2/aug-cc-pVTZ level predicts that the effective barrier, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, is nearly zero for the autocatalytic decomposition mechanism. The results at the CCSD(T)/aug-cc-pVTZ level of calculations suggest that the effective barrier, as defined above, is sensitive to some extent to the levels of calculations used, nevertheless, we find that the effective barrier height predicted at the CCSD(T)/aug-cc-pVTZ level is very small or in other words the autocatalytic decomposition mechanism presented in this work is a near-barrierless process as mentioned above. Thus, we suggest that this new autocatalytic decomposition mechanism has to be considered as the primary mechanism for the decomposition of carbonic acid, especially at its source, where the vapor phase concentration of H2CO3 molecules reaches its highest levels.

Study on the intrinsic defects in tin oxide with first-principles method

NASA Astrophysics Data System (ADS)

Sun, Yu; Liu, Tingyu; Chang, Qiuxiang; Ma, Changmin

2018-04-01

First-principles and thermodynamic methods are used to study the contribution of vibrational entropy to defect formation energy and the stability of the intrinsic point defects in SnO2 crystal. According to thermodynamic calculation results, the contribution of vibrational entropy to defect formation energy is significant and should not be neglected, especially at high temperatures. The calculated results indicate that the oxygen vacancy is the major point defect in undoped SnO2 crystal, which has a higher concentration than that of the other point defect. The property of negative-U is put forward in SnO2 crystal. In order to determine the most stable defects much clearer under different conditions, the most stable intrinsic defect as a function of Fermi level, oxygen partial pressure and temperature are described in the three-dimensional defect formation enthalpy diagrams. The diagram visually provides the most stable point defects under different conditions.

A judging principle of crucial vibrational transmission paths in plates

NASA Astrophysics Data System (ADS)

Wang, Bin; Li, Dong-Xu; Jiang, Jian-Ping; Liao, Yi-Huan

2016-10-01

This paper developed a judging principle of crucial vibrational transmission path (VTP) in plates. Novel generalized definitions of VTPs are given referred to the meaning of streamlines. And by comparing governing equations, the similarity between energy flow and fluid motion is firstly found so that an analytic method of VTPs in plates is proposed by analogy with fluid motion. Hereafter, the crucial VTP is defined for energy flows at objective points and relative judging criteria is given. Finally, based on two numerical experiments of passive control, the judging principle is indirectly verified by comparing the reduction effects of energy flows at focused points and relative judgment results of crucial VTPs. This paper is meaningful for analyzing and applying the VTPs in plates to guide the control design in future.

Non-contact measurement of facial surface vibration patterns during singing by scanning laser Doppler vibrometer.

PubMed

Kitamura, Tatsuya; Ohtani, Keisuke

2015-01-01

This paper presents a method of measuring the vibration patterns on facial surfaces by using a scanning laser Doppler vibrometer (LDV). The surfaces of the face, neck, and body vibrate during phonation and, according to Titze (2001), these vibrations occur when aerodynamic energy is efficiently converted into acoustic energy at the glottis. A vocalist's vibration velocity patterns may therefore indicate his or her phonatory status or singing skills. LDVs enable laser-based non-contact measurement of the vibration velocity and displacement of a certain point on a vibrating object, and scanning LDVs permit multipoint measurements. The benefits of scanning LDVs originate from the facts that they do not affect the vibrations of measured objects and that they can rapidly measure the vibration patterns across planes. A case study is presented herein to demonstrate the method of measuring vibration velocity patterns with a scanning LDV. The objective of the experiment was to measure the vibration velocity differences between the modal and falsetto registers while three professional soprano singers sang sustained vowels at four pitch frequencies. The results suggest that there is a possibility that pitch frequency are correlated with vibration velocity. However, further investigations are necessary to clarify the relationships between vibration velocity patterns and phonation status and singing skills.

Non-contact measurement of facial surface vibration patterns during singing by scanning laser Doppler vibrometer

PubMed Central

Kitamura, Tatsuya; Ohtani, Keisuke

2015-01-01

This paper presents a method of measuring the vibration patterns on facial surfaces by using a scanning laser Doppler vibrometer (LDV). The surfaces of the face, neck, and body vibrate during phonation and, according to Titze (2001), these vibrations occur when aerodynamic energy is efficiently converted into acoustic energy at the glottis. A vocalist's vibration velocity patterns may therefore indicate his or her phonatory status or singing skills. LDVs enable laser-based non-contact measurement of the vibration velocity and displacement of a certain point on a vibrating object, and scanning LDVs permit multipoint measurements. The benefits of scanning LDVs originate from the facts that they do not affect the vibrations of measured objects and that they can rapidly measure the vibration patterns across planes. A case study is presented herein to demonstrate the method of measuring vibration velocity patterns with a scanning LDV. The objective of the experiment was to measure the vibration velocity differences between the modal and falsetto registers while three professional soprano singers sang sustained vowels at four pitch frequencies. The results suggest that there is a possibility that pitch frequency are correlated with vibration velocity. However, further investigations are necessary to clarify the relationships between vibration velocity patterns and phonation status and singing skills. PMID:26579054

A new approach to detecting gravitational waves via the coupling of gravity to the zero-point energy of the phonon modes of a superconductor

NASA Astrophysics Data System (ADS)

Inan, Nader A.

The response of a superconductor to a gravitational wave is shown to obey a London-like constituent equation. The Cooper pairs are described by the Ginzburg-Landau free energy density embedded in curved spacetime. The lattice ions are modeled by quantum harmonic oscillators characterized by quasi-energy eigenvalues. This formulation is shown to predict a dynamical Casimir effect since the zero-point energy of the ionic lattice phonons is modulated by the gravitational wave. It is also shown that the response to a gravitational wave is far less for the Cooper pair density than for the ionic lattice. This predicts a “charge separation effect” which can be used to detect the passage of a gravitational wave.

High-energy zero-norm states and symmetries of string theory.

PubMed

Chan, Chuan-Tsung; Ho, Pei-Ming; Lee, Jen-Chi; Teraguchi, Shunsuke; Yang, Yi

2006-05-05

High-energy limit of zero-norm states in the old covariant first quantized spectrum of the 26D open bosonic string, together with the assumption of a smooth behavior of string theory in this limit, are used to derive infinitely many linear relations among the leading high-energy, fixed-angle behavior of four-point functions of different string states. As a result, ratios among all high-energy scattering amplitudes of four arbitrary string states can be calculated algebraically and the leading order amplitudes can be expressed in terms of that of four tachyons as conjectured by Gross in 1988. A dual calculation can also be performed and equivalent results are obtained by taking the high-energy limit of Virasoro constraints. Finally, we compute all high-energy scattering amplitudes of three tachyons and one massive state at the leading order by saddle-point approximation to verify our results.

Near-Infrared Spectroscopy of Ethynyl Radical, C2H

NASA Astrophysics Data System (ADS)

Le, Anh T.; Hall, Gregory; Sears, Trevor

2016-06-01

The ethynyl radical, C_2H, is a reactive intermediate important in various combustion processes and also widely observed in the interstellar medium. In spite of extensive previous spectroscopic studies, the characterization of the near infrared transitions from the tilde{X}2Σ+ state to the mixed vibrational overtone and tilde{A}2Π states is incomplete. A strong band of C_2H at 7064 cm-1 was first observed in a neon matrix and assigned as the tilde{A}2Π(002)1 - tilde{X}2Σ+ transition by Forney et al. Subsequent theoretical work of Tarroni and Carter attributed the strong absorptions in this region to transitions terminating in two upper states, each a mixture of vibrationally excited tilde{X} states and different zero-order tilde{A}-state bending levels: a 2Σ+ symmetry combination of tilde{X}(0,20,3) and tilde{A}(0,3,0)0κ and a 2Π symmetry combination of tilde{X}(0,31,3) and tilde{A}(0,0,2)1. Transitions to them from the zero point level of the tilde{X} state are calculated to differ in energy by less than 10 cm-1 and to be within a factor of two in intensity. Diode laser transient absorption was used to record Doppler-limited spectra between 7020 and 7130 cm-1, using 193 nm photolysis of CF_3C_2H as a source of C_2H. Two interleaved, rotationally resolved bands were observed, consistent with a 2Σ - 2Σ transition at 7088 cm-1 and a 2Π - 2Σ transition at 7108 cm-1, in good accord with the Tarroni and Carter calculation. Progress on the assignment and fitting of the spectra will be reported. Acknowledgements: Work at Brookhaven National Laboratory was carried out under Contract No. DE-SC0012704 with the U.S. Department of Energy, Office of Science, and supported by its Division of Chemical Sciences, Geosciences, and Biosciences. D. Forney, M.E. Jacox, and W.E. Thompson, J. Mol. Spectrosc. 170, 178 (1995). R. Tarroni and S. Carter, Mol. Phys. 102, 2167 (2004)

Ultrafast atomic-scale visualization of acoustic phonons generated by optically excited quantum dots

PubMed Central

Vanacore, Giovanni M.; Hu, Jianbo; Liang, Wenxi; Bietti, Sergio; Sanguinetti, Stefano; Carbone, Fabrizio; Zewail, Ahmed H.

2017-01-01

Understanding the dynamics of atomic vibrations confined in quasi-zero dimensional systems is crucial from both a fundamental point-of-view and a technological perspective. Using ultrafast electron diffraction, we monitored the lattice dynamics of GaAs quantum dots—grown by Droplet Epitaxy on AlGaAs—with sub-picosecond and sub-picometer resolutions. An ultrafast laser pulse nearly resonantly excites a confined exciton, which efficiently couples to high-energy acoustic phonons through the deformation potential mechanism. The transient behavior of the measured diffraction pattern reveals the nonequilibrium phonon dynamics both within the dots and in the region surrounding them. The experimental results are interpreted within the theoretical framework of a non-Markovian decoherence, according to which the optical excitation creates a localized polaron within the dot and a travelling phonon wavepacket that leaves the dot at the speed of sound. These findings indicate that integration of a phononic emitter in opto-electronic devices based on quantum dots for controlled communication processes can be fundamentally feasible. PMID:28852685

Deuteration as a Means to Tune Crystallinity of Conducting Polymers

DOE PAGES

Jakowski, Jacek; Huang, Jingsong; Garashchuk, Sophya; ...

2017-08-25

The effects of deuterium isotope substitution on conjugated polymer chain stacking of poly(3-hexylthiophene) is studied in this paper experimentally by X-ray diffraction (XRD) in combination with gel permeation chromatography and theoretically using density functional theory and quantum molecular dynamics. For four P3HT materials with different levels of deuteration (pristine, main-chain deuterated, side-chain deuterated, and fully deuterated), the XRD measurements show that main-chain thiophene deuteration significantly reduces crystallinity, regardless of the side-chain deuteration. The reduction of crystallinity due to the main-chain deuteration is a quantum nuclear effect resulting from a static zero-point vibrational energy combined with a dynamic correlation of themore » dipole fluctuations. The quantum molecular dynamics simulations confirm the interchain correlation of the proton–proton and deuteron–deuteron motions but not of the proton–deuteron motion. Thus and finally, isotopic purity is an important factor affecting stability and properties of conjugated polymer crystals, which should be considered in the design of electronic and spintronic devices.« less

Deuteration as a Means to Tune Crystallinity of Conducting Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jakowski, Jacek; Huang, Jingsong; Garashchuk, Sophya

The effects of deuterium isotope substitution on conjugated polymer chain stacking of poly(3-hexylthiophene) is studied in this paper experimentally by X-ray diffraction (XRD) in combination with gel permeation chromatography and theoretically using density functional theory and quantum molecular dynamics. For four P3HT materials with different levels of deuteration (pristine, main-chain deuterated, side-chain deuterated, and fully deuterated), the XRD measurements show that main-chain thiophene deuteration significantly reduces crystallinity, regardless of the side-chain deuteration. The reduction of crystallinity due to the main-chain deuteration is a quantum nuclear effect resulting from a static zero-point vibrational energy combined with a dynamic correlation of themore » dipole fluctuations. The quantum molecular dynamics simulations confirm the interchain correlation of the proton–proton and deuteron–deuteron motions but not of the proton–deuteron motion. Thus and finally, isotopic purity is an important factor affecting stability and properties of conjugated polymer crystals, which should be considered in the design of electronic and spintronic devices.« less

Lock-in in forced vibration of a circular cylinder

NASA Astrophysics Data System (ADS)

Kumar, Samvit; Navrose, Mittal, Sanjay

2016-11-01

The phenomenon of lock-in/synchronization in uniform flow past an oscillating cylinder is investigated via a stabilized finite element method at Re = 100. Computations are carried out for various amplitudes and frequencies of cylinder oscillation to accurately obtain the boundary of the lock-in regime. Results from earlier studies show a significant scatter in the lock-in boundary. The scatter might be an outcome of the difference in data collection or the use of a different criterion for identifying lock-in. A new criterion for lock-in is proposed, wherein the following two conditions are to be satisfied. (i) The most dominant frequency in the power spectrum of lift coefficient matches the frequency of cylinder oscillation (fy) and (ii) other peaks in the power spectrum, if any, are present only at super-harmonics of fy. Utilizing this criterion, three flow regimes are identified on the frequency-amplitude plane: lock-in, transition, and no lock-in. The behaviour of the wake is also investigated by examining the power spectra of the velocity traces at various locations downstream of the cylinder. Wake-lock-in is observed during lock-in. A wake-transition regime is identified wherein the near wake, up to a certain streamwise location, is in a lock-in state while the downstream region is in a desynchronized state. For a fixed fy, the location beyond which the wake is desynchronized moves downstream as the amplitude of oscillation is increased. The proposed criterion for lock-in addresses the wide scatter in the boundary of the lock-in regime among earlier studies. Energy transfer from the fluid to the structure, per cycle of cylinder oscillation, is computed from the data for forced vibration. The data is utilized to generate iso-energy transfer contours in the frequency-amplitude plane. The free vibration response with zero structural damping is found to be in very good agreement with the contour corresponding to zero energy transfer.

Explicit hydration of ammonium ion by correlated methods employing molecular tailoring approach

NASA Astrophysics Data System (ADS)

Singh, Gurmeet; Verma, Rahul; Wagle, Swapnil; Gadre, Shridhar R.

2017-11-01

Explicit hydration studies of ions require accurate estimation of interaction energies. This work explores the explicit hydration of the ammonium ion (NH4+) employing Møller-Plesset second order (MP2) perturbation theory, an accurate yet relatively less expensive correlated method. Several initial geometries of NH4+(H2O)n (n = 4 to 13) clusters are subjected to MP2 level geometry optimisation with correlation consistent aug-cc-pVDZ (aVDZ) basis set. For large clusters (viz. n > 8), molecular tailoring approach (MTA) is used for single point energy evaluation at MP2/aVTZ level for the estimation of MP2 level binding energies (BEs) at complete basis set (CBS) limit. The minimal nature of the clusters upto n ≤ 8 is confirmed by performing vibrational frequency calculations at MP2/aVDZ level of theory, whereas for larger clusters (9 ≤ n ≤ 13) such calculations are effected via grafted MTA (GMTA) method. The zero point energy (ZPE) corrections are done for all the isomers lying within 1 kcal/mol of the lowest energy one. The resulting frequencies in N-H region (2900-3500 cm-1) and in O-H stretching region (3300-3900 cm-1) are in found to be in excellent agreement with the available experimental findings for 4 ≤ n ≤ 13. Furthermore, GMTA is also applied for calculating the BEs of these clusters at coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory with aVDZ basis set. This work thus represents an art of the possible on contemporary multi-core computers for studying explicit molecular hydration at correlated level theories.

Symmetry breaking in the zero-energy Landau level in bilayer graphene.

PubMed

Zhao, Y; Cadden-Zimansky, P; Jiang, Z; Kim, P

2010-02-12

The quantum Hall effect near the charge neutrality point in bilayer graphene is investigated in high magnetic fields of up to 35 T using electronic transport measurements. In the high-field regime, the eightfold degeneracy in the zero-energy Landau level is completely lifted, exhibiting new quantum Hall states corresponding to filling factors nu=0, 1, 2, and 3. Measurements of the activation energy gaps for the nu=2 and 3 filling factors in tilted magnetic fields exhibit no appreciable dependence on the in-plane magnetic field, suggesting that these Landau level splittings are independent of spin. In addition, measurements taken at the nu=0 charge neutral point show that, similar to single layer graphene, the bilayer becomes insulating at high fields.

Estimating the intrinsic limit of the Feller-Peterson-Dixon composite approach when applied to adiabatic ionization potentials in atoms and small molecules

NASA Astrophysics Data System (ADS)

Feller, David

2017-07-01

Benchmark adiabatic ionization potentials were obtained with the Feller-Peterson-Dixon (FPD) theoretical method for a collection of 48 atoms and small molecules. In previous studies, the FPD method demonstrated an ability to predict atomization energies (heats of formation) and electron affinities well within a 95% confidence level of ±1 kcal/mol. Large 1-particle expansions involving correlation consistent basis sets (up to aug-cc-pV8Z in many cases and aug-cc-pV9Z for some atoms) were chosen for the valence CCSD(T) starting point calculations. Despite their cost, these large basis sets were chosen in order to help minimize the residual basis set truncation error and reduce dependence on approximate basis set limit extrapolation formulas. The complementary n-particle expansion included higher order CCSDT, CCSDTQ, or CCSDTQ5 (coupled cluster theory with iterative triple, quadruple, and quintuple excitations) corrections. For all of the chemical systems examined here, it was also possible to either perform explicit full configuration interaction (CI) calculations or to otherwise estimate the full CI limit. Additionally, corrections associated with core/valence correlation, scalar relativity, anharmonic zero point vibrational energies, non-adiabatic effects, and other minor factors were considered. The root mean square deviation with respect to experiment for the ionization potentials was 0.21 kcal/mol (0.009 eV). The corresponding level of agreement for molecular enthalpies of formation was 0.37 kcal/mol and for electron affinities 0.20 kcal/mol. Similar good agreement with experiment was found in the case of molecular structures and harmonic frequencies. Overall, the combination of energetic, structural, and vibrational data (655 comparisons) reflects the consistent ability of the FPD method to achieve close agreement with experiment for small molecules using the level of theory applied in this study.

Vibration isolation by exploring bio-inspired structural nonlinearity.

PubMed

Wu, Zhijing; Jing, Xingjian; Bian, Jing; Li, Fengming; Allen, Robert

2015-10-08

Inspired by the limb structures of animals/insects in motion vibration control, a bio-inspired limb-like structure (LLS) is systematically studied for understanding and exploring its advantageous nonlinear function in passive vibration isolation. The bio-inspired system consists of asymmetric articulations (of different rod lengths) with inside vertical and horizontal springs (as animal muscle) of different linear stiffness. Mathematical modeling and analysis of the proposed LLS reveal that, (a) the system has very beneficial nonlinear stiffness which can provide flexible quasi-zero, zero and/or negative stiffness, and these nonlinear stiffness properties are adjustable or designable with structure parameters; (b) the asymmetric rod-length ratio and spring-stiffness ratio present very beneficial factors for tuning system equivalent stiffness; (c) the system loading capacity is also adjustable with the structure parameters which presents another flexible benefit in application. Experiments and comparisons with existing quasi-zero-stiffness isolators validate the advantageous features above, and some discussions are also given about how to select structural parameters for practical applications. The results would provide an innovative bio-inspired solution to passive vibration control in various engineering practice.

The iron-isotope fractionation dictated by the carboxylic functional: An ab-initio investigation

NASA Astrophysics Data System (ADS)

Ottonello, G.; Vetuschi Zuccolini, M.

2008-12-01

The ground-state geometries, electronic energies and vibrational properties of carboxylic complexes of iron were investigated both in vacuo and under the effect of a reaction field, to determine thermodynamic properties of iron-acetates and the role of the carboxylic functional on the isotopic imprinting of this metal in metalorganic complexation. The electronic energy, zero point corrections and thermal corrections of these substances at variational state were investigated at the DFT/B3LYP level of theory with different basis set expansions and the effect of the reaction field on the variational structures was investigated through the Polarized Continuun Model. Thermochemical cycle calculations, combined with solvation energy calculations and appropriate scaling from absolute to conventional properties allowed to compute the Gibbs free energy of formation from the elements of the investigated aqueous species and to select the best procedure to be applied in the successive vibrational analysis. The best compliance with the few existing thermodynamic data for these substances was obtained by coupling the gas phase calculations at DFT/B3LYP level with the [6-31G(d,p)]-[6-31G+(d,p)] (for cations and neutral molecules - anions; respectively) with solvation calculations adopting atomic radii optimized for the HF/6-31G(d) level of theory (UAHF). A vibrational analysis conducted on 54Fe, 56Fe, 57Fe and 58Fe gaseous isotopomers yielded reduced partition function ratios which increased not only with the nominal valence of the central cation, as expected, but, more importantly, with the extent of the complexation operated by the organic functional. Coupling thermodynamic data with separative effects it was shown that this last is controlled, as expected, by the relative bond strength of the complex in both aggregation states. Through the Integral Equation Formalism of the Polarized Continuum Model (IEFPCM) the effect of the ionic strength of the solution and of a T-dependent permittivity on the energy and separative effects of the solvated metalorganic complexes were analyzed in detail. The solvent effect in the standard state (hypothetical one-molal solution referred to infinite dilution; T = 298.15 K, P = 1 bar) is a limited reduction of the separative effects of all the isotopomeric couples. With an increase in T (and the concomitant decrease in the dielectric constant of the solvent) this effect diminishes progressively.

Isotopomer-selective spectra of a single intact H2O molecule in the Cs+(D2O)5H2O isotopologue: Going beyond pattern recognition to harvest the structural information encoded in vibrational spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolke, Conrad T.; Fournier, Joseph A.; Miliordos, Evangelos

We report the vibrational signatures of a single H2O water molecule occupying distinct sites of the hydration network in the Cs+(H2O)6 cluster. This is accomplished using isotopomer selective IR-IR hole-burning on the Cs+(D2O)5(H2O) clusters formed by gas-phase exchange of a single, intact H2O molecule for D2O in the Cs+(D2O)6 ion. The OH stretching pattern of the Cs+(H2O)6 isotopologue is accurately recovered by superposition of the isotopomer spectra, thus establishing that the H2O incorporation is random and that the OH stretching manifold is largely due to contributions from decoupled water molecules. This behavior enables a powerful new way to extract structuralmore » information from vibrational spectra of size-selected clusters by explicitly identifying the local environments responsible for specific infrared features. The Cs+(H2O)6 structure was unambiguously assigned to the 4.1.1 isomer (a homodromic water tetramer with two additional flanking water molecules) from the fact that its computed IR spectrum matches the observed overall pattern and recovers the embedded correlations in the two OH stretching bands of the water molecule in the Cs+(D2O)5(H2O) isotopomers. The 4.1.1 isomer is the lowest in energy among other candidate networks at advanced (e.g., CCSD(T)) levels of theoretical treatment after corrections for (anharmonic) zero-point energy (ZPE). With the structure in hand, we then explore the mechanical origin of the various band locations using a local electric field formalism. This approach promises to provide a transferrable scheme for the prediction of the OH stretching fundamentals displayed by water networks in close proximity to solute ions.« less

Hydrogen bond spectroscopy in the near infrared: Out-of-plane torsion and antigeared bend combination bands in (HF)2

NASA Astrophysics Data System (ADS)

Anderson, David T.; Davis, Scott; Nesbitt, David J.

1996-09-01

High-resolution near infrared spectra of the two ``high'' frequency intermolecular modes of (HF)2 have been characterized in HF-stretch excited states using a slit jet spectrometer. In the spectral region between 4280 and 4480 cm-1, four vibration-rotation-tunneling (VRT) bands are observed and assigned to tunneling pairs of the out-of-plane torsion (ν6) and antigeared bend (ν3) intermolecular modes, in combination with the hydrogen bond donor (ν2) and acceptor (ν1) high-frequency intramolecular HF stretches, respectively. Analysis of the jet-cooled, rotationally resolved spectra provide intermolecular frequencies, rotational constants, tunneling splittings, and predissociation rates for the ν3/ν6 intermolecular excited states. The relatively small changes in the hydrogen bond interconversion tunneling splitting with either ν3 or ν6 excitation indicate that neither intermolecular mode is strongly coupled to the tunneling coordinate. The high-resolution VRT linewidths reveal mode specific predissociation broadening sensitive predominantly to intramolecular excitation, but with significant additional effects due to low-frequency intermolecular excitation as well. The intermolecular vibrational frequencies in the combination states display a systematic dependence on intramolecular redshift that allows all four intermolecular fundamental frequencies to be extrapolated from the near-ir data. Agreement between full 6-D quantum calculations and experiment for the out-of-plane torsion (ν6) vibration is remarkably good (0.5%). However, significant discrepancies (≳10%) between theory and experiment are obtained for the antigeared bend (ν3), indicating the need for further refinement of the HF dimer potential surface. Finally, the observation of all four intermolecular modes allows zero-point contributions to the binding energy to be reliably estimated. The revised value for the binding energy, De=1580(35) cm-1, is slightly higher than semiempirical estimates but now in excellent agreement with recent high level ab initio calculations.

Wave-packet formation at the zero-dispersion point in the Gardner-Ostrovsky equation.

PubMed

Whitfield, A J; Johnson, E R

2015-05-01

The long-time effect of weak rotation on an internal solitary wave is the decay into inertia-gravity waves and the eventual emergence of a coherent, steadily propagating, nonlinear wave packet. There is currently no entirely satisfactory explanation as to why these wave packets form. Here the initial value problem is considered within the context of the Gardner-Ostrovsky, or rotation-modified extended Korteweg-de Vries, equation. The linear Gardner-Ostrovsky equation has maximum group velocity at a critical wave number, often called the zero-dispersion point. It is found here that a nonlinear splitting of the wave-number spectrum at the zero-dispersion point, where energy is shifted into the modulationally unstable regime of the Gardner-Ostrovsky equation, is responsible for the wave-packet formation. Numerical comparisons of the decay of a solitary wave in the Gardner-Ostrovsky equation and a derived nonlinear Schrödinger equation at the zero-dispersion point are used to confirm the spectral splitting.

Numerical simulation of hydrogen fluorine overtone chemical lasers

NASA Astrophysics Data System (ADS)

Chen, Jinbao; Jiang, Zhongfu; Hua, Weihong; Liu, Zejin; Shu, Baihong

1998-08-01

A two-dimensional program was applied to simulate the chemical dynamic process, gas dynamic process and lasing process of a combustion-driven CW HF overtone chemical lasers. Some important parameters in the cavity were obtained. The calculated results included HF molecule concentration on each vibration energy level while lasing, averaged pressure and temperature, zero power gain coefficient of each spectral line, laser spectrum, the averaged laser intensity, output power, chemical efficiency and the length of lasing zone.

Transonic streamline of symmetric wing under the influence unilateral oscillations characterized by the spectrum of two frequencies

NASA Astrophysics Data System (ADS)

Zamuraev, V. P.; Kalinina, A. P.

2017-10-01

Forced high-frequency vibrations of the airfoil surface part with the amplitude almost equal to the sound velocity can change significantly the lift force of the symmetric profile streamlined at zero angle of attack. The oscillation consists of two harmonics. The ratio of harmonics frequencies values is equal to 2. The present work shows that the aerodynamic properties depend significantly on the specific energy contribution of each frequency.

Construction of a coarse-grain quasi-classical trajectory method. II. Comparison against the direct molecular simulation method

NASA Astrophysics Data System (ADS)

Macdonald, R. L.; Grover, M. S.; Schwartzentruber, T. E.; Panesi, M.

2018-02-01

This work presents the analysis of non-equilibrium energy transfer and dissociation of nitrogen molecules (N2(g+1Σ) ) using two different approaches: the direct molecular simulation (DMS) method and the coarse-grain quasi-classical trajectory (CG-QCT) method. The two methods are used to study thermochemical relaxation in a zero-dimensional isochoric and isothermal reactor in which the nitrogen molecules are heated to several thousand degrees Kelvin, forcing the system into strong non-equilibrium. The analysis considers thermochemical relaxation for temperatures ranging from 10 000 to 25 000 K. Both methods make use of the same potential energy surface for the N2(g+1Σ ) -N2(g+1Σ ) system taken from the NASA Ames quantum chemistry database. Within the CG-QCT method, the rovibrational energy levels of the electronic ground state of the nitrogen molecule are lumped into a reduced number of bins. Two different grouping strategies are used: the more conventional vibrational-based grouping, widely used in the literature, and energy-based grouping. The analysis of both the internal state populations and concentration profiles show excellent agreement between the energy-based grouping and the DMS solutions. During the energy transfer process, discrepancies arise between the energy-based grouping and DMS solution due to the increased importance of mode separation for low energy states. By contrast, the vibrational grouping, traditionally considered state-of-the-art, captures well the behavior of the energy relaxation but fails to consistently predict the dissociation process. The deficiency of the vibrational grouping model is due to the assumption of strict mode separation and equilibrium of rotational energy states. These assumptions result in errors predicting the energy contribution to dissociation from the rotational and vibrational modes, with rotational energy actually contributing 30%-40% of the energy required to dissociate a molecule. This work confirms the findings discussed in Paper I [R. L. Macdonald et al., J. Chem. Phys. 148, 054309 (2018)], which underlines the importance of rotational energy to the dissociation process, and demonstrates that an accurate non-equilibrium chemistry model must accurately predict the deviation of rovibrational distribution from equilibrium.

Construction of a coarse-grain quasi-classical trajectory method. II. Comparison against the direct molecular simulation method.

PubMed

Macdonald, R L; Grover, M S; Schwartzentruber, T E; Panesi, M

2018-02-07

This work presents the analysis of non-equilibrium energy transfer and dissociation of nitrogen molecules (N 2 (Σg+1)) using two different approaches: the direct molecular simulation (DMS) method and the coarse-grain quasi-classical trajectory (CG-QCT) method. The two methods are used to study thermochemical relaxation in a zero-dimensional isochoric and isothermal reactor in which the nitrogen molecules are heated to several thousand degrees Kelvin, forcing the system into strong non-equilibrium. The analysis considers thermochemical relaxation for temperatures ranging from 10 000 to 25 000 K. Both methods make use of the same potential energy surface for the N 2 (Σg+1)-N 2 (Σg+1) system taken from the NASA Ames quantum chemistry database. Within the CG-QCT method, the rovibrational energy levels of the electronic ground state of the nitrogen molecule are lumped into a reduced number of bins. Two different grouping strategies are used: the more conventional vibrational-based grouping, widely used in the literature, and energy-based grouping. The analysis of both the internal state populations and concentration profiles show excellent agreement between the energy-based grouping and the DMS solutions. During the energy transfer process, discrepancies arise between the energy-based grouping and DMS solution due to the increased importance of mode separation for low energy states. By contrast, the vibrational grouping, traditionally considered state-of-the-art, captures well the behavior of the energy relaxation but fails to consistently predict the dissociation process. The deficiency of the vibrational grouping model is due to the assumption of strict mode separation and equilibrium of rotational energy states. These assumptions result in errors predicting the energy contribution to dissociation from the rotational and vibrational modes, with rotational energy actually contributing 30%-40% of the energy required to dissociate a molecule. This work confirms the findings discussed in Paper I [R. L. Macdonald et al., J. Chem. Phys. 148, 054309 (2018)], which underlines the importance of rotational energy to the dissociation process, and demonstrates that an accurate non-equilibrium chemistry model must accurately predict the deviation of rovibrational distribution from equilibrium.

Accurate bond energies of hydrocarbons from complete basis set extrapolated multi-reference singles and doubles configuration interaction.

PubMed

Oyeyemi, Victor B; Pavone, Michele; Carter, Emily A

2011-12-09

Quantum chemistry has become one of the most reliable tools for characterizing the thermochemical underpinnings of reactions, such as bond dissociation energies (BDEs). The accurate prediction of these particular properties (BDEs) are challenging for ab initio methods based on perturbative corrections or coupled cluster expansions of the single-determinant Hartree-Fock wave function: the processes of bond breaking and forming are inherently multi-configurational and require an accurate description of non-dynamical electron correlation. To this end, we present a systematic ab initio approach for computing BDEs that is based on three components: 1) multi-reference single and double excitation configuration interaction (MRSDCI) for the electronic energies; 2) a two-parameter scheme for extrapolating MRSDCI energies to the complete basis set limit; and 3) DFT-B3LYP calculations of minimum-energy structures and vibrational frequencies to account for zero point energy and thermal corrections. We validated our methodology against a set of reliable experimental BDE values of CC and CH bonds of hydrocarbons. The goal of chemical accuracy is achieved, on average, without applying any empirical corrections to the MRSDCI electronic energies. We then use this composite scheme to make predictions of BDEs in a large number of hydrocarbon molecules for which there are no experimental data, so as to provide needed thermochemical estimates for fuel molecules. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantum effects of translational motions in solid para-hydrogen and ortho-deuterium: anharmonic extension of the Einstein model.

PubMed

Kühn, O; Manz, J; Schild, A

2010-04-07

An anharmonic extension of the Einstein model is developed in order to describe the effect of translational zero point motion on structural and thermodynamic properties of para-H(2) and ortho-D(2) crystals in the zero temperature limit. Accordingly, the molecules carry out large amplitude translational motions in their matrix cage, which are formed by the frozen environment of all other molecules. These translations lead from the molecular equilibrium positions via the harmonic to the anharmonic domain of the potential energy surface. The resulting translational distributions are roughly isotropic, and they have approximately Gaussian shapes, with rather broad full widths at half-maximum, FWHM(para-H(2)/ortho-D(2)) = 1.36/1.02 Å. The translational zero point energies induce expansions of the crystals, in nearly quantitative agreement with experimental results. Furthermore, they make significant contributions to the sublimation energies and zero pressure bulk moduli. These quantum effects decrease with heavier molecular masses. The corresponding isotope effects for ortho-D(2) compared to para-H(2) are confirmed by application of the model to Ar crystals. The results imply consequences for laser induced reaction dynamics of dopants with their host crystals.

Ab Initio Vibrational Levels For HO2 and Vibrational Splittings for Hydrogen Atom Transfer

NASA Technical Reports Server (NTRS)

Barclay, V. J.; Dateo, Christopher E.; Hamilton, I. P.; Arnold, James O. (Technical Monitor)

1994-01-01

We calculate vibrational levels and wave functions for HO2 using the recently reported ab initio potential energy surface of Walch and Duchovic. There is intramolecular hydrogen atom transfer when the hydrogen atom tunnels through a T-shaped saddle point separating two equivalent equilibrium geometries, and correspondingly, the energy levels are split. We focus on vibrational levels and wave functions with significant splitting. The first three vibrational levels with splitting greater than 2/cm are (15 0), (0 7 1) and (0 8 0) where V(sub 2) is the O-O-H bend quantum number. We discuss the dynamics of hydrogen atom transfer; in particular, the O-O distances at which hydrogen atom transfer is most probable for these vibrational levels. The material of the proposed presentation was reviewed and the technical content will not reveal any information not already in the public domain and will not give any foreign industry or government a competitive advantage.

Electronic Zero-Point Oscillations in the Strong-Interaction Limit of Density Functional Theory.

PubMed

Gori-Giorgi, Paola; Vignale, Giovanni; Seidl, Michael

2009-04-14

The exchange-correlation energy in Kohn-Sham density functional theory can be expressed exactly in terms of the change in the expectation of the electron-electron repulsion operator when, in the many-electron Hamiltonian, this same operator is multiplied by a real parameter λ varying between 0 (Kohn-Sham system) and 1 (physical system). In this process, usually called adiabatic connection, the one-electron density is kept fixed by a suitable local one-body potential. The strong-interaction limit of density functional theory, defined as the limit λ→∞, turns out to be like the opposite noninteracting Kohn-Sham limit (λ→0) mathematically simpler than the physical (λ = 1) case and can be used to build an approximate interpolation formula between λ→0 and λ→∞ for the exchange-correlation energy. Here we extend the systematic treatment of the λ→∞ limit [Phys. Rev. A 2007, 75, 042511] to the next leading term, describing zero-point oscillations of strictly correlated electrons, with numerical examples for small spherical atoms. We also propose an improved approximate functional for the zero-point term and a revised interpolation formula for the exchange-correlation energy satisfying more exact constraints.

Atomic motion from the mean square displacement in a monatomic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallace, Duane C.; De Lorenzi-Venneri, Giulia; Chisolm, Eric D.

V-T theory is constructed in the many-body Hamiltonian formulation, and is being developed as a novel approach to liquid dynamics theory. In this theory the liquid atomic motion consists of two contributions, normal mode vibrations in a single representative potential energy valley, and transits, which carry the system across boundaries between valleys. The mean square displacement time correlation function (the MSD) is a direct measure of the atomic motion, and our goal is to determine if the V-T formalism can produce a physically sensible account of this motion. We employ molecular dynamics (MD) data for a system representing liquid Na,more » and find the motion evolves in three successive time intervals: on the first 'vibrational' interval, the vibrational motion alone gives a highly accurate account of the MD data; on the second 'crossover' interval, the vibrational MSD saturates to a constant while the transit motion builds up from zero; on the third 'random walk' interval, the transit motion produces a purely diffusive random walk of the vibrational equilibrium positions. Furthermore, this motional evolution agrees with, and adds refinement to, the MSD atomic motion as described by current liquid dynamics theories.« less

Atomic motion from the mean square displacement in a monatomic liquid

DOE PAGES

Wallace, Duane C.; De Lorenzi-Venneri, Giulia; Chisolm, Eric D.

2016-04-08

V-T theory is constructed in the many-body Hamiltonian formulation, and is being developed as a novel approach to liquid dynamics theory. In this theory the liquid atomic motion consists of two contributions, normal mode vibrations in a single representative potential energy valley, and transits, which carry the system across boundaries between valleys. The mean square displacement time correlation function (the MSD) is a direct measure of the atomic motion, and our goal is to determine if the V-T formalism can produce a physically sensible account of this motion. We employ molecular dynamics (MD) data for a system representing liquid Na,more » and find the motion evolves in three successive time intervals: on the first 'vibrational' interval, the vibrational motion alone gives a highly accurate account of the MD data; on the second 'crossover' interval, the vibrational MSD saturates to a constant while the transit motion builds up from zero; on the third 'random walk' interval, the transit motion produces a purely diffusive random walk of the vibrational equilibrium positions. Furthermore, this motional evolution agrees with, and adds refinement to, the MSD atomic motion as described by current liquid dynamics theories.« less

Exploring mechanisms of a tropospheric archetype: CH{sub 3}O{sub 2} + NO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Launder, Andrew M.; Agarwal, Jay; Schaefer, Henry F., E-mail: ccq@uga.edu

Methylperoxy radical (CH{sub 3}O{sub 2}) and nitric oxide (NO) contribute to the propagation of photochemical smog in the troposphere via the production of methoxy radical (CH{sub 3}O) and nitrogen dioxide (NO{sub 2}). This reaction system also furnishes trace quantities of methyl nitrate (CH{sub 3}ONO{sub 2}), a sink for reactive NO{sub x} species. Here, the CH{sub 3}O{sub 2} + NO reaction is examined with highly reliable coupled-cluster methods. Specifically, equilibrium geometries for the reactants, products, intermediates, and transition states of the ground-state potential energy surface are characterized. Relative reaction enthalpies at 0 K (ΔH{sub 0K}) are reported; these values are comprisedmore » of electronic energies extrapolated to the complete basis set limit of CCSDT(Q) and zero-point vibrational energies computed at CCSD(T)/cc-pVTZ. A two-part mechanism involving CH{sub 3}O and NO{sub 2} production followed by radical recombination to CH{sub 3}ONO{sub 2} is determined to be the primary channel for formation of CH{sub 3}ONO{sub 2} under tropospheric conditions. Constrained optimizations of the reaction paths at CCSD(T)/cc-pVTZ suggest that the homolytic bond dissociations involved in this reaction path are barrierless.« less

Features extraction algorithm about typical railway perimeter intrusion event

NASA Astrophysics Data System (ADS)

Zhou, Jieyun; Wang, Chaodong; Liu, Lihai

2017-10-01

Research purposes: Optical fiber vibration sensing system has been widely used in the oil, gas, frontier defence, prison and power industries. But, there are few reports about the application in railway defence. That is because the surrounding environment is complicated and there are many challenges to be overcomed in the optical fiber vibration sensing system application. For example, how to eliminate the effects of vibration caused by train, the natural environments such as wind and rain and how to identify and classify the intrusion events. In order to solve these problems, the feature signals of these events should be extracted firstly. Research conclusions: (1) In optical fiber vibration sensing system based on Sagnac interferometer, the peak-to-peak value, peak-to-average ratio, standard deviation, zero-crossing rate, short-term energy and kurtosis may serve as feature signals. (2) The feature signals of resting state, climbing concrete fence, breaking barbed wire, knocking concrete fence and rainstorm have been extracted, which shows significant difference among each other. (3) The research conclusions can be used in the identification and classification of intrusion events.

Quasiparticle lifetime broadening in resonant x-ray scattering of NH4NO3

NASA Astrophysics Data System (ADS)

Vinson, John; Jach, Terrence; Müller, Matthias; Unterumsberger, Rainer; Beckhoff, Burkhard

2016-07-01

It has been previously shown that two effects cause dramatic changes in the x-ray absorption and emission spectra from the N K edge of the insulating crystal ammonium nitrate. First, vibrational disorder causes major changes in the absorption spectrum, originating not only from the thermal population of phonons, but, significantly, from zero-point motion as well. Second, the anomalously large broadening (˜4 eV) of the emission originating from nitrate σ states is due to the unusually short lifetimes of quasiparticles in an otherwise extremely narrow band. In this work, we investigate the coupling of these effects to core and valence excitons that are created as the initial x-ray excitation energy is progressively reduced toward the N edge. Using a G W /Bethe-Salpeter approach, we show the extent to which this anomalous broadening is captured by the G W approximation. The data and calculations demonstrate the importance that the complex self-energies (finite lifetimes) of the valence bands have on the interpretation of emission spectra. We produce a scheme to explain why extreme lifetimes should appear in σ states of other similar compounds.

Remarkable influence of slack on the vibration of a single-walled carbon nanotube resonator

NASA Astrophysics Data System (ADS)

Ning, Zhiyuan; Fu, Mengqi; Wu, Gongtao; Qiu, Chenguang; Shu, Jiapei; Guo, Yao; Wei, Xianlong; Gao, Song; Chen, Qing

2016-04-01

We for the first time quantitatively investigate experimentally the remarkable influence of slack on the vibration of a single-walled carbon nanotube (SWCNT) resonator with a changeable channel length fabricated in situ inside a scanning electron microscope, compare the experimental results with the theoretical predictions calculated from the measured geometric and mechanical parameters of the same SWCNT, and find the following novel points. We demonstrate experimentally that as the slack s is increased from about zero to 1.8%, the detected vibration transforms from single-mode to multimode vibration, and the gate-tuning ability gradually attenuates for all the vibration modes. The quadratic tuning coefficient α decreases linearly with when the gate voltage Vdcg is small and the nanotube resonator operates in the beam regime. The linear tuning coefficient γ decreases linearly with when Vdcg has an intermediate value and the nanotube resonator operates in the catenary regime. The calculated α and γ fit the experimental values of the even in-plane mode reasonably well. As the slack is increased, the quality factor Q of the resonator linearly goes up, but the increase is far less steep than that predicted by the previous theoretical study. Our results are important to understand and design resonators based on CNT and other nanomaterials.

Hybrid Light-Matter States in a Molecular and Material Science Perspective.

PubMed

Ebbesen, Thomas W

2016-11-15

The notion that light and matter states can be hybridized the way s and p orbitals are mixed is a concept that is not familiar to most chemists and material scientists. Yet it has much potential for molecular and material sciences that is just beginning to be explored. For instance, it has already been demonstrated that the rate and yield of chemical reactions can be modified and that the conductivity of organic semiconductors and nonradiative energy transfer can be enhanced through the hybridization of electronic transitions. The hybridization is not limited to electronic transitions; it can be applied for instance to vibrational transitions to selectively perturb a given bond, opening new possibilities to change the chemical reactivity landscape and to use it as a tool in (bio)molecular science and spectroscopy. Such results are not only the consequence of the new eigenstates and energies generated by the hybridization. The hybrid light-matter states also have unusual properties: they can be delocalized over a very large number of molecules (up to ca. 10 5 ), and they become dispersive or momentum-sensitive. Importantly, the hybridization occurs even in the absence of light because it is the zero-point energies of the molecular and optical transitions that generate the new light-matter states. The present work is not a review but rather an Account from the author's point of view that first introduces the reader to the underlying concepts and details of the features of hybrid light-matter states. It is shown that light-matter hybridization is quite easy to achieve: all that is needed is to place molecules or a material in a resonant optical cavity (e.g., between two parallel mirrors) under the right conditions. For vibrational strong coupling, microfluidic IR cells can be used to study the consequences for chemistry in the liquid phase. Examples of modified properties are given to demonstrate the full potential for the molecular and material sciences. Finally an outlook of future directions for this emerging subject is given.

Effective response theory for zero-energy Majorana bound states in three spatial dimensions

NASA Astrophysics Data System (ADS)

Lopes, Pedro L. e. S.; Teo, Jeffrey C. Y.; Ryu, Shinsei

2015-05-01

We propose a gravitational response theory for point defects (hedgehogs) binding Majorana zero modes in (3 + 1)-dimensional superconductors. Starting in 4 + 1 dimensions, where the point defect is extended into a line, a coupling of the bulk defect texture with the gravitational field is introduced. Diffeomorphism invariance then leads to an S U (2) 2 Kac-Moody current running along the defect line. The S U (2) 2 Kac-Moody algebra accounts for the non-Abelian nature of the zero modes in 3 + 1 dimensions. It is then shown to also encode the angular momentum density which permeates throughout the bulk between hedgehog-antihedgehog pairs.

Substitution structure of cyanogen, NCCN, from high-resolution far infrared spectra

NASA Astrophysics Data System (ADS)

Grecu, John C.; Winnewisser, Brenda P.; Winnewisser, Manfred

2003-04-01

The lowest lying vibrational bands of the gas-phase spectra of cyanogen, NCCN, and four of its isotopomers, 15NCCN, N13CCN, 15NCC15N, and N13C13CN, were recorded with a Fourier transform interferometer. The resolution was limited by the maximum optical path difference (MOPD) attainable with the interferometer to FWHM=0.0012 cm-1. Rovibrational transitions of the ν5 ( ≈230 cm-1) and also the ν2- ν5 ( ≈610 cm-1) band systems were assigned for all five isotopomers. The use of an effective Hamiltonian for linear molecules to fit the data yielded precise spectroscopic vibrational and rotational constants for the vibrational states ( v1v2v3v4v5) or ( v4v5)=(00), (01), (02), (03), and (01000). These data include the first rotationally resolved transitions involving (01000). Complete substitution ( rs) structures of cyanogen, based on both single and double isotopic substitution of the parent species, were calculated. The derived structure is rCC=138.48(17) pm and rCN=115.66(13) pm. The two rs structures coincide within the errors due to remaining contributions of zero-point vibrations.

Vibration characteristics of aluminum surface subjected to ultrasonic waves and their effect on wetting behavior of solder droplets.

PubMed

Ma, Lin; Xu, Zhiwu; Zheng, Kun; Yan, Jiuchun; Yang, Shiqin

2014-03-01

The vibration characteristics of an aluminum surface subjected to ultrasonic waves were investigated with a combination of numerical simulation and experimental testing. The wetting behavior of solder droplets on the vibrating aluminum surface was also examined. The results show that the vibration pattern of the aluminum surface is inhomogeneous. The amplitude of the aluminum surface exceeds the excitation amplitude in some zones, while the amplitude decreases nearly to zero in other zones. The distribution of the zero-amplitude zones is much less dependent on the strength of the vibration than on the location of the vibration source. The surface of the liquid solder vibrates at an ultrasonic frequency that is higher than the vibration source, and the amplitude of the liquid solder is almost twice that of the aluminum surface. The vibration of the surface of the base metal (liquid solder) correlates with the oxide film removal effect. Significant removal of the oxide film can be achieved within 2s when the amplitude of the aluminum surface is higher than 5.4 μm or when the amplitude of the liquid solder surface is higher than 10.2 μm. Copyright © 2013 Elsevier B.V. All rights reserved.

Above Saddle-Point Regions of Order in a Sea of Chaos in the Vibrational Dynamics of KCN.

PubMed

Párraga, H; Arranz, F J; Benito, R M; Borondo, F

2018-04-05

The dynamical characteristics of a region of regular vibrational motion in the sea of chaos above the saddle point corresponding to the linear C-N-K configuration is examined in detail. To explain the origin of this regularity, the associated phase space structures were characterized using suitably defined Poincaré surfaces of section, identifying the different resonances between the stretching and bending modes, as a function of excitation energy. The corresponding topology is elucidated by means of periodic orbit analysis.

Anisotropic lattice thermal expansion of PbFeBO 4: A study by X-ray and neutron diffraction, Raman spectroscopy and DFT calculations

DOE PAGES

Murshed, M. Mangir; Mendive, Cecilia B.; Curti, Mariano; ...

2014-11-01

We present the lattice thermal expansion of mullite-type PbFeBO 4 in this study. The thermal expansion coefficients of the metric parameters were obtained from composite data collected from temperature-dependent neutron and X-ray powder diffraction between 10 K and 700 K. The volume thermal expansion was modeled using extended Grüneisen first-order approximation to the zero-pressure equation of state. The additive frame of the model includes harmonic, quasi-harmonic and intrinsic anharmonic potentials to describe the change of the internal energy as a function of temperature. Moreover, the unit-cell volume at zero-pressure and 0 K was optimized during the DFT simulations. Harmonic frequenciesmore » of the optical Raman modes at the Γ-point of the Brillouin zone at 0 K were also calculated by DFT, which help to assign and crosscheck the experimental frequencies. The low-temperature Raman spectra showed significant anomaly in the antiferromagnetic regions, leading to softening or hardening of some phonons. Selected modes were analyzed using a modified Klemens model. The shift of the frequencies and the broadening of the line-widths helped to understand the anharmonic vibrational behaviors of the PbO4, FeO6 and BO3 polyhedra as a function of temperature.« less

Implications of the (H2O)n + CO ↔ trans-HCOOH + (H2O)n-1 (n = 1, 2, and 3) reactions for primordial atmospheres of Venus and Earth

NASA Astrophysics Data System (ADS)

Vichietti, R. M.; Spada, R. F. K.; da Silva, A. B. F.; Machado, F. B. C.; Haiduke, R. L. A.

2018-04-01

The forward and backward (H2O)n + CO ↔ HCOOH + (H2O)n-1 (n = 1, 2, and 3) reactions were studied in order to furnish trustworthy thermochemical and kinetic data. Stationary point structures involved in these chemical processes were achieved at the B2PLYP/cc-pVTZ level so that the corresponding vibrational frequencies, zero-point energies, and thermal corrections were scaled to consider anharmonicity effects. A complete basis set extrapolation was also employed with the CCSD(T) method in order to improve electronic energy descriptions and providing therefore more accurate results for enthalpies, Gibbs energies, and rate constants. Forward and backward rate constants were encountered at the high-pressure limit between 200 and 4000 K. In turn, modified Arrhenius' equations were fitted from these rate constants (between 700 and 4000 K). Next, considering physical and chemical conditions that have supposedly prevailed on primitive atmospheres of Venus and Earth, our main results indicate that 85-88 per cent of all water forms on these atmospheres were monomers, whereas (H2O)2 and (H2O)3 complexes would represent 12-15 and ˜0 per cent, respectively. Besides, we estimate that Earth's and Venus' primitive atmospheres could have been composed by ˜0.001-0.003 per cent of HCOOH when their temperatures were around 1000-2000 K. Finally, the water loss process on Venus may have occurred by a mechanism that includes the formic acid as intermediate species.

I + (H2O)2 → HI + (H2O)OH Forward and Reverse Reactions. CCSD(T) Studies Including Spin-Orbit Coupling.

PubMed

Wang, Hui; Li, Guoliang; Li, Qian-Shu; Xie, Yaoming; Schaefer, Henry F

2016-03-03

The potential energy profile for the atomic iodine plus water dimer reaction I + (H2O)2 → HI + (H2O)OH has been explored using the "Gold Standard" CCSD(T) method with quadruple-ζ correlation-consistent basis sets. The corresponding information for the reverse reaction HI + (H2O)OH → I + (H2O)2 is also derived. Both zero-point vibrational energies (ZPVEs) and spin-orbit (SO) coupling are considered, and these notably alter the classical energetics. On the basis of the CCSD(T)/cc-pVQZ-PP results, including ZPVE and SO coupling, the forward reaction is found to be endothermic by 47.4 kcal/mol, implying a significant exothermicity for the reverse reaction. The entrance complex I···(H2O)2 is bound by 1.8 kcal/mol, and this dissociation energy is significantly affected by SO coupling. The reaction barrier lies 45.1 kcal/mol higher than the reactants. The exit complex HI···(H2O)OH is bound by 3.0 kcal/mol relative to the asymptotic limit. At every level of theory, the reverse reaction HI + (H2O)OH → I + (H2O)2 proceeds without a barrier. Compared with the analogous water monomer reaction I + H2O → HI + OH, the additional water molecule reduces the relative energies of the entrance stationary point, transition state, and exit complex by 3-5 kcal/mol. The I + (H2O)2 reaction is related to the valence isoelectronic bromine and chlorine reactions but is distinctly different from the F + (H2O)2 system.

Phase stability of TiO 2 polymorphs from diffusion Quantum Monte Carlo

DOE PAGES

Luo, Ye; Benali, Anouar; Shulenburger, Luke; ...

2016-11-24

Titanium dioxide, TiO 2, has multiple applications in catalysis, energy conversion and memristive devices because of its electronic structure. Most of applications utilize the naturally existing phases: rutile, anatase and brookite. In spite of the simple form of TiO 2 and its wide uses, there is long- standing disagreement between theory and experiment on the energetic ordering of these phases that has never been resolved. We present the first analysis of phase stability at zero temperature using the highly accurate many-body fixed node diffusion Quantum Monte Carlo (QMC) method. We include temperature effects by calculating the Helmholtz free energy includingmore » both internal energy corrected by QMC and vibrational contributions from phonon calculations within the quasi harmonic approximation via density functional perturbation theory. Our QMC calculations find that anatase is the most stable phase at zero temperature, consistent with many previous mean- field calculations. Furthermore, at elevated temperatures, rutile becomes the most stable phase. For all finite temperatures, brookite is always the least stable phase.« less

On the widths of Stokes lines in Raman scattering from molecules adsorbed at metal surfaces and in molecular conduction junctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Yi, E-mail: yig057@ucsd.edu; Galperin, Michael, E-mail: migalperin@ucsd.edu; Nitzan, Abraham, E-mail: nitzan@post.tau.ac.il

Within a generic model we analyze the Stokes linewidth in surface enhanced Raman scattering (SERS) from molecules embedded as bridges in molecular junctions. We identify four main contributions to the off-resonant Stokes signal and show that under zero voltage bias (a situation pertaining also to standard SERS experiments) and at low bias junctions only one of these contributions is pronounced. The linewidth of this component is determined by the molecular vibrational relaxation rate, which is dominated by interactions with the essentially bosonic thermal environment when the relevant molecular electronic energy is far from the metal(s) Fermi energy(ies). It increases whenmore » the molecular electronic level is close to the metal Fermi level so that an additional vibrational relaxation channel due to electron-hole (eh) exciton in the molecule opens. Other contributions to the Raman signal, of considerably broader linewidths, can become important at larger junction bias.« less

Meshless Local Petrov-Galerkin Method for Solving Contact, Impact and Penetration Problems

DTIC Science & Technology

2006-11-30

Crack Growth 3 point of view, this approach makes the full use of the ex- isting FE models to avoid any model regeneration , which is extremely high in...process, at point C, the pressure reduces to zero, but the volumet- ric strain does not go to zero due to the collapsed void volume. 2.2 Damage...lease rate to go beyond the critical strain energy release rate. Thus, the micro-cracks begin to growth inside these areas. At 10 micro-seconds, these

Eckart frame vibration-rotation Hamiltonians: Contravariant metric tensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pesonen, Janne, E-mail: janne.pesonen@helsinki.fi

2014-02-21

Eckart frame is a unique embedding in the theory of molecular vibrations and rotations. It is defined by the condition that the Coriolis coupling of the reference structure of the molecule is zero for every choice of the shape coordinates. It is far from trivial to set up Eckart kinetic energy operators (KEOs), when the shape of the molecule is described by curvilinear coordinates. In order to obtain the KEO, one needs to set up the corresponding contravariant metric tensor. Here, I derive explicitly the Eckart frame rotational measuring vectors. Their inner products with themselves give the rotational elements, andmore » their inner products with the vibrational measuring vectors (which, in the absence of constraints, are the mass-weighted gradients of the shape coordinates) give the Coriolis elements of the contravariant metric tensor. The vibrational elements are given as the inner products of the vibrational measuring vectors with themselves, and these elements do not depend on the choice of the body-frame. The present approach has the advantage that it does not depend on any particular choice of the shape coordinates, but it can be used in conjunction with all shape coordinates. Furthermore, it does not involve evaluation of covariant metric tensors, chain rules of derivation, or numerical differentiation, and it can be easily modified if there are constraints on the shape of the molecule. Both the planar and non-planar reference structures are accounted for. The present method is particular suitable for numerical work. Its computational implementation is outlined in an example, where I discuss how to evaluate vibration-rotation energies and eigenfunctions of a general N-atomic molecule, the shape of which is described by a set of local polyspherical coordinates.« less

First principles investigation of structural, vibrational and thermal properties of black and blue phosphorene

NASA Astrophysics Data System (ADS)

Arif Khalil, R. M.; Ahmad, Javed; Rana, Anwar Manzoor; Bukhari, Syed Hamad; Tufiq Jamil, M.; Tehreem, Tuba; Nissar, Umair

2018-05-01

In this investigation, structural, dynamical and thermal properties of black and blue phosphorene (P) are presented through the first principles calculations based on the density functional theory (DFT). These DFT calculations depict that due to the approximately same values of ground state energy at zero Kelvin and Helmholtz free energy at room-temperature, it is expected that both structures can coexist at transition temperature. Lattice dynamics of both phases were investigated by using the finite displacement supercell approach. It is noticed on the basis of harmonic approximation thermodynamic calculations that the blue phase is thermodynamically more stable than the black phase above 155 K.

Reducing injection loss in drill strings

DOEpatents

Drumheller, Douglas S.

2004-09-14

A system and method for transferring wave energy into or out of a periodic structure having a characteristic wave impedance profile at a prime frequency, the characteristic wave impedance profile comprising a real portion and an imaginary portion, comprising: locating one or more energy transfer elements each having a wave impedance at the prime frequency approximately equal to the real portion of the characteristic wave impedance at one or more points on the periodic structure with the imaginary portion approximately equaling zero; and employing the one or more energy transfer elements to transfer wave energy into or out of the periodic structure. The energy transfer may be repeaters. Quarter-wave transformers can be provided at one or more points on the periodic structure with the imaginary portion approximately equaling zero to transmit waves across one or more discontinuities. A terminator can be employed for cancellation of waves. The invention substantially eliminates reflections of the wave energy at the prime frequency by joints between sections of the periodic structure.

Epistemic uncertainty propagation in energy flows between structural vibrating systems

NASA Astrophysics Data System (ADS)

Xu, Menghui; Du, Xiaoping; Qiu, Zhiping; Wang, Chong

2016-03-01

A dimension-wise method for predicting fuzzy energy flows between structural vibrating systems coupled by joints with epistemic uncertainties is established. Based on its Legendre polynomial approximation at α=0, both the minimum and maximum point vectors of the energy flow of interest are calculated dimension by dimension within the space spanned by the interval parameters determined by fuzzy those at α=0 and the resulted interval bounds are used to assemble the concerned fuzzy energy flows. Besides the proposed method, vertex method as well as two current methods is also applied. Comparisons among results by different methods are accomplished by two numerical examples and the accuracy of all methods is simultaneously verified by Monte Carlo simulation.

Zero-point energy conservation in classical trajectory simulations: Application to H2CO

NASA Astrophysics Data System (ADS)

Lee, Kin Long Kelvin; Quinn, Mitchell S.; Kolmann, Stephen J.; Kable, Scott H.; Jordan, Meredith J. T.

2018-05-01

A new approach for preventing zero-point energy (ZPE) violation in quasi-classical trajectory (QCT) simulations is presented and applied to H2CO "roaming" reactions. Zero-point energy may be problematic in roaming reactions because they occur at or near bond dissociation thresholds and these channels may be incorrectly open or closed depending on if, or how, ZPE has been treated. Here we run QCT simulations on a "ZPE-corrected" potential energy surface defined as the sum of the molecular potential energy surface (PES) and the global harmonic ZPE surface. Five different harmonic ZPE estimates are examined with four, on average, giving values within 4 kJ/mol—chemical accuracy—for H2CO. The local harmonic ZPE, at arbitrary molecular configurations, is subsequently defined in terms of "projected" Cartesian coordinates and a global ZPE "surface" is constructed using Shepard interpolation. This, combined with a second-order modified Shepard interpolated PES, V, allows us to construct a proof-of-concept ZPE-corrected PES for H2CO, Veff, at no additional computational cost to the PES itself. Both V and Veff are used to model product state distributions from the H + HCO → H2 + CO abstraction reaction, which are shown to reproduce the literature roaming product state distributions. Our ZPE-corrected PES allows all trajectories to be analysed, whereas, in previous simulations, a significant proportion was discarded because of ZPE violation. We find ZPE has little effect on product rotational distributions, validating previous QCT simulations. Running trajectories on V, however, shifts the product kinetic energy release to higher energy than on Veff and classical simulations of kinetic energy release should therefore be viewed with caution.

Transmission of Helium Isotopes through Graphdiyne Pores: Tunneling versus Zero Point Energy Effects.

PubMed

Hernández, Marta I; Bartolomei, Massimiliano; Campos-Martínez, José

2015-10-29

Recent progress in the production of new two-dimensional (2D) nanoporous materials is attracting considerable interest for applications to isotope separation in gases. In this paper we report a computational study of the transmission of (4)He and (3)He through the (subnanometer) pores of graphdiyne, a recently synthesized 2D carbon material. The He-graphdiyne interaction is represented by a force field parametrized upon ab initio calculations, and the (4)He/(3)He selectivity is analyzed by tunneling-corrected transition state theory. We have found that both zero point energy (of the in-pore degrees of freedom) and tunneling effects play an extraordinary role at low temperatures (≈20-30 K). However, both quantum features work in opposite directions in such a way that the selectivity ratio does not reach an acceptable value. Nevertheless, the efficiency of zero point energy is in general larger, so that (4)He tends to diffuse faster than (3)He through the graphdiyne membrane, with a maximum performance at 23 K. Moreover, it is found that the transmission rates are too small in the studied temperature range, precluding practical applications. It is concluded that the role of the in-pore degrees of freedom should be included in computations of the transmission probabilities of molecules through nanoporous materials.

Quantum chemical characterization of the X((1)A'), a((3)A'') and A((1)A'') states of CHBr and CHI and computed heats of formation for CHI and CI.

PubMed

Bacskay, George B

2010-08-26

The relative energies of the X, a, and A states of CHBr and CHI and their atomization and dissociation energies in the complete basis limit were determined by extrapolating (R/U)CCSD(T) and Davidson corrected MRCI energies calculated with the aug-cc-pVxZ (x = T,Q,5) basis sets, which were corrected for core-valence correlation, spin-orbit coupling, and zero point energies. The all-electron calculations on the bromine containing molecules were explicitly corrected for scalar relativity, while in the iodo systems they are implicit in the ECP28MDF pseudopotential of iodine. The geometries and vibrational frequencies were calculated at the CASPT2/cc-pVTZ level of theory. The computed singlet-triplet splittings (5.7 and 3.7 kcal mol(-1) for CHBr and CHI respectively) are in close agreement with the recent experimental values, while the predicted A <-- X excitation energies are within approximately 1 kcal mol(-1) of experiment. The barriers to linearity and dissociation on the A surface were also characterized. For CHI and CI, the predicted heats of formation at 298 K are 134.5 +/- 1.0 and 103.9 +/- 1.0 kcal mol(-1), respectively. The spin-orbit splitting in iodomethylidyne (CI) is computed to be 746 cm(-1), although that value may be an underestimate by approximately 20%.

A Gaussian Wave Packet Propagation Approach to Vibrationally Resolved Optical Spectra at Non-Zero Temperatures.

PubMed

Reddy, Ch Sridhar; Prasad, M Durga

2016-04-28

An effective time dependent approach based on a method that is similar to the Gaussian wave packet propagation (GWP) technique of Heller is developed for the computation of vibrationally resolved electronic spectra at finite temperatures in the harmonic, Franck-Condon/Hertzberg-Teller approximations. Since the vibrational thermal density matrix of the ground electronic surface and the time evolution operator on that surface commute, it is possible to write the spectrum generating correlation function as a trace of the time evolved doorway state. In the stated approximations, the doorway state is a superposition of the harmonic oscillator zero and one quantum eigenfunctions and thus can be propagated by the GWP. The algorithm has an O(N(3)) dependence on the number of vibrational modes. An application to pyrene absorption spectrum at two temperatures is presented as a proof of the concept.

Deuterium kinetic isotope effects on the dissociation of a protein-fatty acid complex in the gas phase.

PubMed

Liu, Lan; Michelsen, Klaus; Kitova, Elena N; Schnier, Paul D; Brown, Alex; Klassen, John S

2012-04-04

Deuterium kinetic isotope effects (KIEs) are reported for the first time for the dissociation of a protein-ligand complex in the gas phase. Temperature-dependent rate constants were measured for the loss of neutral ligand from the deprotonated ions of the 1:1 complex of bovine β-lactoglobulin (Lg) and palmitic acid (PA), (Lg + PA)(n-) → Lg(n-) + PA, at the 6- and 7- charge states. At 25 °C, partial or complete deuteration of the acyl chain of PA results in a measurable inverse KIE for both charge states. The magnitude of the KIEs is temperature dependent, and Arrhenius analysis of the rate constants reveals that deuteration of PA results in a decrease in activation energy. In contrast, there is no measurable deuterium KIE for the dissociation of the (Lg + PA) complex in aqueous solution at pH 8. Deuterium KIEs were calculated using conventional transition-state theory with an assumption of a late dissociative transition state (TS), in which the ligand is free of the binding pocket. The vibrational frequencies of deuterated and non-deuterated PA in the gas phase and in various solvents (n-hexane, 1-chlorohexane, acetone, and water) were established computationally. The KIEs calculated from the corresponding differences in zero-point energies account qualitatively for the observation of an inverse KIE but do not account for the magnitude of the KIEs nor their temperature dependence. It is proposed that the dissociation of the (Lg + PA) complex in aqueous solution also proceeds through a late TS in which the acyl chain is extensively hydrated such that there is no significant differential change in the vibrational frequencies along the reaction coordinate and, consequently, no significant KIE.

Zero point energy of polyhedral water clusters.

PubMed

Anick, David J

2005-06-30

Polyhedral water clusters (PWCs) are cage-like (H2O)n clusters where every O participates in exactly three H bonds. For a database of 83 PWCs, 8 < or = n < or = 20, geometry was optimized and zero point energy (ZPE) was calculated at the B3LYP/6-311++G** level. ZPE correlates negatively with electronic energy (E0): each increase of 1 kcal/mol in E0 corresponds to a decrease of about 0.11 kcal/mol in ZPE. For each n, a set of four connectivity parameters accounts for 98% or more of the variance in ZPE. Linear regression of ZPE against n and this set gives an RMS error of 0.13 kcal/mol. The contributions to ZPE from stretch modes only (ZPE(S)) and from torsional modes only (ZPE(T)) also correlate strongly with E0 and with each other.

Molecular symmetry group analysis of the low-wavenumber torsions and vibration-torsions in the S1 state and ground state cation of p-xylene: An investigation using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William D.; Groner, Peter; Wright, Timothy G.

2017-03-01

For the first time, a molecular symmetry group (MSG) analysis has been undertaken in the investigation of the electronic spectroscopy of p-xylene (p-dimethylbenzene). Torsional and vibration-torsional (vibtor) levels in the S1 state and ground state of the cation of p-xylene are investigated using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy. In the present work, we concentrate on the 0-350 cm-1 region, where there are a number of torsional and vibtor bands and we discuss the assignment of this region. In Paper II [W. D. Tuttle et al., J. Chem. Phys. 146, 124309 (2017)], we examine the 350-600 cm-1 region where vibtor levels are observed as part of a Fermi resonance. The similarity of much of the observed spectral activity to that in the related substituted benzenes, toluene and para-fluorotoluene, is striking, despite the different symmetries. The discussion necessitates a consideration of the MSG of p-xylene, which has been designated G72, but we shall also designate [{3,3}]D2h and we include the symmetry operations, character table, and direct product table for this. We also discuss the symmetries of the internal rotor (torsional) levels and the selection rules for the particular electronic transition of p-xylene investigated here.

Design and vibration control of vehicle engine mount activated by MR fluid and piezoelectric actuator

NASA Astrophysics Data System (ADS)

Lee, D. Y.; Park, Y. K.; Choi, S. B.; Lee, H. G.

2009-07-01

An engine is one of the most dominant noise and vibration sources in vehicle systems. Therefore, in order to resolve noise and vibration problems due to engine, various types of engine mounts have been proposed. This work presents a new type of active engine mount system featuring a magneto-rheological (MR) fluid and a piezostack actuator. As a first step, six degrees-of freedom dynamic model of an in-line four-cylinder engine which has three points mounting system is derived by considering the dynamic behaviors of MR mount and piezostack mount. In the configuration of engine mount system, two MR mounts are installed for vibration control of roll mode motion whose energy is very high in low frequency range, while one piezostack mount is installed for vibration control of bounce and pitch mode motion whose energy is relatively high in high frequency range. As a second step, linear quadratic regulator (LQR) controller is synthesized to actively control the imposed vibration. In order to demonstrate the effectiveness of the proposed active engine mount, vibration control performances are evaluated under various engine operating speeds (wide frequency range).

Coupling strength assumption in statistical energy analysis

PubMed Central

Lafont, T.; Totaro, N.

2017-01-01

This paper is a discussion of the hypothesis of weak coupling in statistical energy analysis (SEA). The examples of coupled oscillators and statistical ensembles of coupled plates excited by broadband random forces are discussed. In each case, a reference calculation is compared with the SEA calculation. First, it is shown that the main SEA relation, the coupling power proportionality, is always valid for two oscillators irrespective of the coupling strength. But the case of three subsystems, consisting of oscillators or ensembles of plates, indicates that the coupling power proportionality fails when the coupling is strong. Strong coupling leads to non-zero indirect coupling loss factors and, sometimes, even to a reversal of the energy flow direction from low to high vibrational temperature. PMID:28484335

Nonlinear modal resonances in low-gravity slosh-spacecraft systems

NASA Technical Reports Server (NTRS)

Peterson, Lee D.

1991-01-01

Nonlinear models of low gravity slosh, when coupled to spacecraft vibrations, predict intense nonlinear eigenfrequency shifts at zero gravity. These nonlinear frequency shifts are due to internal quadratic and cubic resonances between fluid slosh modes and spacecraft vibration modes. Their existence has been verified experimentally, and they cannot be correctly modeled by approximate, uncoupled nonlinear models, such as pendulum mechanical analogs. These predictions mean that linear slosh assumptions for spacecraft vibration models can be invalid, and may lead to degraded control system stability and performance. However, a complete nonlinear modal analysis will predict the correct dynamic behavior. This paper presents the analytical basis for these results, and discusses the effect of internal resonances on the nonlinear coupled response at zero gravity.

Remarkable influence of slack on the vibration of a single-walled carbon nanotube resonator.

PubMed

Ning, Zhiyuan; Fu, Mengqi; Wu, Gongtao; Qiu, Chenguang; Shu, Jiapei; Guo, Yao; Wei, Xianlong; Gao, Song; Chen, Qing

2016-04-28

We for the first time quantitatively investigate experimentally the remarkable influence of slack on the vibration of a single-walled carbon nanotube (SWCNT) resonator with a changeable channel length fabricated in situ inside a scanning electron microscope, compare the experimental results with the theoretical predictions calculated from the measured geometric and mechanical parameters of the same SWCNT, and find the following novel points. We demonstrate experimentally that as the slack s is increased from about zero to 1.8%, the detected vibration transforms from single-mode to multimode vibration, and the gate-tuning ability gradually attenuates for all the vibration modes. The quadratic tuning coefficient α decreases linearly with 1/√s when the gate voltage V(g)dc is small and the nanotube resonator operates in the beam regime. The linear tuning coefficient γ decreases linearly with 1/ (4√S) when V(g)dc has an intermediate value and the nanotube resonator operates in the catenary regime. The calculated α and γ fit the experimental values of the even in-plane mode reasonably well. As the slack is increased, the quality factor Q of the resonator linearly goes up, but the increase is far less steep than that predicted by the previous theoretical study. Our results are important to understand and design resonators based on CNT and other nanomaterials.

Ab initio molecular orbital calculations on the associated complexes of lithium cyanide with ammonia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohandas, P.; Shivaglal, M.C.; Chandrasekhar, J.

Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets are carried out on a series of complexes of NH{sub 3} with Li{sup +}, C{triple_bond}N{sup -}, LiCN, and its isomer LiNC. The BSSE-corrected interaction energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies are evaluated for 15 species. Complexes with trifurcated (C{sub 3v}) structures are calculated to be saddle points on the potential energy surfaces and have one imaginary frequency each. Calculated energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies of the various species considered are discussed in terms of the nature of associationmore » of LiCN with ammonia. The vibrational frequencies of the relevant complexed species are compared with the experimental frequencies reported earlier for solutions of lithium cyanide in liquid ammonia. 40 refs., 1 fig., 4 tabs.« less

A neural network potential energy surface for the NaH2 system and dynamics studies on the H(2S) + NaH(X1Σ+) → Na(2S) + H2(X1Σg+) reaction.

PubMed

Wang, Shufen; Yuan, Jiuchuang; Li, Huixing; Chen, Maodu

2017-08-02

In order to study the dynamics of the reaction H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), a new potential energy surface (PES) for the ground state of the NaH 2 system is constructed based on 35 730 ab initio energy points. Using basis sets of quadruple zeta quality, multireference configuration interaction calculations with Davidson correction were carried out to obtain the ab initio energy points. The neural network method is used to fit the PES, and the root mean square error is very small (0.00639 eV). The bond lengths, dissociation energies, zero-point energies and spectroscopic constants of H 2 (X 1 Σ g + ) and NaH(X 1 Σ + ) obtained on the new NaH 2 PES are in good agreement with the experiment data. On the new PES, the reactant coordinate-based time-dependent wave packet method is applied to study the reaction dynamics of H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), and the reaction probabilities, integral cross-sections (ICSs) and differential cross-sections (DCSs) are obtained. There is no threshold in the reaction due to the absence of an energy barrier on the minimum energy path. When the collision energy increases, the ICSs decrease from a high value at low collision energy. The DCS results show that the angular distribution of the product molecules tends to the forward direction. Compared with the LiH 2 system, the NaH 2 system has a larger mass and the PES has a larger well at the H-NaH configuration, which leads to a higher ICS value in the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction. Because the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction releases more energy, the product molecules can be excited to a higher vibrational state.

Simulation of adsorbed hydrogen on tungsten surface

NASA Astrophysics Data System (ADS)

Degtyarenko, N. N.; Pisarev, A. A.

2017-12-01

Calculations of the energy of the H-W system were performed using DFT method based on plane waves. Adsorption energies, equilibrium states, vibration spectra, saddle points, activation energies of jumps, and diffusion paths have been analyzed for H atom on W(100) and W(110). Diffusion coefficient for H on W(110) agrees very well with experimental data.

Improvement of force factor of magnetostrictive vibration power generator for high efficiency

NASA Astrophysics Data System (ADS)

Kita, Shota; Ueno, Toshiyuki; Yamada, Sotoshi

2015-05-01

We develop high power magnetostrictive vibration power generator for battery-free wireless electronics. The generator is based on a cantilever of parallel beam structure consisting of coil-wound Galfenol and stainless plates with permanent magnet for bias. Oscillating force exerted on the tip bends the cantilever in vibration yields stress variation of Galfenol plate, which causes flux variation and generates voltage on coil due to the law of induction. This generator has advantages over conventional, such as piezoelectric or moving magnet types, in the point of high efficiency, highly robust, and low electrical impedance. Our concern is the improvement of energy conversion efficiency dependent on the dimension. Especially, force factor, the conversion ratio of the electromotive force (voltage) on the tip velocity in vibration, has an important role in energy conversion process. First, the theoretical value of the force factor is formulated and then the validity was verified by experiments, where we compare four types of prototype with parameters of the dimension using 7.0 × 1.5 × 50 mm beams of Galfenol with 1606-turn wound coil. In addition, the energy conversion efficiency of the prototypes depending on load resistance was measured. The most efficient prototype exhibits the maximum instantaneous power of 0.73 W and energy of 4.7 mJ at a free vibration of frequency of 202 Hz in the case of applied force is 25 N. Further, it was found that energy conversion efficiency depends not only on the force factor but also on the damping (mechanical loss) of the vibration.

Lattice model calculation of elastic and thermodynamic properties at high pressure and temperature. [for alkali halides in NaCl lattice

NASA Technical Reports Server (NTRS)

Demarest, H. H., Jr.

1972-01-01

The elastic constants and the entire frequency spectrum were calculated up to high pressure for the alkali halides in the NaCl lattice, based on an assumed functional form of the inter-atomic potential. The quasiharmonic approximation is used to calculate the vibrational contribution to the pressure and the elastic constants at arbitrary temperature. By explicitly accounting for the effect of thermal and zero point motion, the adjustable parameters in the potential are determined to a high degree of accuracy from the elastic constants and their pressure derivatives measured at zero pressure. The calculated Gruneisen parameter, the elastic constants and their pressure derivatives are in good agreement with experimental results up to about 600 K. The model predicts that for some alkali halides the Grunesen parameter may decrease monotonically with pressure, while for others it may increase with pressure, after an initial decrease.

A maximally particle-hole asymmetric spectrum emanating from a semi-Dirac point.

PubMed

Quan, Yundi; Pickett, Warren E

2018-02-21

Tight binding models have proven an effective means of revealing Dirac (massless) dispersion, flat bands (infinite mass), and intermediate cases such as the semi-Dirac (sD) dispersion. This approach is extended to a three band model that yields, with chosen parameters in a two-band limit, a closed line with maximally asymmetric particle-hole dispersion: infinite mass holes, zero mass particles. The model retains the sD points for a general set of parameters. Adjacent to this limiting case, hole Fermi surfaces are tiny and needle-like. A pair of large electron Fermi surfaces at low doping merge and collapse at half filling to a flat (zero energy) closed contour with infinite mass along the contour and enclosing no carriers on either side, while the hole Fermi surface has shrunk to a point at zero energy, also containing no carriers. The tight binding model is used to study several characteristics of the dispersion and density of states. The model inspired generalization of sD dispersion to a general  ±[Formula: see text] form, for which analysis reveals that both n and m must be odd to provide a diabolical point with topological character. Evolution of the Hofstadter spectrum of this three band system with interband coupling strength is presented and discussed.

A maximally particle-hole asymmetric spectrum emanating from a semi-Dirac point

NASA Astrophysics Data System (ADS)

Quan, Yundi; Pickett, Warren E.

2018-02-01

Tight binding models have proven an effective means of revealing Dirac (massless) dispersion, flat bands (infinite mass), and intermediate cases such as the semi-Dirac (sD) dispersion. This approach is extended to a three band model that yields, with chosen parameters in a two-band limit, a closed line with maximally asymmetric particle-hole dispersion: infinite mass holes, zero mass particles. The model retains the sD points for a general set of parameters. Adjacent to this limiting case, hole Fermi surfaces are tiny and needle-like. A pair of large electron Fermi surfaces at low doping merge and collapse at half filling to a flat (zero energy) closed contour with infinite mass along the contour and enclosing no carriers on either side, while the hole Fermi surface has shrunk to a point at zero energy, also containing no carriers. The tight binding model is used to study several characteristics of the dispersion and density of states. The model inspired generalization of sD dispersion to a general  ± \\sqrt{k_x2n +k_y2m} form, for which analysis reveals that both n and m must be odd to provide a diabolical point with topological character. Evolution of the Hofstadter spectrum of this three band system with interband coupling strength is presented and discussed.

Quantum chemical modeling of zeolite-catalyzed methylation reactions: toward chemical accuracy for barriers.

PubMed

Svelle, Stian; Tuma, Christian; Rozanska, Xavier; Kerber, Torsten; Sauer, Joachim

2009-01-21

The methylation of ethene, propene, and t-2-butene by methanol over the acidic microporous H-ZSM-5 catalyst has been investigated by a range of computational methods. Density functional theory (DFT) with periodic boundary conditions (PBE functional) fails to describe the experimentally determined decrease of apparent energy barriers with the alkene size due to inadequate description of dispersion forces. Adding a damped dispersion term expressed as a parametrized sum over atom pair C(6) contributions leads to uniformly underestimated barriers due to self-interaction errors. A hybrid MP2:DFT scheme is presented that combines MP2 energy calculations on a series of cluster models of increasing size with periodic DFT calculations, which allows extrapolation to the periodic MP2 limit. Additionally, errors caused by the use of finite basis sets, contributions of higher order correlation effects, zero-point vibrational energy, and thermal contributions to the enthalpy were evaluated and added to the "periodic" MP2 estimate. This multistep approach leads to enthalpy barriers at 623 K of 104, 77, and 48 kJ/mol for ethene, propene, and t-2-butene, respectively, which deviate from the experimentally measured values by 0, +13, and +8 kJ/mol. Hence, enthalpy barriers can be calculated with near chemical accuracy, which constitutes significant progress in the quantum chemical modeling of reactions in heterogeneous catalysis in general and microporous zeolites in particular.

Picosecond excite-and-probe absorption measurement of the intra-2E(g)E(3/2)-state vibrational relaxation time in Ti(3+):Al2O3

NASA Technical Reports Server (NTRS)

Gayen, S. K.; Wang, W. B.; Petricevic, V.; Yoo, K. M.; Alfano, R. R.

1987-01-01

The Ti(3+)-doped Al2O3 has been recently demonstrated to be a tunable solid-state laser system with Ti(3+) as the laser-active ion. In this paper, the kinetics of vibrational transitions in the 2E(g)E(3/2) electronic state of Ti(3+):Al2O3a (crucial for characterizing new host materials for the Ti ion) was investigated. A 527-nm 5-ps pulse was used to excite a band of higher vibrational levels of the 2E(g)E(3/2) state, and the subsequent growth of population in the zero vibrational level and lower vibrational levels was monitored by a 3.9-micron picosecond probe pulse. The time evolution curve in the excited 2E(g)E(3/2) state at room temperature was found to be characterized by a sharp rise followed by a long decay, the long lifetime decay reflecting the depopulation of the zero and the lower vibrational levels of the 2E(g)E(3/2) state via radiative transitions. An upper limit of 3.5 ps was estimated for intra-2E(g)E(3/2)-state vibrational relaxation time.

Tight-binding modeling and low-energy behavior of the semi-Dirac point.

PubMed

Banerjee, S; Singh, R R P; Pardo, V; Pickett, W E

2009-07-03

We develop a tight-binding model description of semi-Dirac electronic spectra, with highly anisotropic dispersion around point Fermi surfaces, recently discovered in electronic structure calculations of VO2-TiO2 nanoheterostructures. We contrast their spectral properties with the well-known Dirac points on the honeycomb lattice relevant to graphene layers and the spectra of bands touching each other in zero-gap semiconductors. We also consider the lowest order dispersion around one of the semi-Dirac points and calculate the resulting electronic energy levels in an external magnetic field. In spite of apparently similar electronic structures, Dirac and semi-Dirac systems support diverse low-energy physics.

Features of the Percolation Scheme of Vibrational Spectrum Reconstruction in the Ga1 - x Al x P Alloy

NASA Astrophysics Data System (ADS)

Kozyrev, S. P.

2018-04-01

Specific features of the properties of Ga-P lattice vibrations have been investigated using the percolation model of a mixed Ga1 - x Al x P crystal (alloy) with zero lattice mismatch between binary components of the alloy. In contrast to other two-mode alloy systems, in Ga1 - x Al x P a percolation splitting of δ 13 cm-1 is observed for the low-frequency mode of GaP-like vibrations. An additional GaP mode (one of the percolation doublet components) split from the fundamental mode is observed for the GaP-rich alloy, which coincides in frequency with the gap corresponding to the zero density of one-phonon states of the GaP crystal. The vibrational spectrum of impurity Al in the GaP crystal has been calculated using the theory of crystal lattice dynamics. Upon substitution of lighter Al for the Ga atom, the calculated spectrum includes, along with the local mode, a singularity near the gap with the zero density of phonon states of the GaP crystal, which coincides with the mode observed experimentally at a frequency of 378 cm-1 in the Ga1 - x Al x P ( x < 0.4) alloy.

Computational simulations of vocal fold vibration: Bernoulli versus Navier-Stokes.

PubMed

Decker, Gifford Z; Thomson, Scott L

2007-05-01

The use of the mechanical energy (ME) equation for fluid flow, an extension of the Bernoulli equation, to predict the aerodynamic loading on a two-dimensional finite element vocal fold model is examined. Three steady, one-dimensional ME flow models, incorporating different methods of flow separation point prediction, were compared. For two models, determination of the flow separation point was based on fixed ratios of the glottal area at separation to the minimum glottal area; for the third model, the separation point determination was based on fluid mechanics boundary layer theory. Results of flow rate, separation point, and intraglottal pressure distribution were compared with those of an unsteady, two-dimensional, finite element Navier-Stokes model. Cases were considered with a rigid glottal profile as well as with a vibrating vocal fold. For small glottal widths, the three ME flow models yielded good predictions of flow rate and intraglottal pressure distribution, but poor predictions of separation location. For larger orifice widths, the ME models were poor predictors of flow rate and intraglottal pressure, but they satisfactorily predicted separation location. For the vibrating vocal fold case, all models resulted in similar predictions of mean intraglottal pressure, maximum orifice area, and vibration frequency, but vastly different predictions of separation location and maximum flow rate.

Computing Wigner distributions and time correlation functions using the quantum thermal bath method: application to proton transfer spectroscopy.

PubMed

Basire, Marie; Borgis, Daniel; Vuilleumier, Rodolphe

2013-08-14

Langevin dynamics coupled to a quantum thermal bath (QTB) allows for the inclusion of vibrational quantum effects in molecular dynamics simulations at virtually no additional computer cost. We investigate here the ability of the QTB method to reproduce the quantum Wigner distribution of a variety of model potentials, designed to assess the performances and limits of the method. We further compute the infrared spectrum of a multidimensional model of proton transfer in the gas phase and in solution, using classical trajectories sampled initially from the Wigner distribution. It is shown that for this type of system involving large anharmonicities and strong nonlinear coupling to the environment, the quantum thermal bath is able to sample the Wigner distribution satisfactorily and to account for both zero point energy and tunneling effects. It leads to quantum time correlation functions having the correct short-time behavior, and the correct associated spectral frequencies, but that are slightly too overdamped. This is attributed to the classical propagation approximation rather than the generation of the quantized initial conditions themselves.

Eddy Current Analysis and Optimization for Superconducting Magnetic Bearing of Flywheel Energy Storage System

NASA Astrophysics Data System (ADS)

Arai, Yuuki; Yamashita, Tomohisa; Hasegawa, Hitoshi; Matsuoka, Taro; Kaimori, Hiroyuki; Ishihara, Terumasa

Levitation and guidance force is electromagnetic generated between a superconducting coil and zero field cooled bulk superconductors used in our flywheel energy storage system (FESS). Because the magnetic field depends on the configuration of the coil and the bulks, the eccentricity and the vibration of a rotor cause fluctuation in the magnetic field which induces eddy current and consequent Joule heat on electric conductors such as cooling plates. Heat generation in the cryogenic region critically reduces the efficiency of the FESS. In this paper, we will report the result of the electromagnetic analysis of the SMB and propose an optimal divided cooling plate for reducing the eddy current and Joule heat.

Influence of Fröhlich polaron coupling on renormalized electron bands in polar semiconductors: Results for zinc-blende GaN

NASA Astrophysics Data System (ADS)

Nery, Jean Paul; Allen, Philip B.

2016-09-01

We develop a simple method to study the zero-point and thermally renormalized electron energy ɛk n(T ) for k n the conduction band minimum or valence maximum in polar semiconductors. We use the adiabatic approximation, including an imaginary broadening parameter i δ to suppress noise in the density-functional integrations. The finite δ also eliminates the polar divergence which is an artifact of the adiabatic approximation. Nonadiabatic Fröhlich polaron methods then provide analytic expressions for the missing part of the contribution of the problematic optical phonon mode. We use this to correct the renormalization obtained from the adiabatic approximation. Test calculations are done for zinc-blende GaN for an 18 ×18 ×18 integration grid. The Fröhlich correction is of order -0.02 eV for the zero-point energy shift of the conduction band minimum, and +0.03 eV for the valence band maximum; the correction to renormalization of the 3.28 eV gap is -0.05 eV, a significant fraction of the total zero point renormalization of -0.15 eV.

Tsallis entropy and decoherence of CsI quantum pseudo dot qubit

NASA Astrophysics Data System (ADS)

Tiotsop, M.; Fotue, A. J.; Fotsin, H. B.; Fai, L. C.

2017-05-01

Polaron in CsI quantum pseudo dot under an electromagnetic field was considered, and the ground and first excited state energies were derived by employing the combining Pekar variational and unitary transformation methods. With the two-level system obtained, single qubit was envisioned and the decoherence was studied using non-extensive entropy (Tsallis entropy). Numerical results showed: (i) the increase (decrease) of the energy levels (period of oscillation) with the increase of chemical potential, the zero point of pseudo dot, cyclotron frequency, and transverse and longitudinal confinements; (ii) the Tsallis entropy evolved as a wave envelop that increase with the increase of non-extenxive parameter and with the increase of electric field strength, zero point of pseudo dot and cyclotron frequency the wave envelop evolve periodically with reduction of period; (iii) The transition probability increases from the boundary to the centre of the dot where it has its maximum value. It was also noted that the probability density oscillate with period T0 = ℏ / Δ Ε with the tunnelling of the chemical potential and zero point of the pseudo dot. These results are helpful in the control of decoherence in quantum systems and may also be useful for the design of quantum computers.

Nodeless vibrational amplitudes and quantum nonadiabatic dynamics in the nested funnel for a pseudo Jahn-Teller molecule or homodimer

NASA Astrophysics Data System (ADS)

Peters, William K.; Tiwari, Vivek; Jonas, David M.

2017-11-01

The nonadiabatic states and dynamics are investigated for a linear vibronic coupling Hamiltonian with a static electronic splitting and weak off-diagonal Jahn-Teller coupling through a single vibration with a vibrational-electronic resonance. With a transformation of the electronic basis, this Hamiltonian is also applicable to the anti-correlated vibration in a symmetric homodimer with marginally strong constant off-diagonal coupling, where the non-adiabatic states and dynamics model electronic excitation energy transfer or self-exchange electron transfer. For parameters modeling a free-base naphthalocyanine, the nonadiabatic couplings are deeply quantum mechanical and depend on wavepacket width; scalar couplings are as important as the derivative couplings that are usually interpreted to depend on vibrational velocity in semiclassical curve crossing or surface hopping theories. A colored visualization scheme that fully characterizes the non-adiabatic states using the exact factorization is developed. The nonadiabatic states in this nested funnel have nodeless vibrational factors with strongly avoided zeroes in their vibrational probability densities. Vibronic dynamics are visualized through the vibrational coordinate dependent density of the time-dependent dipole moment in free induction decay. Vibrational motion is amplified by the nonadiabatic couplings, with asymmetric and anisotropic motions that depend upon the excitation polarization in the molecular frame and can be reversed by a change in polarization. This generates a vibrational quantum beat anisotropy in excess of 2/5. The amplitude of vibrational motion can be larger than that on the uncoupled potentials, and the electronic population transfer is maximized within one vibrational period. Most of these dynamics are missed by the adiabatic approximation, and some electronic and vibrational motions are completely suppressed by the Condon approximation of a coordinate-independent transition dipole between adiabatic states. For all initial conditions investigated, the initial nonadiabatic electronic motion is driven towards the lower adiabatic state, and criteria for this directed motion are discussed.

Nodeless vibrational amplitudes and quantum nonadiabatic dynamics in the nested funnel for a pseudo Jahn-Teller molecule or homodimer.

PubMed

Peters, William K; Tiwari, Vivek; Jonas, David M

2017-11-21

The nonadiabatic states and dynamics are investigated for a linear vibronic coupling Hamiltonian with a static electronic splitting and weak off-diagonal Jahn-Teller coupling through a single vibration with a vibrational-electronic resonance. With a transformation of the electronic basis, this Hamiltonian is also applicable to the anti-correlated vibration in a symmetric homodimer with marginally strong constant off-diagonal coupling, where the non-adiabatic states and dynamics model electronic excitation energy transfer or self-exchange electron transfer. For parameters modeling a free-base naphthalocyanine, the nonadiabatic couplings are deeply quantum mechanical and depend on wavepacket width; scalar couplings are as important as the derivative couplings that are usually interpreted to depend on vibrational velocity in semiclassical curve crossing or surface hopping theories. A colored visualization scheme that fully characterizes the non-adiabatic states using the exact factorization is developed. The nonadiabatic states in this nested funnel have nodeless vibrational factors with strongly avoided zeroes in their vibrational probability densities. Vibronic dynamics are visualized through the vibrational coordinate dependent density of the time-dependent dipole moment in free induction decay. Vibrational motion is amplified by the nonadiabatic couplings, with asymmetric and anisotropic motions that depend upon the excitation polarization in the molecular frame and can be reversed by a change in polarization. This generates a vibrational quantum beat anisotropy in excess of 2/5. The amplitude of vibrational motion can be larger than that on the uncoupled potentials, and the electronic population transfer is maximized within one vibrational period. Most of these dynamics are missed by the adiabatic approximation, and some electronic and vibrational motions are completely suppressed by the Condon approximation of a coordinate-independent transition dipole between adiabatic states. For all initial conditions investigated, the initial nonadiabatic electronic motion is driven towards the lower adiabatic state, and criteria for this directed motion are discussed.

Equilibrium isotope effects on noncovalent interactions in a supramolecular host-guest system.

PubMed

Mugridge, Jeffrey S; Bergman, Robert G; Raymond, Kenneth N

2012-02-01

The self-assembled supramolecular complex [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) can act as a molecular host in aqueous solution and bind cationic guest molecules to its highly charged exterior surface or within its hydrophobic interior cavity. The distinct internal cavity of host 1 modifies the physical properties and reactivity of bound guest molecules and can be used to catalyze a variety of chemical transformations. Noncovalent host-guest interactions in large part control guest binding, molecular recognition and the chemical reactivity of bound guests. Herein we examine equilibrium isotope effects (EIEs) on both exterior and interior guest binding to host 1 and use these effects to probe the details of noncovalent host-guest interactions. For both interior and exterior binding of a benzylphosphonium guest in aqueous solution, protiated guests are found to bind more strongly to host 1 (K(H)/K(D) > 1) and the preferred association of protiated guests is driven by enthalpy and opposed by entropy. Deuteration of guest methyl and benzyl C-H bonds results in a larger EIE than deuteration of guest aromatic C-H bonds. The observed EIEs can be well explained by considering changes in guest vibrational force constants and zero-point energies. DFT calculations further confirm the origins of these EIEs and suggest that changes in low-frequency guest C-H/D vibrational motions (bends, wags, etc.) are primarily responsible for the observed EIEs. © 2011 American Chemical Society

Energy harvesting for self-powered aerostructure actuation

NASA Astrophysics Data System (ADS)

Bryant, Matthew; Pizzonia, Matthew; Mehallow, Michael; Garcia, Ephrahim

2014-04-01

This paper proposes and experimentally investigates applying piezoelectric energy harvesting devices driven by flow induced vibrations to create self-powered actuation of aerostructure surfaces such as tabs, flaps, spoilers, or morphing devices. Recently, we have investigated flow-induced vibrations and limit cycle oscillations due to aeroelastic flutter phenomena in piezoelectric structures as a mechanism to harvest energy from an ambient fluid flow. We will describe how our experimental investigations in a wind tunnel have demonstrated that this harvested energy can be stored and used on-demand to actuate a control surface such as a trailing edge flap in the airflow. This actuated control surface could take the form of a separate and discrete actuated flap, or could constitute rotating or deflecting the oscillating energy harvester itself to produce a non-zero mean angle of attack. Such a rotation of the energy harvester and the associated change in aerodynamic force is shown to influence the operating wind speed range of the device, its limit cycle oscillation (LCO) amplitude, and its harvested power output; hence creating a coupling between the device's performance as an energy harvester and as a control surface. Finally, the induced changes in the lift, pitching moment, and drag acting on a wing model are quantified and compared for a control surface equipped with an oscillating energy harvester and a traditional, static control surface of the same geometry. The results show that when operated in small amplitude LCO the energy harvester adds negligible aerodynamic drag.

TOPICAL REVIEW: Experimental study of organic zero-gap conductor α-(BEDT-TTF)2I3

NASA Astrophysics Data System (ADS)

Tajima, Naoya; Kajita, Koji

2009-04-01

A zero-gap state with a Dirac cone type energy dispersion was discovered in the organic conductor α-(BEDT-TTF)2I3 under high hydrostatic pressures. This is the first two-dimensional (2D) zero-gap state discovered in bulk crystals with a layered structure. In contrast to the case of graphene, the Dirac cone in this system is highly anisotropic. The present system, therefore, provides a new type of massless Dirac fermion system with anisotropic Fermi velocity. This system exhibits remarkable transport phenomena characteristic to electrons on the Dirac cone type energy structure. The carrier density, written as n~T2, is a characteristic feature of the 2D zero-gap structure. On the other hand, the resistivity per layer (sheet resistance RS) is given as RS=h/e2 and is independent of temperature. The effect of a magnetic field on samples in the zero-gap system was examined. The difference between zero-gap conductors and conventional conductors is the appearance of a Landau level called the zero mode at the contact points when a magnetic field is applied normal to the conductive layer. Zero-mode Landau carriers give rise to strong negative out-of-plane magnetoresistance.

Magnetic properties of graphene quantum dots

NASA Astrophysics Data System (ADS)

Espinosa-Ortega, T.; Luk'yanchuk, I. A.; Rubo, Y. G.

2013-05-01

Using the tight-binding approximation we calculated the diamagnetic susceptibility of graphene quantum dots (GQDs) of different geometrical shapes and characteristic sizes of 2-10 nm, when the magnetic properties are governed by the electron edge states. Two types of edge states can be discerned: the zero-energy states (ZESs), located exactly at the zero-energy Dirac point, and the dispersed edge states (DESs), with the energy close but not exactly equal to zero. DESs are responsible for a temperature-independent diamagnetic response, while ZESs provide a temperature-dependent spin paramagnetism. Hexagonal, circular, and randomly shaped GQDs contain mainly DESs, and, as a result, they are diamagnetic. The edge states of the triangular GQDs are of ZES type. These dots reveal the crossover between spin paramagnetism, dominating for small dots and at low temperatures, and orbital diamagnetism, dominating for large dots and at high temperatures.

Kelvin-Voigt model of wave propagation in fragmented geomaterials with impact damping

NASA Astrophysics Data System (ADS)

Khudyakov, Maxim; Pasternak, Elena; Dyskin, Arcady

2017-04-01

When a wave propagates through real materials, energy dissipation occurs. The effect of loss of energy in homogeneous materials can be accounted for by using simple viscous models. However, a reliable model representing the effect in fragmented geomaterials has not been established yet. The main reason for that is a mechanism how vibrations are transmitted between the elements (fragments) in these materials. It is hypothesised that the fragments strike against each other, in the process of oscillation, and the impacts lead to the energy loss. We assume that the energy loss is well represented by the restitution coefficient. The principal element of this concept is the interaction of two adjacent blocks. We model it by a simple linear oscillator (a mass on an elastic spring) with an additional condition: each time the system travels through the neutral point, where the displacement is equal to zero, the velocity reduces by multiplying itself by the restitution coefficient, which characterises an impact of the fragments. This additional condition renders the system non-linear. We show that the behaviour of such a model averaged over times much larger than the system period can approximately be represented by a conventional linear oscillator with linear damping characterised by a damping coefficient expressible through the restitution coefficient. Based on this the wave propagation at times considerably greater than the resonance period of oscillations of the neighbouring blocks can be modelled using the Kelvin-Voigt model. The wave velocities and the dispersion relations are obtained.

Coupled-cluster and density functional theory studies of the electronic 0-0 transitions of the DNA bases.

PubMed

Ovchinnikov, Vasily A; Sundholm, Dage

2014-04-21

The 0-0 transitions of the electronic excitation spectra of the lowest tautomers of the four nucleotide (DNA) bases have been studied using linear-response approximate coupled-cluster singles and doubles (CC2) calculations. Excitation energies have also been calculated at the linear-response time-dependent density functional theory (TDDFT) level using the B3LYP functional. Large basis sets have been employed for ensuring that the obtained excitation energies are close to the basis-set limit. Zero-point vibrational energy corrections have been calculated at the B3LYP and CC2 levels for the ground and excited states rendering direct comparisons with high-precision spectroscopy measurements feasible. The obtained excitation energies for the 0-0 transitions of the first excited states of guanine tautomers are in good agreement with experimental values confirming the experimental assignment of the energetic order of the tautomers of the DNA bases. For the experimentally detected guanine tautomers, the first excited state corresponds to a π→π* transition, whereas for the tautomers of adenine, thymine, and the lowest tautomer of cytosine the transition to the first excited state has n →π* character. The calculations suggest that the 0-0 transitions of adenine, thymine, and cytosine are not observed in the absorption spectrum due to the weak oscillator strength of the formally symmetry-forbidden transitions, while 0-0 transitions of thymine have been detected in fluorescence excitation spectra.

A new method for testing pile by single-impact energy and P-S curve

NASA Astrophysics Data System (ADS)

Xu, Zhao-Yong; Duan, Yong-Kang; Wang, Bin; Hu, Yi-Li; Yang, Run-Hai; Xu, Jun; Zhao, Jin-Ming

2004-11-01

By studying the pile-formula and stress-wave methods ( e.g., CASE method), the authors propose a new method for testing piles using the single-impact energy and P-S curves. The vibration and wave figures are recorded, and the dynamic and static displacements are measured by different transducers near the top of piles when the pile is impacted by a heavy hammer or micro-rocket. By observing the transformation coefficient of driving energy (total energy), the consumed energy of wave motion and vibration and so on, the vertical bearing capacity for single pile is measured and calculated. Then, using the vibration wave diagram, the dynamic relation curves between the force ( P) and the displacement ( S) is calculated and the yield points are determined. Using the static-loading test, the dynamic results are checked and the relative constants of dynamic-static P-S curves are determined. Then the subsidence quantity corresponding to the bearing capacity is determined. Moreover, the shaped quality of the pile body can be judged from the formation of P-S curves.

Magnification of signatures of a topological phase transition by quantum zero point motion

NASA Astrophysics Data System (ADS)

Lopes, Pedro L. e. S.; Ghaemi, Pouyan

2015-08-01

We show that the zero point motion of a vortex in superconducting doped topological insulators leads to significant changes in the electronic spectrum at the topological phase transition in this system. This topological phase transition is tuned by the doping level, and the corresponding effects are manifest in the density of states at energies which are on the order of the vortex fluctuation frequency. Although the electronic energy gap in the spectrum generated by a stationary vortex is but a small fraction of the bulk superconducting gap, the vortex fluctuation frequency may be much larger. As a result, this quantum zero point motion can induce a discontinuous change in the spectral features of the system at the topological vortex phase transition to energies which are well within the resolution of scanning tunneling microscopy. This discontinuous change is exclusive to superconducting systems in which we have a topological phase transition. Moreover, the phenomena studied in this paper present effects of Magnus forces on the vortex spectrum which are not present in the ordinary s -wave superconductors. Finally, we demonstrate explicitly that the vortex in this system is equivalent to a Kitaev chain. This allows for the mapping of the vortex fluctuating scenario in three dimensions into similar one-dimensional situations in which one may search for other novel signatures of topological phase transitions.

Quasisaddles as relevant points of the potential energy surface in the dynamics of supercooled liquids

NASA Astrophysics Data System (ADS)

Angelani, L.; Di Leonardo, R.; Ruocco, G.; Scala, A.; Sciortino, F.

2002-06-01

The supercooled dynamics of a Lennard-Jones model liquid is numerically investigated studying relevant points of the potential energy surface, i.e., the minima of the square gradient of total potential energy V. The main findings are (i) the number of negative curvatures n of these sampled points appears to extrapolate to zero at the mode coupling critical temperature Tc; (ii) the temperature behavior of n(T) has a close relationship with the temperature behavior of the diffusivity; (iii) the potential energy landscape shows a high regularity in the distances among the relevant points and in their energy location. Finally we discuss a model of the landscape, previously introduced by Madan and Keyes [J. Chem. Phys. 98, 3342 (1993)], able to reproduce the previous findings.

Active damping using a control structure interaction approach

NASA Astrophysics Data System (ADS)

Umland, Jeffrey W.

1991-12-01

The vibration control of flexible structures using electromagnetic actuators is investigated. A model of an electromagnetic voice coil actuator is developed from elementary theory, and the required parameters are measured. Given a constant magnetic field, the force output of the voice coil varies linearly with the current flowing through the coil. The primary damping mechanism of the actuator used is found to be Coulomb friction. It is seen that Coulomb friction inhibits the response of the actuator to low levels of excitation. It is also seen that the actuator displayed a nonlinear relationship between force and current indicating that the applied magnetic field was not constant. This nonlinearity leads to a closed loop instability. Several design improvements are considered. Four different feedback control laws are developed to add active damping to a structure. The actuator is used as both a point force source and as a link in a mechanism that applies bending moments at two places on the structure. The actuator is used as both a point force source and as a link in a mechanism that applies bending moments at two places on the structure. The first control law uses the actuator as a traditional passive vibration absorber. The second control law is direct structural velocity feedback plus direct proof mass position feedback. The third control strategy is also direct structural velocity feedback but using compensated feedback of the proof mass position. The compensator is designed according to an H infinity optimization technique. The fourth control law uses the actuator as an equivalent mechanical viscous damper connected to two points on the structure. The results show that using direct structural velocity feedback provides improved vibration suppression in comparison to a traditional vibration absorber. Furthermore, the tuning criteria is only restricted to maintaining the actuator's single degree of freedom natural frequency below those of the structure to which it is attached.

Two-dimensional Dirac fermions in thin films of C d3A s2

NASA Astrophysics Data System (ADS)

Galletti, Luca; Schumann, Timo; Shoron, Omor F.; Goyal, Manik; Kealhofer, David A.; Kim, Honggyu; Stemmer, Susanne

2018-03-01

Two-dimensional states in confined thin films of the three-dimensional Dirac semimetal C d3A s2 are probed by transport and capacitance measurements under applied magnetic and electric fields. The results establish the two-dimensional Dirac electronic spectrum of these states. We observe signatures of p -type conduction in the two-dimensional states as the Fermi level is tuned across their charge neutrality point and the presence of a zero-energy Landau level, all of which indicate topologically nontrivial states. The resistance at the charge neutrality point is approximately h /e2 and increases rapidly under the application of a magnetic field. The results open many possibilities for gate-tunable topological devices and for the exploration of novel physics in the zero-energy Landau level.

Vibrational Spectroscopy of CO2- Radical Anion in Water

NASA Astrophysics Data System (ADS)

Janik, Ireneusz; Tripathi, G. N. R.

2016-06-01

The reductive conversion of CO2 into industrial products (e.g., oxalic acid, formic acid, and methanol) can occur via aqueous CO2- as a transient intermediate. While the formation, structure and reaction pathways of this radical anion have been modelled for decades using various spectroscopic and theoretical approaches, we present here, for the first time, a vibrational spectroscopic investigation in liquid water, using pulse radiolysis time-resolved resonance Raman spectroscopy for its preparation and observation. Excitation of the radical in resonance with its 235 nm absorption displays a transient Raman band at 1298 wn, attributed to the symmetric CO stretch, which is at 45 wn higher frequency than in inert matrices. Isotopic substitution at C (13CO2-) shifts the frequency downwards by 22 wn which confirms its origin and the assignment. A Raman band of moderate intensity compared to the stronger 1298 wn band also appears at 742 wn, and is assignable to the OCO bending mode. A reasonable resonance enhancement of this mode is possible only in a bent CO2-(C2v/Cs) geometry. These resonance Raman features suggest a strong solute-solvent interaction, the water molecules acting as constituents of the radical structure, rather than exerting a minor solvent perturbation. However, there is no evidence of the non-equivalence (Cs) of the two CO bonds. A surprising resonance Raman feature is the lack of overtones of the symmetric CO stretch, which we interpret due to the detachment of the electron from the CO2- moiety towards the solvation shell. Electron detachment occurs at the energies of 0.28+/-0.03 eV or higher with respect to the zero point energy of the ground electronic state. The issue of acid-base equilibrium of the radical which has been in contention for decades, as reflected in a wide variation in the reported pKa (-0.2 to 3.9), has been resolved. A value of 3.4+/-0.2 measured in this work is consistent with the vibrational properties, bond structure and charge distribution in aqueous CO2-.

Experimental and ab initio characterization of HC3N+ vibronic structure. II. High-resolution VUV PFI-ZEKE spectroscopy.

PubMed

Gans, Bérenger; Lamarre, Nicolas; Broquier, Michel; Liévin, Jacques; Boyé-Péronne, Séverine

2016-12-21

Vacuum-ultraviolet pulsed-field-ionization zero-kinetic-energy photoelectron spectra of X + Π2←XΣ+1 and B + Π2←XΣ+1 transitions of the HC 3 14 N and HC 3 15 N isotopologues of cyanoacetylene have been recorded. The resolution of the photoelectron spectra allowed us to resolve the vibrational structures and the spin-orbit splittings in the cation. Accurate values of the adiabatic ionization potentials of the two isotopologues (E I /hc(HC 3 14 N)=93 909(2) cm -1 and E I /hc(HC 3 15 N)=93 912(2) cm -1 ), the vibrational frequencies of the ν 2 , ν 6 , and ν 7 vibrational modes, and the spin-orbit coupling constant (A SO = -44(2) cm -1 ) of the X + Π2 cationic ground state have been derived from the measurements. Using ab initio calculations, the unexpected structure of the B + Π2←XΣ+1 transition is tentatively attributed to a conical intersection between the A + and B + electronic states of the cation.

Mapping quadrupole collectivity in the Cd isotopes: The breakdown of harmonic vibrational motion

NASA Astrophysics Data System (ADS)

Garrett, P. E.; Green, K. L.; Bangay, J.; Varela, A. Diaz; Sumithrarachchi, C. S.; Austin, R. A. E.; Ball, G. C.; Bandyopadhyay, D. S.; Bianco, L.; Colosimo, S.; Cross, D. S.; Demand, G. A.; Finlay, P.; Garnsworthy, A. B.; Grinyer, G. F.; Hackman, G.; Kulp, W. D.; Leach, K. G.; Morton, A. C.; Orce, J. N.; Pearson, C. J.; Phillips, A. A.; Schumaker, M. A.; Svensson, C. E.; Triambak, S.; Wong, J.; Wood, J. L.; Yates, S. W.

2011-10-01

The stable Cd isotopes have long been used as paradigms for spherical vibrational motion. Extensive investigations with in-beam γ spectroscopy have resulted in very-well-established level schemes, including many lifetimes or lifetime limits. A programme has been initiated to complement these studies with very-high-statistics β decay using the 8π spectrometer at the TRIUMF radioactive beam facility. The decays of 112In and 112Ag have been studied with an emphasis on the observation of, or the placement of stringent limits on, low-energy branches between potential multi-phonon levels. A lack of suitable 0+ or 2+ three-phonon candidates has been revealed. Further, the sum of the B(E2) strength from spin 0+ and 2+ states up to 3 MeV in excitation energy to the assigned two-phonon levels falls far short of the harmonic-vibrational expectations. This lack of strength points to the failing of collective models based on vibrational phonon structures.

DFT and experimental studies of the structure and vibrational spectra of curcumin

NASA Astrophysics Data System (ADS)

Kolev, Tsonko M.; Velcheva, Evelina A.; Stamboliyska, Bistra A.; Spiteller, Michael

The potential energy surface of curcumin [1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione] was explored with the DFT correlation functional B3LYP method using 6-311G* basis. The single-point calculations were performed at levels up to B3LYP/6-311++G**//B3LYP/6-311G*. All isomers were located and relative energies determined. According to the calculation the planar enol form is more stable than the nonplanar diketo form. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. In addition, harmonic vibrational frequencies of the molecule were evaluated theoretically using B3LYP density functional methods. The computed vibrational frequencies were used to determine the types of molecular motions associated with each of the experimental bands observed. Our vibrational data show that in both the solid state and in all studied solutions curcumin exists in the enol form.

Ground-state-entanglement bound for quantum energy teleportation of general spin-chain models

NASA Astrophysics Data System (ADS)

Hotta, Masahiro

2013-03-01

Many-body quantum systems in the ground states have zero-point energy due to the uncertainty relation. In many cases, the system in the ground state accompanies spatially entangled energy density fluctuation via the noncommutativity of the energy density operators, though the total energy takes a fixed value, i.e., the lowest eigenvalue of the Hamiltonian. Quantum energy teleportation (QET) is a protocol for the extraction of the zero-point energy out of one subsystem using information of a remote measurement of another subsystem. From an operational viewpoint of protocol users, QET can be regarded as an effective rapid energy transportation without breaking all physical laws, including causality and local energy conservation. In the protocol, the ground-state entanglement plays a crucial role. In this paper, we show analytically for a general class of spin-chain systems that the entanglement entropy is lower bounded by a positive quadratic function of the teleported energy between the regions of a QET protocol. This supports a general conjecture that ground-state entanglement is an evident physical resource for energy transportation in the context of QET. The result may also deepen our understanding of the energy density fluctuation in condensed-matter systems from a perspective of quantum information theory.

Acoustic analysis of trill sounds.

PubMed

Dhananjaya, N; Yegnanarayana, B; Bhaskararao, Peri

2012-04-01

In this paper, the acoustic-phonetic characteristics of steady apical trills--trill sounds produced by the periodic vibration of the apex of the tongue--are studied. Signal processing methods, namely, zero-frequency filtering and zero-time liftering of speech signals, are used to analyze the excitation source and the resonance characteristics of the vocal tract system, respectively. Although it is natural to expect the effect of trilling on the resonances of the vocal tract system, it is interesting to note that trilling influences the glottal source of excitation as well. The excitation characteristics derived using zero-frequency filtering of speech signals are glottal epochs, strength of impulses at the glottal epochs, and instantaneous fundamental frequency of the glottal vibration. Analysis based on zero-time liftering of speech signals is used to study the dynamic resonance characteristics of vocal tract system during the production of trill sounds. Qualitative analysis of trill sounds in different vowel contexts, and the acoustic cues that may help spotting trills in continuous speech are discussed.

Chaos in a restricted problem of rotation of a rigid body with a fixed point

NASA Astrophysics Data System (ADS)

Borisov, A. V.; Kilin, A. A.; Mamaev, I. S.

2008-06-01

In this paper, we consider the transition to chaos in the phase portrait of a restricted problem of rotation of a rigid body with a fixed point. Two interrelated mechanisms responsible for chaotization are indicated: (1) the growth of the homoclinic structure and (2) the development of cascades of period doubling bifurcations. On the zero level of the area integral, an adiabatic behavior of the system (as the energy tends to zero) is noted. Meander tori induced by the break of the torsion property of the mapping are found.

Theoretical and simulation analysis of piezoelectric liquid resistance captor filled with pipeline

NASA Astrophysics Data System (ADS)

Zheng, Li; Zhigang, Yang; Junwu, Kan; Lisheng; Bo, Yan; Dan, Lu

2018-03-01

This paper designs a kind of Piezoelectric liquid resistance capture energy device, by using the superposition theory of the sheet deformation, the calculation model of the displacement curve of the circular piezoelectric vibrator and the power generation capacity under the concentrated load is established. The results show that the radius ratio, thickness ratio and Young’s modulus of the circular piezoelectric vibrator have greater influence on the power generation capacity. When the material of piezoelectric oscillator is determined, the best radius ratio and thickness ratio make the power generation capacity the largest. Excessive or small radius ratio and thickness ratio will reduce the generating capacity and even generate zero power. In addition, the electromechanical equivalent model is established. Equivalent analysis is made by changing the circuit impedance. The results are consistent with the theoretical simulation results, indicating that the established circuit model can truly reflect the characteristics of the theoretical model.

Infrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway

DOE PAGES

Brice, Joseph T.; Liang, Tao; Raston, Paul L.; ...

2016-09-27

Here, sequential capture of OH and CO by superfluid helium droplets leads exclusively to the formation of the linear, entrance-channel complex, OH-CO. This species is characterized by infrared laser Stark and Zeeman spectroscopy via measurements of the fundamental OH stretching vibration. Experimental dipole moments are in disagreement with ab initio calculations at the equilibrium geometry, indicating large-amplitude motion on the ground state potential energy surface. Vibrational averaging along the hydroxyl bending coordinate recovers 80% of the observed deviation from the equilibrium dipole moment. Inhomogeneous line broadening in the zero-field spectrum is modeled with an effective Hamiltonian approach that aims tomore » account for the anisotropic molecule-helium interaction potential that arises as the OH-CO complex is displaced from the center of the droplet.« less

Free-vibration acoustic resonance of a nonlinear elastic bar

NASA Astrophysics Data System (ADS)

Tarumi, Ryuichi; Oshita, Yoshihito

2011-02-01

Free-vibration acoustic resonance of a one-dimensional nonlinear elastic bar was investigated by direct analysis in the calculus of variations. The Lagrangian density of the bar includes a cubic term of the deformation gradient, which is responsible for both geometric and constitutive nonlinearities. By expanding the deformation function into a complex Fourier series, we derived the action integral in an analytic form and evaluated its stationary conditions numerically with the Ritz method for the first three resonant vibration modes. This revealed that the bar shows the following prominent nonlinear features: (i) amplitude dependence of the resonance frequency; (ii) symmetry breaking in the vibration pattern; and (iii) excitation of the high-frequency mode around nodal-like points. Stability of the resonant vibrations was also addressed in terms of a convex condition on the strain energy density.

Clamped seismic metamaterials: ultra-low frequency stop bands

NASA Astrophysics Data System (ADS)

Achaoui, Y.; Antonakakis, T.; Brûlé, S.; Craster, R. V.; Enoch, S.; Guenneau, S.

2017-06-01

The regularity of earthquakes, their destructive power, and the nuisance of ground vibration in urban environments, all motivate designs of defence structures to lessen the impact of seismic and ground vibration waves on buildings. Low frequency waves, in the range 1-10 Hz for earthquakes and up to a few tens of Hz for vibrations generated by human activities, cause a large amount of damage, or inconvenience; depending on the geological conditions they can travel considerable distances and may match the resonant fundamental frequency of buildings. The ultimate aim of any seismic metamaterial, or any other seismic shield, is to protect over this entire range of frequencies; the long wavelengths involved, and low frequency, have meant this has been unachievable to date. Notably this is scalable and the effects also hold for smaller devices in ultrasonics. There are three approaches to obtaining shielding effects: bragg scattering, locally resonant sub-wavelength inclusions and zero-frequency stop-band media. The former two have been explored, but the latter has not and is examined here. Elastic flexural waves, applicable in the mechanical vibrations of thin elastic plates, can be designed to have a broad zero-frequency stop-band using a periodic array of very small clamped circles. Inspired by this experimental and theoretical observation, all be it in a situation far removed from seismic waves, we demonstrate that it is possible to achieve elastic surface (Rayleigh) wave reflectors at very large wavelengths in structured soils modelled as a fully elastic layer periodically clamped to bedrock. We identify zero frequency stop-bands that only exist in the limit of columns of concrete clamped at their base to the bedrock. In a realistic configuration of a sedimentary basin 15 m deep we observe a zero frequency stop-band covering a broad frequency range of 0-30 Hz.

Proposed Use of Zero Bias Diode Arrays as Thermal Electric Noise Rectifiers and Non-Thermal Energy Harvesters

NASA Astrophysics Data System (ADS)

Valone, Thomas F.

2009-03-01

The well known built-in voltage potential for some select semiconductor p-n junctions and various rectifying devices is proposed to be favorable for generating DC electricity at "zero bias" (with no DC bias voltage applied) in the presence of Johnson noise or 1/f noise which originates from the quantum vacuum (Koch et al., 1982). The 1982 Koch discovery that certain solid state devices exhibit measurable quantum noise has also recently been labeled a finding of dark energy in the lab (Beck and Mackey, 2004). Tunnel diodes are a class of rectifiers that are qualified and some have been credited with conducting only because of quantum fluctuations. Microwave diodes are also good choices since many are designed for zero bias operation. A completely passive, unamplified zero bias diode converter/detector for millimeter (GHz) waves was developed by HRL Labs in 2006 under a DARPA contract, utilizing a Sb-based "backward tunnel diode" (BTD). It is reported to be a "true zero-bias diode." It was developed for a "field radiometer" to "collect thermally radiated power" (in other words, 'night vision'). The diode array mounting allows a feed from horn antenna, which functions as a passive concentrating amplifier. An important clue is the "noise equivalent power" of 1.1 pW per root hertz and the "noise equivalent temperature difference" of 10° K, which indicate sensitivity to Johnson noise (Lynch, et al., 2006). There also have been other inventions such as "single electron transistors" that also have "the highest signal to noise ratio" near zero bias. Furthermore, "ultrasensitive" devices that convert radio frequencies have been invented that operate at outer space temperatures (3 degrees above zero point: 3° K). These devices are tiny nanotech devices which are suitable for assembly in parallel circuits (such as a 2-D array) to possibly produce zero point energy direct current electricity with significant power density (Brenning et al., 2006). Photovoltaic p-n junction cells are also considered for possible higher frequency ZPE transduction. Diode arrays of self-assembled molecular rectifiers or preferably, nano-sized cylindrical diodes are shown to reasonably provide for rectification of electron fluctuations from thermal and non-thermal ZPE sources to create an alternative energy DC electrical generator in the picowatt per diode range.

Palpation simulator with stable haptic feedback.

PubMed

Kim, Sang-Youn; Ryu, Jee-Hwan; Lee, WooJeong

2015-01-01

The main difficulty in constructing palpation simulators is to compute and to generate stable and realistic haptic feedback without vibration. When a user haptically interacts with highly non-homogeneous soft tissues through a palpation simulator, a sudden change of stiffness in target tissues causes unstable interaction with the object. We propose a model consisting of a virtual adjustable damper and an energy measuring element. The energy measuring element gauges energy which is stored in a palpation simulator and the virtual adjustable damper dissipates the energy to achieve stable haptic interaction. To investigate the haptic behavior of the proposed method, impulse and continuous inputs are provided to target tissues. If a haptic interface point meets with the hardest portion in the target tissues modeled with a conventional method, we observe unstable motion and feedback force. However, when the target tissues are modeled with the proposed method, a palpation simulator provides stable interaction without vibration. The proposed method overcomes a problem in conventional haptic palpation simulators where unstable force or vibration can be generated if there is a big discrepancy in material property between an element and its neighboring elements in target tissues.

Vibrational spectra and normal coordinate analysis of diazepam, phenytoin and phenobarbitone

NASA Astrophysics Data System (ADS)

Gunasekaran, S.; Thilak Kumar, R.; Ponnusamy, S.

2006-12-01

Vibrational spectroscopy is an important tool for the structural investigation of the organic molecules. In the present investigation, a normal coordinate analysis has been carried out on some anti-epileptic drugs, viz. diazepam, phenytoin and phenobarbitone. Diazepam is a derivative of benzodiazepine, phenytoin is a derivative of hydanation and pheonobarbitone is a barbiturate. The infrared spectra of the compounds are recorded in the region 4000-400 cm -1 and Raman spectra are recorded in the region 3500-50 cm -1. From the structural point of view, diazepam, phenytoin and phenobarbitone have been assumed to C s point group. A systematic set of symmetry coordinates has been constructed for these compounds and Wilson's FG matrix method has been applied for the normal coordinate analysis using general quadratic valance force field. The potential energy distribution is also calculated to check the vibrational band assignments.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kita, Shota, E-mail: happiest3.7@gmail.com; Ueno, Toshiyuki; Yamada, Sotoshi

We develop high power magnetostrictive vibration power generator for battery-free wireless electronics. The generator is based on a cantilever of parallel beam structure consisting of coil-wound Galfenol and stainless plates with permanent magnet for bias. Oscillating force exerted on the tip bends the cantilever in vibration yields stress variation of Galfenol plate, which causes flux variation and generates voltage on coil due to the law of induction. This generator has advantages over conventional, such as piezoelectric or moving magnet types, in the point of high efficiency, highly robust, and low electrical impedance. Our concern is the improvement of energy conversionmore » efficiency dependent on the dimension. Especially, force factor, the conversion ratio of the electromotive force (voltage) on the tip velocity in vibration, has an important role in energy conversion process. First, the theoretical value of the force factor is formulated and then the validity was verified by experiments, where we compare four types of prototype with parameters of the dimension using 7.0 × 1.5 × 50 mm beams of Galfenol with 1606-turn wound coil. In addition, the energy conversion efficiency of the prototypes depending on load resistance was measured. The most efficient prototype exhibits the maximum instantaneous power of 0.73 W and energy of 4.7 mJ at a free vibration of frequency of 202 Hz in the case of applied force is 25 N. Further, it was found that energy conversion efficiency depends not only on the force factor but also on the damping (mechanical loss) of the vibration.« less

Blurring out hydrogen: The dynamical structure of teflic acid

NASA Astrophysics Data System (ADS)

Herbers, S.; Obenchain, D. A.; Kraus, P.; Wachsmuth, D.; Grabow, J.-U.

2018-05-01

The microwave spectra of 10 teflic acid isotopologues were recorded in the frequency range of 3-25 GHz using supersonic jet-expansion Fourier transform microwave spectroscopy. Despite being asymmetric in its equilibrium structure, the delocalization of the hydrogen atom leads to a symmetric top vibrational ground state structure. In this work, we present the zero point structure obtained from the experimental rotational constants and an approach to determine the semi-experimental equilibrium structure aided by ab initio data. The Te-O bond length determined in the equilibrium structure is accurate to the picometer and can be used as a benchmark for computational methods treating relativistic effects.

Anharmonic contribution to the stabilization of Mg(OH)2 from first principles.

PubMed

Treviño, P; Garcia-Castro, A C; López-Moreno, S; Bautista-Hernández, A; Bobocioiu, E; Reynard, B; Caracas, R; Romero, A H

2018-06-20

Geometrical and vibrational characterization of magnesium hydroxide was performed using density functional theory. Four possible crystal symmetries were explored: P3[combining macron] (No. 147, point group -3), C2/m (No. 12, point group 2), P3m1 (No. 156, point group 3m) and P3[combining macron]m1 (No. 164, point group -3m) which are the currently accepted geometries found in the literature. While a lot of work has been performed on Mg(OH)2, in particular for the P3[combining macron]m1 phase, there is still a debate on the observed ground state crystal structure and the anharmonic effects of the OH vibrations on the stabilization of the crystal structure. In particular, the stable positions of hydrogen are not yet defined precisely, which have implications in the crystal symmetry, the vibrational excitations, and the thermal stability. Previous work has assigned the P3[combining macron]m1 polymorph as the low energy phase, but it has also proposed that hydrogens are disordered and they could move from their symmetric position in the P3[combining macron]m1 structure towards P3[combining macron]. In this paper, we examine the stability of the proposed phases by using different descriptors. We compare the XRD patterns with reported experimental results, and a fair agreement is found. While harmonic vibrational analysis shows that most phases have imaginary modes at 0 K, anharmonic vibrational analysis indicates that at room temperature only the C2/m phase is stabilized, whereas at higher temperatures, other phases become thermally competitive.

A piezoelectric six-DOF vibration energy harvester based on parallel mechanism: dynamic modeling, simulation, and experiment

NASA Astrophysics Data System (ADS)

Yuan, G.; Wang, D. H.

2017-03-01

Multi-directional and multi-degree-of-freedom (multi-DOF) vibration energy harvesting are attracting more and more research interest in recent years. In this paper, the principle of a piezoelectric six-DOF vibration energy harvester based on parallel mechanism is proposed to convert the energy of the six-DOF vibration to single-DOF vibrations of the limbs on the energy harvester and output voltages. The dynamic model of the piezoelectric six-DOF vibration energy harvester is established to estimate the vibrations of the limbs. On this basis, a Stewart-type piezoelectric six-DOF vibration energy harvester is developed and explored. In order to validate the established dynamic model and the analysis results, the simulation model of the Stewart-type piezoelectric six-DOF vibration energy harvester is built and tested with different vibration excitations by SimMechanics, and some preliminary experiments are carried out. The results show that the vibration of the limbs on the piezoelectric six-DOF vibration energy harvester can be estimated by the established dynamic model. The developed Stewart-type piezoelectric six-DOF vibration energy harvester can harvest the energy of multi-directional linear vibration and multi-axis rotating vibration with resonance frequencies of 17 Hz, 25 Hz, and 47 Hz. Moreover, the resonance frequencies of the developed piezoelectric six-DOF vibration energy harvester are not affected by the direction changing of the vibration excitation.

Theory of action spectroscopy for single-molecule reactions induced by vibrational excitations with STM

NASA Astrophysics Data System (ADS)

Frederiksen, T.; Paulsson, M.; Ueba, H.

2014-01-01

A theory of action spectroscopy, i.e., a reaction rate or yield as a function of bias voltage, is presented for single-molecule reactions induced by the inelastic tunneling current with a scanning tunneling microscope. A formula for the reaction yield is derived using the adsorbate resonance model, which provides a versatile tool to analyze vibrationally mediated reactions of single adsorbates on conductive surfaces. This allows us to determine the energy quantum of the excited vibrational mode, the effective broadening of the vibrational density of states (as described by Gaussian or Lorentzian functions), and a prefactor characterizing the elementary process behind the reaction. The underlying approximations are critically discussed. We point out that observation of reaction yields at both bias voltage polarities can provide additional insight into the adsorbate density of states near the Fermi level. As an example, we apply the theory to the case of flip motion of a hydroxyl dimer (OD)2 on Cu(110) which was experimentally observed by Kumagai et al. [Phys. Rev. B 79, 035423 (2009), 10.1103/PhysRevB.79.035423]. In combination with density functional theory calculations for the vibrational modes, the vibrational damping due to electron-hole pair generation, and the potential energy landscape for the flip motion, a detailed microscopic picture for the switching process is established. This picture reveals that the predominant mechanism is excitation of the OD stretch modes which couple anharmonically to the low-energy frustrated rotation mode.

Water and energy link in the cities of the future - achieving net zero carbon and pollution emissions footprint.

PubMed

Novotny, V

2011-01-01

This article discusses the link between water conservation, reclamation, reuse and energy use as related to the goal of achieving the net zero carbon emission footprint in future sustainable cities. It defines sustainable ecocities and outlines quantitatively steps towards the reduction of energy use due to water and used water flows, management and limits in linear and closed loop water/stormwater/wastewater management systems. The three phase water energy nexus diagram may have a minimum inflection point beyond which reduction of water demand may not result in a reduction of energy and carbon emissions. Hence, water conservation is the best alternative solution to water shortages and minimizing the carbon footprint. A marginal water/energy chart is developed and proposed to assist planners in developing future ecocities and retrofitting older communities to achieve sustainability.

Pulsed, high-current, in-line reversal electron attachment detector

NASA Technical Reports Server (NTRS)

Bernius, Mark T.; Chutjian, Ara

1989-01-01

A new, pulsed, high-current, in-line reversal electron attachment ionizer/detector is described. The ionizer is capable of delivering a beam of electrons into an electrostatic mirror field to form a planar wall of electrons having zero kinetic energy. Electron attachment to a molecular target at the reversal point produces either parent or fragment negative ions through a zero-energy (s-wave) state. The atomic or molecular ion is pulsed out of the attachment region approximately 2 microsec after the electrons are pulsed off, and focused onto the entrance plane of a quadrupole mass analyzer. The sensitivity of the apparatus is preliminarily assessed, and its higher-energy behavior with regard to molecular attachment and ionization is described.

Optimized energy harvesting from mechanical vibrations through piezoelectric actuators, based on a synchronized switching technique

NASA Astrophysics Data System (ADS)

Tsampas, P.; Roditis, G.; Papadimitriou, V.; Chatzakos, P.; Gan, Tat-Hean

2013-05-01

Increasing demand in mobile, autonomous devices has made energy harvesting a particular point of interest. Systems that can be powered up by a few hundreds of microwatts could feature their own energy extraction module. Energy can be harvested from the environment close to the device. Particularly, the ambient mechanical vibrations conversion via piezoelectric transducers is one of the most investigated fields for energy harvesting. A technique for optimized energy harvesting using piezoelectric actuators called "Synchronized Switching Harvesting" is explored. Comparing to a typical full bridge rectifier, the proposed harvesting technique can highly improve harvesting efficiency, even in a significantly extended frequency window around the piezoelectric actuator's resonance. In this paper, the concept of design, theoretical analysis, modeling, implementation and experimental results using CEDRAT's APA 400M-MD piezoelectric actuator are presented in detail. Moreover, we suggest design guidelines for optimum selection of the storage unit in direct relation to the characteristics of the random vibrations. From a practical aspect, the harvesting unit is based on dedicated electronics that continuously sense the charge level of the actuator's piezoelectric element. When the charge is sensed, to come to a maximum, it is directed to speedily flow into a storage unit. Special care is taken so that electronics operate at low voltages consuming a very small amount of the energy stored. The final prototype developed includes the harvesting circuit implemented with miniaturized, low cost and low consumption electronics and a storage unit consisting of a super capacitors array, forming a truly self-powered system drawing energy from ambient random vibrations of a wide range of characteristics.

Femtosecond Multidimensional Imaging - Watching Chemistry from the Molecule's Point of View

NASA Astrophysics Data System (ADS)

Geßner, O.; Lee, A. M. D.; Chrysostom, E. t.-H.; Hayden, C. C.; Stolow, Albert

Using Femtosecond Multidimensional Imaging we disentangle the complex neutral dissociation mechanism of the NO dimer. We characterize all electronic configurations from start to finish and directly observe the evolution of intramolecular vibrational energy redistribution (IVR).

Breakdown of the Migdal approximation at Lifshitz transitions with giant zero-point motion in the H3S superconductor.

PubMed

Jarlborg, Thomas; Bianconi, Antonio

2016-04-20

While 203 K high temperature superconductivity in H3S has been interpreted by BCS theory in the dirty limit here we focus on the effects of hydrogen zero-point-motion and the multiband electronic structure relevant for multigap superconductivity near Lifshitz transitions. We describe how the topology of the Fermi surfaces evolves with pressure giving different Lifshitz-transitions. A neck-disrupting Lifshitz-transition (type 2) occurs where the van Hove singularity, vHs, crosses the chemical potential at 210 GPa and new small 2D Fermi surface portions appear with slow Fermi velocity where the Migdal-approximation becomes questionable. We show that the neglected hydrogen zero-point motion ZPM, plays a key role at Lifshitz transitions. It induces an energy shift of about 600 meV of the vHs. The other Lifshitz-transition (of type 1) for the appearing of a new Fermi surface occurs at 130 GPa where new Fermi surfaces appear at the Γ point of the Brillouin zone here the Migdal-approximation breaks down and the zero-point-motion induces large fluctuations. The maximum Tc = 203 K occurs at 160 GPa where EF/ω0 = 1 in the small Fermi surface pocket at Γ. A Feshbach-like resonance between a possible BEC-BCS condensate at Γ and the BCS condensate in different k-space spots is proposed.

Negative-ion formation in the explosives RDX, PETN, and TNT by using the reversal electron attachment detection technique

NASA Technical Reports Server (NTRS)

Boumsellek, S.; Alajajian, S. H.; Chutjian, A.

1992-01-01

First results of a beam-beam, single-collision study of negative-ion mass spectra produced by attachment of zero-energy electrons to the molecules of the explosives RDX, PETN, and TNT are presented. The technique used is reversal electron attachment detection (READ) wherein the zero-energy electrons are produced by focusing an intense electron beam into a shaped electrostatic field which reverses the trajectory of electrons. The target beam is introduced at the reversal point, and attachment occurs because the electrons have essentially zero longitudinal and radial velocity. The READ technique is used to obtain the 'signature' of molecular ion formation and/or fragmentation for each explosive. Present data are compared with results from atmospheric-pressure ionization and negative-ion chemical ionization methods.

Fragile surface zero-energy flat bands in three-dimensional chiral superconductors

NASA Astrophysics Data System (ADS)

Kobayashi, Shingo; Tanaka, Yukio; Sato, Masatoshi

2015-12-01

We study surface zero-energy flat bands in three-dimensional chiral superconductors with pz(px+i py) ν -wave pairing symmetry (ν is a nonzero integer), based on topological arguments and tunneling conductance. It is shown that the surface flat bands are fragile against (i) the surface misorientation and (ii) the surface Rashba spin-orbit interaction. The fragility of (i) is specific to chiral SCs, whereas that of (ii) happens for general odd-parity SCs. We demonstrate that these flat-band instabilities vanish or suppress a zero-bias conductance peak in a normal/insulator/superconductor junction, which behavior is clearly different from high-Tc cuprates and noncentrosymmetric superconductors. By calculating the angle-resolved conductance, we also discuss a topological surface state associated with the coexistence of line and point nodes.

Prediction of novel alloy phases of Al with Sc or Ta

PubMed Central

Bilić, Ante; Gale, Julian D.; Gibson, Mark A.; Wilson, Nick; McGregor, Kathie

2015-01-01

Using the evolutionary optimization algorithm, as implemented in the USPEX crystal predictor program, and first principles total energy calculations, the compositional phase diagrams for Al-Sc and Al-Ta alloy systems at zero temperature and pressure have been calculated. In addition to the known binary intermetallic phases, new potentially stable alloys, AlSc3 and AlTa7, have been identified in the Al-poor region of the phase diagram. The dynamic and thermal stability of their lattices has been confirmed from the calculated vibrational normal mode spectra in the harmonic approximation. PMID:25950915

A full-dimensional ab initio potential energy surface and rovibrational energies of the Ar–HF complex

NASA Astrophysics Data System (ADS)

Huang, Jing; Zhou, Yanzi; Xie, Daiqian

2018-04-01

We report a new full-dimensional ab initio potential energy surface for the Ar-HF van der Waals complex at the level of coupled-cluster singles and doubles with noniterative inclusion of connected triples levels [CCSD(T)] using augmented correlation-consistent quintuple-zeta basis set (aV5Z) plus bond functions. Full counterpoise correction was employed to correct the basis-set superposition error. The hypersurface was fitted using artificial neural network method with a root mean square error of 0.1085 cm-1 for more than 8000 ab initio points. The complex was found to prefer a linear Ar-H-F equilibrium structure. The three-dimensional discrete variable representation method and the Lanczos propagation algorithm were then employed to calculate the rovibrational states without separating inter- and intra- molecular nuclear motions. The calculated vibrational energies of Ar-HF differ from the experiment values within about 1 cm-1 on the first four HF vibrational states, and the predicted pure rotational energies on (0000) and (1000) vibrational states are deviated from the observed value by about 1%, which shows the accuracy of our new PES.

Comparison of Degrees of Potential-Energy-Surface Anharmonicity for Complexes and Clusters with Hydrogen Bonds

NASA Astrophysics Data System (ADS)

Kozlovskaya, E. N.; Doroshenko, I. Yu.; Pogorelov, V. E.; Vaskivskyi, Ye. V.; Pitsevich, G. A.

2018-01-01

Previously calculated multidimensional potential-energy surfaces of the MeOH monomer and dimer, water dimer, malonaldehyde, formic acid dimer, free pyridine-N-oxide/trichloroacetic acid complex, and protonated water dimer were analyzed. The corresponding harmonic potential-energy surfaces near the global minima were constructed for series of clusters and complexes with hydrogen bonds of different strengths based on the behavior of the calculated multidimensional potential-energy surfaces. This enabled the introduction of an obvious anharmonicity parameter for the calculated potential-energy surfaces. The anharmonicity parameter was analyzed as functions of the size of the analyzed area near the energy minimum, the number of points over which energies were compared, and the dimensionality of the solved vibrational problem. Anharmonicity parameters for potential-energy surfaces in complexes with strong, medium, and weak H-bonds were calculated under identical conditions. The obtained anharmonicity parameters were compared with the corresponding diagonal anharmonicity constants for stretching vibrations of the bridging protons and the lengths of the hydrogen bridges.

The origins of intra- and inter-molecular vibrational couplings: A case study of H{sub 2}O-Ar on full and reduced-dimensional potential energy surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hou, Dan; Ma, Yong-Tao; Zhang, Xiao-Long

2016-01-07

The origin and strength of intra- and inter-molecular vibrational coupling is difficult to probe by direct experimental observations. However, explicitly including or not including some specific intramolecular vibrational modes to study intermolecular interaction provides a precise theoretical way to examine the effects of anharmonic coupling between modes. In this work, a full-dimension intra- and inter-molecular ab initio potential energy surface (PES) for H{sub 2}O–Ar, which explicitly incorporates interdependence on the intramolecular (Q{sub 1},  Q{sub 2},  Q{sub 3}) normal-mode coordinates of the H{sub 2}O monomer, has been calculated. In addition, four analytic vibrational-quantum-state-specific PESs are obtained by least-squares fitting vibrationally averagedmore » interaction energies for the (v{sub 1},  v{sub 2},  v{sub 3}) =  (0,  0,  0), (0,  0,  1), (1,  0,  0), (0,  1,  0) states of H{sub 2}O to the three-dimensional Morse/long-range potential function. Each vibrationally averaged PES fitted to 442 points has root-mean-square (rms) deviation smaller than 0.15 cm{sup −1}, and required only 58 parameters. With the 3D PESs of H{sub 2}O–Ar dimer system, we employed the combined radial discrete variable representation/angular finite basis representation method and Lanczos algorithm to calculate rovibrational energy levels. This showed that the resulting vibrationally averaged PESs provide good representations of the experimental infrared data, with rms discrepancies smaller than 0.02 cm{sup −1} for all three rotational branches of the asymmetric stretch fundamental transitions. The infrared band origin shifts associated with three fundamental bands of H{sub 2}O in H{sub 2}O–Ar complex are predicted for the first time and are found to be in good agreement with the (extrapolated) experimental values. Upon introduction of additional intramolecular degrees of freedom into the intermolecular potential energy surface, there is clear spectroscopic evidence of intra- and intermolecular vibrational couplings.« less

A zero phase adaptive fuzzy Kalman filter for physiological tremor suppression in robotically assisted minimally invasive surgery.

PubMed

Sang, Hongqiang; Yang, Chenghao; Liu, Fen; Yun, Jintian; Jin, Guoguang; Chen, Fa

2016-12-01

Hand physiological tremor of surgeons can cause vibration at the surgical instrument tip, which may make it difficult for the surgeon to perform fine manipulations of tissue, needles, and sutures. A zero phase adaptive fuzzy Kalman filter (ZPAFKF) is proposed to suppress hand tremor and vibration of a robotic surgical system. The involuntary motion can be reduced by adding a compensating signal that has the same magnitude and frequency but opposite phase with the tremor signal. Simulations and experiments using different filters were performed. Results show that the proposed filter can avoid the loss of useful motion information and time delay, and better suppress minor and varying tremor. The ZPAFKF can provide less error, preferred accuracy, better tremor estimation, and more desirable compensation performance, to suppress hand tremor and decrease vibration at the surgical instrument tip. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Mesoscopic structure formation in condensed matter due to vacuum fluctuations

NASA Astrophysics Data System (ADS)

Sen, Siddhartha; Gupta, Kumar S.; Coey, J. M. D.

2015-10-01

An observable influence of zero-point fluctuations of the vacuum electromagnetic field on bound electrons is well known in the hydrogen atom, where it produces the Lamb shift. Here, we adapt an approach used to explain the Lamb shift in terms of a slight expansion of the orbits due to interaction with the zero-point field and apply it to assemblies of N electrons that are modeled as independent atomically bound two-level systems. The effect is to stabilize a collective ground-state energy, which leads to a prediction of novel effects at room temperature for quasi-two-dimensional systems over a range of parameters in the model, namely, N , the two-level excitation energy ℏ ω and the ionization energy ℏ ω +ɛ . Some mesoscopic systems where these effects may be observable include water sheaths on protein or DNA, surfaces of gaseous nanobubbles, and the magnetic response of inhomogeneous, electronically dilute oxides. No such effects are envisaged for uniform three-dimensional systems.

Solvent effects on the excited-state double proton transfer mechanism in the 7-azaindole dimer: a TDDFT study with the polarizable continuum model.

PubMed

Yu, Xue-Fang; Yamazaki, Shohei; Taketsugu, Tetsuya

2017-08-30

Solvent effects on the excited-state double proton transfer (ESDPT) mechanism in the 7-azaindole (7AI) dimer were investigated using the time-dependent density functional theory (TDDFT) method. Excited-state potential energy profiles along the reaction paths in a locally excited (LE) state and a charge transfer (CT) state were calculated using the polarizable continuum model (PCM) to include the solvent effect. A series of non-polar and polar solvents with different dielectric constants were used to examine the polarity effect on the ESDPT mechanism. The present results suggest that in a non-polar solvent and a polar solvent with a small dielectric constant, ESDPT follows a concerted mechanism, similar to the case in the gas phase. In a polar solvent with a relatively large dielectric constant, however, ESDPT is likely to follow a stepwise mechanism via a stable zwitterionic intermediate in the LE state on the adiabatic potential energy surface, although inclusion of zero-point vibrational energy (ZPE) corrections again suggests the concerted mechanism. In the meantime, the stepwise reaction path involving the CT state with neutral intermediates is also examined, and is found to be less competitive than the concerted or stepwise path in the LE state in both non-polar and polar solvents. The present study provides a new insight into the experimental controversy of the ESDPT mechanism of the 7AI dimer in a solution.

Spontaneous Droplet Motion on a Periodically Compliant Substrate.

PubMed

Liu, Tianshu; Nadermann, Nichole; He, Zhenping; Strogatz, Steven H; Hui, Chung-Yuen; Jagota, Anand

2017-05-23

Droplet motion arises in many natural phenomena, ranging from the familiar gravity-driven slip and arrest of raindrops on windows to the directed transport of droplets for water harvesting by plants and animals under dry conditions. Deliberate transportation and manipulation of droplets are also important in many technological applications, including droplet-based microfluidic chemical reactors and for thermal management. Droplet motion usually requires gradients of surface energy or temperature or external vibration to overcome contact angle hysteresis. Here, we report a new phenomenon in which a drying droplet placed on a periodically compliant surface undergoes spontaneous, erratic motion in the absence of surface energy gradients and external stimuli such as vibration. By modeling the droplet as a mass-spring system on a substrate with periodically varying compliance, we show that the stability of equilibrium depends on the size of the droplet. Specifically, if the center of mass of the drop lies at a stable equilibrium point of the system, it will stay there until evaporation reduces its size and this fixed point becomes unstable; with any small perturbation, the droplet then moves to one of its neighboring fixed points.

Computational Chemistry Modeling of the Atmospheric Fate of Toxic Industrial Compounds (TICs)

DTIC Science & Technology

2007-06-01

1+G(3df,2p) number of atoms and number of basis functions) of the (LRG) compounds under study precludes the use of coupled 0 Zero Point Energy ( ZPE ...overlap (NDDO) The extrapolated energy = E(QCI) + E(LRG) - Hamiltonian that is reparameterized to accurately E(SML) + ZPE reproduce coupled cluster

Spectroscopic (FT-IR, FT-Raman, and UV-visible) and quantum chemical studies on molecular geometry, Frontier molecular orbitals, NBO, NLO and thermodynamic properties of 1-acetylindole.

PubMed

Shukla, Vikas K; Al-Abdullah, Ebtehal S; El-Emam, Ali A; Sachan, Alok K; Pathak, Shilendra K; Kumar, Amarendra; Prasad, Onkar; Bishnoi, Abha; Sinha, Leena

2014-12-10

Quantum chemical calculations of ground state energy, geometrical structure and vibrational wavenumbers of 1-acetylindole were carried out using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. The FT-IR and FT-Raman spectra were recorded in the condensed state. The fundamental vibrational wavenumbers were calculated and a good correlation between experimental and scaled calculated wavenumbers has been accomplished. Electric dipole moment, polarizability and first static hyperpolarizability values of 1-acetylindole have been calculated at the same level of theory and basis set. The results show that the 1-acetylindole molecule possesses nonlinear optical (NLO) behavior with non-zero values. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-Visible spectrum of the molecule was recorded in the region 200-500nm and the electronic properties like HOMO and LUMO energies and composition were obtained using TD-DFT method. The calculated energies and oscillator strengths are in good correspondence with the experimental data. The thermodynamic properties of the compound under investigation were calculated at different temperatures. Copyright © 2014 Elsevier B.V. All rights reserved.

Ultralow Energy Electron Attachment at Sub-Millielectron Volt Resolution

NASA Astrophysics Data System (ADS)

Chutjian, Ara

1999-10-01

The technique of rare-gas photoionization(J. M. Ajello and A. Chutjian, J. Chem. Phys. 65), 5524 (1976). has been extended(A. Kortyna, M. Darrach and A. Chutjian, Bull. Am. Phys. Soc. 43), 1336 (1998). by use of direct laser ionization to electron energies ɛ in the range 0-100 meV, with a resolution Δɛ of 0.4-0.5 meV (FWHM). Tunable UV light at λ276 nm is produced using a pulsed Nd:YAG laser and nonlinear mixing techniques. The beam is frequency tripled in a pulsed jet of xenon. The VUV radiation, tunable at λ92 nm, is then used to photoionize Xe at its ^2P_1/2 threshold (single-photon ionization). The photoelectrons produced interact with admixed target gas to generate negative ions through the s-wave capture process. Recent results in electron attachment to SF6 will be reported which show resonance structure at the opening of the ground-state vibrational channels.^3,(H. Hotop et al., AIP Conf. Proc. Ser. 360 (AIP, New York, 1995), and private communication.) This structure corresponds to the process of vibrational excitation + attachment, which is superimposed on the underlying s-wave (direct) capture process. It should be a general phenomenon, present in a wide variety of zero-energy electron attaching molecules.

Molecular structure, spectroscopic studies and first-order molecular hyperpolarizabilities of ferulic acid by density functional study

NASA Astrophysics Data System (ADS)

Sebastian, S.; Sundaraganesan, N.; Manoharan, S.

2009-10-01

Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of ferulic acid (FA) (4-hydroxy-3-methoxycinnamic acid) were carried out by using density functional (DFT/B3LYP/BLYP) method with 6-31G(d,p) as basis set. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The vibrational spectral data obtained from solid phase FT-IR and FT-Raman spectra are assigned based on the results of the theoretical calculations. The observed spectra are found to be in good agreement with calculated values. The electric dipole moment ( μ) and the first hyperpolarizability ( β) values of the investigated molecule have been computed using ab initio quantum mechanical calculations. The calculation results also show that the FA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the infrared and Raman spectra of FA was also reported. The energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) results complements with the experimental findings. The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. The theoretical FT-IR and FT-Raman spectra for the title molecule have been constructed.

Analytic energy gradients for the orbital-optimized third-order Møller-Plesset perturbation theory

NASA Astrophysics Data System (ADS)

Bozkaya, Uǧur

2013-09-01

Analytic energy gradients for the orbital-optimized third-order Møller-Plesset perturbation theory (OMP3) [U. Bozkaya, J. Chem. Phys. 135, 224103 (2011)], 10.1063/1.3665134 are presented. The OMP3 method is applied to problematic chemical systems with challenging electronic structures. The performance of the OMP3 method is compared with those of canonical second-order Møller-Plesset perturbation theory (MP2), third-order Møller-Plesset perturbation theory (MP3), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] for investigating equilibrium geometries, vibrational frequencies, and open-shell reaction energies. For bond lengths, the performance of OMP3 is in between those of MP3 and CCSD. For harmonic vibrational frequencies, the OMP3 method significantly eliminates the singularities arising from the abnormal response contributions observed for MP3 in case of symmetry-breaking problems, and provides noticeably improved vibrational frequencies for open-shell molecules. For open-shell reaction energies, OMP3 exhibits a better performance than MP3 and CCSD as in case of barrier heights and radical stabilization energies. As discussed in previous studies, the OMP3 method is several times faster than CCSD in energy computations. Further, in analytic gradient computations for the CCSD method one needs to solve λ-amplitude equations, however for OMP3 one does not since λ _{ab}^{ij(1)} = t_{ij}^{ab(1)} and λ _{ab}^{ij(2)} = t_{ij}^{ab(2)}. Additionally, one needs to solve orbital Z-vector equations for CCSD, but for OMP3 orbital response contributions are zero owing to the stationary property of OMP3. Overall, for analytic gradient computations the OMP3 method is several times less expensive than CCSD (roughly ˜4-6 times). Considering the balance of computational cost and accuracy we conclude that the OMP3 method emerges as a very useful tool for the study of electronically challenging chemical systems.

Analytic energy gradients for the orbital-optimized third-order Møller-Plesset perturbation theory.

PubMed

Bozkaya, Uğur

2013-09-14

Analytic energy gradients for the orbital-optimized third-order Møller-Plesset perturbation theory (OMP3) [U. Bozkaya, J. Chem. Phys. 135, 224103 (2011)] are presented. The OMP3 method is applied to problematic chemical systems with challenging electronic structures. The performance of the OMP3 method is compared with those of canonical second-order Møller-Plesset perturbation theory (MP2), third-order Møller-Plesset perturbation theory (MP3), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] for investigating equilibrium geometries, vibrational frequencies, and open-shell reaction energies. For bond lengths, the performance of OMP3 is in between those of MP3 and CCSD. For harmonic vibrational frequencies, the OMP3 method significantly eliminates the singularities arising from the abnormal response contributions observed for MP3 in case of symmetry-breaking problems, and provides noticeably improved vibrational frequencies for open-shell molecules. For open-shell reaction energies, OMP3 exhibits a better performance than MP3 and CCSD as in case of barrier heights and radical stabilization energies. As discussed in previous studies, the OMP3 method is several times faster than CCSD in energy computations. Further, in analytic gradient computations for the CCSD method one needs to solve λ-amplitude equations, however for OMP3 one does not since λ(ab)(ij(1))=t(ij)(ab(1)) and λ(ab)(ij(2))=t(ij)(ab(2)). Additionally, one needs to solve orbital Z-vector equations for CCSD, but for OMP3 orbital response contributions are zero owing to the stationary property of OMP3. Overall, for analytic gradient computations the OMP3 method is several times less expensive than CCSD (roughly ~4-6 times). Considering the balance of computational cost and accuracy we conclude that the OMP3 method emerges as a very useful tool for the study of electronically challenging chemical systems.

Observable consequences of zero-point energy

NASA Astrophysics Data System (ADS)

Sen, Siddhartha; Gupta, Kumar S.

2017-12-01

Spectral line widths, the Lamb shift and the Casimir effect are generally accepted to be observable consequences of the zero-point electromagnetic (ZPEM) fields. A new class of observable consequences of ZPEM field at the mesoscopic scale were recently proposed and observed. Here, we extend this class of observable effects and predict that mesoscopic water layers should have a high value for its solid-liquid phase transition temperature, as illustrated by water inside a single-walled carbon nanotube (CNT). For this case, our analysis predicts that the phase transition temperature scales inversely with the square of the effective radius available for the water flow within the CNT.

A theoretical study of the stability of anionic defects in cubic ZrO 2 at extreme conditions

DOE PAGES

Samanta, Amit

2016-02-19

Using first principles density functional theory calculations, we present a study of the structure, mobility, and the thermodynamic stability of anionic defects in the high-temperature cubic phase of ZrO 2. Our results suggest that the local structure of an oxygen interstitial depends on the charge state and the cubic symmetry of the anionic sublattice is unstable at 0 K. In addition, the oxygen interstitials and the vacancies exhibit symmetry breaking transitions to low-energy structures with tetragonal distortion of the oxygen sublattice at 0 K. However, the vibrational entropy stabilizes the defect structures with cubic symmetry at 2600–2980 K. The formationmore » free energies of the anionic defects and Gibbs free energy changes associated with different defect reactions are calculated by including the vibrational free energy contributions and the effect of pressure on these defect structures. By analyzing the defect chemistry, we obtain the defect concentrations at finite temperature and pressure conditions using the zero temperature ab initio results as input and find that at low oxygen partial pressures, neutral oxygen vacancies are most dominant and at high oxygen partial pressures, doubly charged anionic defects are dominant. As a result, the relevance of the results to the thermal protective coating capabilities of zirconium-based ceramic composites is elucidated.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lifeng, E-mail: walfe@nuaa.edu.cn; Hu, Haiyan

The thermal vibration of a rectangular single-layered graphene sheet is investigated by using a rectangular nonlocal elastic plate model with quantum effects taken into account when the law of energy equipartition is unreliable. The relation between the temperature and the Root of Mean Squared (RMS) amplitude of vibration at any point of the rectangular single-layered graphene sheet in simply supported case is derived first from the rectangular nonlocal elastic plate model with the strain gradient of the second order taken into consideration so as to characterize the effect of microstructure of the graphene sheet. Then, the RMS amplitude of thermalmore » vibration of a rectangular single-layered graphene sheet simply supported on an elastic foundation is derived. The study shows that the RMS amplitude of the rectangular single-layered graphene sheet predicted from the quantum theory is lower than that predicted from the law of energy equipartition. The maximal relative difference of RMS amplitude of thermal vibration appears at the sheet corners. The microstructure of the graphene sheet has a little effect on the thermal vibrations of lower modes, but exhibits an obvious effect on the thermal vibrations of higher modes. The quantum effect is more important for the thermal vibration of higher modes in the case of smaller sides and lower temperature. The relative difference of maximal RMS amplitude of thermal vibration of a rectangular single-layered graphene sheet decreases monotonically with an increase of temperature. The absolute difference of maximal RMS amplitude of thermal vibration of a rectangular single-layered graphene sheet increases slowly with the rising of Winkler foundation modulus.« less

Multibody Parachute Flight Simulations for Planetary Entry Trajectories Using "Equilibrium Points"

NASA Technical Reports Server (NTRS)

Raiszadeh, Ben

2003-01-01

A method has been developed to reduce numerical stiffness and computer CPU requirements of high fidelity multibody flight simulations involving parachutes for planetary entry trajectories. Typical parachute entry configurations consist of entry bodies suspended from a parachute, connected by flexible lines. To accurately calculate line forces and moments, the simulations need to keep track of the point where the flexible lines meet (confluence point). In previous multibody parachute flight simulations, the confluence point has been modeled as a point mass. Using a point mass for the confluence point tends to make the simulation numerically stiff, because its mass is typically much less that than the main rigid body masses. One solution for stiff differential equations is to use a very small integration time step. However, this results in large computer CPU requirements. In the method described in the paper, the need for using a mass as the confluence point has been eliminated. Instead, the confluence point is modeled using an "equilibrium point". This point is calculated at every integration step as the point at which sum of all line forces is zero (static equilibrium). The use of this "equilibrium point" has the advantage of both reducing the numerical stiffness of the simulations, and eliminating the dynamical equations associated with vibration of a lumped mass on a high-tension string.

Fatigue study and improve reliability of cantilever type micro piezoelectric energy harvesters reinforced with flexible adhesive conductive tape

NASA Astrophysics Data System (ADS)

Lin, T. K.; Hsieh, Y. C.; Chen, C. T.; Chen, J. J.; Wu, W. J.

2016-04-01

Cantilever type piezoelectric energy harvester (PEH) is widely adopted in the design of vibration energy harvesters because of simple, effective and easy to fabricate. When the PEH is working under excitation of continuous vibration sources, like mounting on motors, reliability and durability is a major concern. The failure mode and fatigue issues will be important design considerations in field applications. Since the largest strain of a cantilever structure is located in the clamping position of fixed end, the location is therefore the weakest point of the structure and the hot zone of mechanical cracks. The failure mode due to fatigue under long time excitation of vibration sources is typically continuously developing small cracks on the piezoelectric PZT films till tearing the surface electrodes and caused open circuit to the output circuitry. Therefore, extending the lifetime with minimize the surface electrodes cracking becomes a key point for field applications. Previously, we focused on the output performance of PEH. At PowerMEMS 2014 [1], we presented a high performance PEH based on PZT thin films fabricated with a homemade PZT deposition equipment on stainless steel substrates. We confirmed that the stainless steel based PEH can generate better output power than silicon based devices under the same vibration excitation levels, and also the stainless based PEH can have longer lifetime when excited at higher vibration levels due to better mechanical strength. In this study, we tried to further reinforce the PEH with a conductive adhesive tape sticking on the surface electrode near the clamping position. We investigated the change of failure mode and mechanical behaviors, including the frequency bandwidth and non-linearity of the piezoelectric energy harvester. The PEH devices was mounted on a shaker for long time testing with vibration frequency set around 120Hz at 0.5g, 0.6g, and 0.7g acceleration vibration levels. The electrodes of the PEH device were cracked after 13 million cycles under 0.5g and 1 million cycles under 0.6g. The PEH has significant output power decreasing after the electrode is cracked and before being fully open circuit. The cracks of stainless steel substrate was also found after 1 million cycles under 0.7g vibration. For the device reinforced with conductive adhesive tape, we can see a steady output without degradation extended to more than 1.5 million cycles under 0.7g vibration. The other interesting finding in this study is with the added damping after adhering the conductive tape, the frequency bandwidth increased from 1.5Hz to 4Hz under 0.5g vibration level while the resonance frequency increased from 105Hz to 128Hz. Moreover, the reinforced devices have much better stability and linearity performance compared with the original devices. All the experimental details and discussion of the flexible conductive adhesive tape reinforced PEH will all be detailed in this paper.

Does the pressure dependence of kinetic isotope effects report usefully on dynamics in enzyme H-transfer reactions?

PubMed

Hoeven, Robin; Heyes, Derren J; Hay, Sam; Scrutton, Nigel S

2015-08-01

The temperature dependence of kinetic isotope effects (KIEs) has emerged as the main experimental probe of enzymatic H-transfer by quantum tunnelling. Implicit in the interpretation is a presumed role for dynamic coupling of H-transfer chemistry to the protein environment, the so-called 'promoting motions/vibrations hypothesis'. This idea remains contentious, and others have questioned the importance and/or existence of promoting motions/vibrations. New experimental methods of addressing this problem are emerging, including use of mass-modulated enzymes and time-resolved spectroscopy. The pressure dependence of KIEs has been considered as a potential probe of quantum tunnelling reactions, because semi-classical KIEs, which are defined by differences in zero-point vibrational energy, are relatively insensitive to kbar changes in pressure. Reported combined pressure and temperature (p-T) dependence studies of H-transfer reactions are, however, limited. Here, we extend and review the available p-T studies that have utilized well-defined experimental systems in which quantum mechanical tunnelling is established. These include flavoproteins, quinoproteins, light-activated enzymes and chemical model systems. We show that there is no clear general trend between the p-T dependencies of the KIEs in these systems. Given the complex nature of p-T studies, we conclude that computational simulations using determined (e.g. X-ray) structures are also needed alongside experimental measurements of reaction rates/KIEs to guide the interpretation of p-T effects. In providing new insight into H-transfer/environmental coupling, combined approaches that unite both atomistic understanding with experimental rate measurements will require careful evaluation on a case-by-case basis. Although individually informative, we conclude that p-T studies do not provide the more generalized insight that has come from studies of the temperature dependence of KIEs. © 2015 The Authors. FEBS Journal published by John Wiley & Sons Ltd on behalf of FEBS.

Low-energy phonon dispersion in LaFe4Sb12

NASA Astrophysics Data System (ADS)

Leithe-Jasper, Andreas; Boehm, Martin; Mutka, Hannu; Koza, Michael M.

We studied the vibrational dynamics of a single crystal of LaFe4Sb12 by three-axis inelastic neutron spectroscopy. The dispersion of phonons with wave vectors q along [ xx 0 ] and [ xxx ] directions in the energy range of eigenmodes with high amplitudes of lanthanum vibrations, i.e., at ℏω < 12 meV is identified. Symmetry-avoided anticrossing dispersion of phonons is established in both monitored directions and distinct eigenstates at high-symmetry points and at the Brillouin-zone center are discriminated. The experimentally derived phonon dispersion and intensities are compared with and backed up by ab initio lattice dynamics calculations. results of the computer model match well with the experimental data.

Torsion-wagging tunneling and vibrational states in hydrazine determined from its ab initio potential energy surface

NASA Astrophysics Data System (ADS)

Łodyga, Wiesław; Makarewicz, Jan

2012-05-01

Geometries, anharmonic vibrations, and torsion-wagging (TW) multiplets of hydrazine and its deuterated species are studied using high-level ab initio methods employing the second-order Møller-Plesset perturbation theory (MP2) as well as the coupled cluster singles and doubles model including connected triple corrections, CCSD(T), in conjunction with extended basis sets containing diffuse and core functions. To describe the splitting patterns caused by tunneling in TW states, the 3D potential energy surface (PES) for the large-amplitude TW modes is constructed. Stationary points in the 3D PES, including equivalent local minima and saddle points are characterized. Using this 3D PES, a flexible Hamiltonian is built numerically and then employed to solve the vibrational problem for TW coupled motion. The calculated ground state rav structure is expected to be more reliable than the experimental one that has been determined using a simplified structural model. The calculated fundamental frequencies allowed resolution of the assignment problems discussed earlier in the literature. The determined energy barriers, including the contributions from the small-amplitude vibrations, to the tunneling of the symmetric and antisymmetric wagging mode of 1997 cm-1 and 3454 cm-1, respectively, are in reasonable agreement with the empirical estimates of 2072 cm-1 and 3312 cm-1, respectively [W. Łodyga et al. J. Mol. Spectrosc. 183, 374 (1997), 10.1006/jmsp.1997.7271]. However, the empirical torsion barrier of 934 cm-1 appears to be overestimated. The ab initio calculations yield two torsion barriers: cis and trans of 744 cm-1 and 2706 cm-1, respectively. The multiplets of the excited torsion states are predicted from the refined 3D PES.

Plate with decentralised velocity feedback loops: Power absorption and kinetic energy considerations

NASA Astrophysics Data System (ADS)

Gardonio, P.; Miani, S.; Blanchini, F.; Casagrande, D.; Elliott, S. J.

2012-04-01

This paper is focused on the vibration effects produced by an array of decentralised velocity feedback loops that are evenly distributed over a rectangular thin plate to minimise its flexural response. The velocity feedback loops are formed by collocated ideal velocity sensor and point force actuator pairs, which are unconditionally stable and produce 'sky-hook' damping on the plate. The study compares how the overall flexural vibration of the plate and the local absorption of vibration power by the feedback loops vary with the control gains. The analysis is carried out both considering a typical frequency-domain formulation based on kinetic energy and structural power physical quantities, which is normally used to study vibration and noise problems, and a time-domain formulation also based on kinetic energy and structural power, which is usually implemented to investigate control problems. The time-domain formulation shows to be much more computationally efficient and robust with reference to truncation errors. Thus it has been used to perform a parametric study to assess if, and under which conditions, the minimum of the kinetic energy and the maximum of the absorbed power cost functions match with reference to: (a) the number of feedback control loops, (b) the structural damping in the plate, (c) the mutual distance of a pair of control loops and (d) the mutual gains implemented in a pair of feedback loops.

LIF excitation spectra for S 0 → S 1 transition of deuterated anthranilic acid COOD, ND 2 in supersonic-jet expansion

NASA Astrophysics Data System (ADS)

Kolek, Przemysław; Leśniewski, Sebastian; Andrzejak, Marcin; Góra, Maciej; Cias, Pawel; Weģrzynowicz, Adam; Najbar, Jan

2010-12-01

Laser induced fluorescence (LIF) excitation spectrum for the S 0 → S 1 transition of anthranilic acid molecules deuterated in the substituent groups (COOD, ND 2) was investigated. Analysis of the LIF spectrum allowed for the assignment of the six most prominent fundamental in-plane modes of frequencies up to ca. 850 cm. The experimental results show good correlation with the frequency changes upon deuteration computed with CIS (CI-Singles) and TD-DFT for the S 1 state. Deuteration induced red-shifts of the identified fundamental bands are used for examination of the alternative assignments proposed in earlier studies. Potential energy distributions (PED) and overlaps of the in-plane normal modes with frequencies below 850 cm indicate that the correspondence of the respective vibrations of the deuterated and non-deuterated molecule is very good. A blue-shift of the 00 transition due to the isotopic substitution, is equal to 47 cm. This relatively large value is caused primarily by a significant decrease of the N-H stretching frequency associated with the increase of strength of the intramolecular hydrogen bond upon the electronic excitation. The deuteration shift of the 00 band was interpreted in terms of the differences of the zero point energy (ZPE) between the S 0 and S 1 electronic states, computed with DFT and TD-DFT methods, respectively.

Geometric constraints in semiclassical initial value representation calculations in Cartesian coordinates: accurate reduction in zero-point energy.

PubMed

Issack, Bilkiss B; Roy, Pierre-Nicholas

2005-08-22

An approach for the inclusion of geometric constraints in semiclassical initial value representation calculations is introduced. An important aspect of the approach is that Cartesian coordinates are used throughout. We devised an algorithm for the constrained sampling of initial conditions through the use of multivariate Gaussian distribution based on a projected Hessian. We also propose an approach for the constrained evaluation of the so-called Herman-Kluk prefactor in its exact log-derivative form. Sample calculations are performed for free and constrained rare-gas trimers. The results show that the proposed approach provides an accurate evaluation of the reduction in zero-point energy. Exact basis set calculations are used to assess the accuracy of the semiclassical results. Since Cartesian coordinates are used, the approach is general and applicable to a variety of molecular and atomic systems.

Impurity bound states in mesoscopic topological superconducting loops

NASA Astrophysics Data System (ADS)

Jin, Yan-Yan; Zha, Guo-Qiao; Zhou, Shi-Ping

2018-06-01

We study numerically the effect induced by magnetic impurities in topological s-wave superconducting loops with spin-orbit interaction based on spin-generalized Bogoliubov-de Gennes equations. In the case of a single magnetic impurity, it is found that the midgap bound states can cross the Fermi level at an appropriate impurity strength and the circulating spin current jumps at the crossing point. The evolution of the zero-energy mode can be effectively tuned by the located site of a single magnetic impurity. For the effect of many magnetic impurities, two independent midway or edge impurities cannot lead to the overlap of zero modes. The multiple zero-energy modes can be effectively realized by embedding a single Josephson junction with impurity scattering into the system, and the spin current displays oscillatory feature with increasing the layer thickness.

40 CFR 86.1333 - Transient test cycle generation.

Code of Federal Regulations, 2014 CFR

2014-07-01

... zero percent speeds, zero percent torque points, but may be engaged up to two points preceding a non-zero point, and may be engaged for time segments with zero percent speed and torque points of durations...

Distributed measurement of acoustic vibration location with frequency multiplexed phase-OTDR

NASA Astrophysics Data System (ADS)

Iida, Daisuke; Toge, Kunihiro; Manabe, Tetsuya

2017-07-01

All-fiber distributed vibration sensing is attracting attention in relation to structural health monitoring because it is cost effective, offers high coverage of the monitored area and can detect various structural problems. And in particular the demand for high-speed vibration sensing operating at more than 10 kHz has increased because high frequency vibration indicates high energy and severe trouble in the monitored object. Optical fiber vibration sensing with phase-sensitive optical time domain reflectometry (phase-OTDR) has long been studied because it can be used for distributed vibration sensing in optical fiber. However, pulse reflectometry such as OTDR cannot measure high-frequency vibration whose cycle is shorter than the repetition time of the OTDR. That is, the maximum detectable frequency depends on fiber length. In this paper, we describe a vibration sensing technique with frequency-multiplexed OTDR that can detect the entire distribution of a high-frequency vibration thus allowing us to locate a high-speed vibration point. We can measure the position, frequency and dynamic change of a high-frequency vibration whose cycle is shorter than the repetition time. Both frequency and position are visualized simultaneously for a 5-km fiber with an 80-kHz frequency response and a 20-m spatial resolution.

Cloning single wall carbon nanotubes for hydrogen storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tour, James M; Kittrell, Carter

2012-08-30

The purpose of this research is to development the technology required for producing 3-D nano-engineered frameworks for hydrogen storage based on sp 2 carbon media, which will have high gravimetric and especially high volumetric uptake of hydrogen, and in an aligned fibrous array that will take advantage of the exceptionally high thermal conductivity of sp 2 carbon materials to speed up the fueling process while minimizing or eliminating the need for internal cooling systems. A limitation for nearly all storage media using physisorption of the hydrogen molecule is the large amount of surface area (SA) occupied by each H 2more » molecule due to its large zero-point vibrational energy. This creates a conundrum that in order to maximize SA, the physisorption media is made more tenuous and the density is decreased, usually well below 1 kg/L, so that there comes a tradeoff between volumetric and gravimetric uptake. Our major goal was to develop a new type of media with high density H 2 uptake, which favors volumetric storage and which, in turn, has the capability to meet the ultimate DoE H 2 goals.« less

Rocksalt or cesium chloride: Investigating the relative stability of the cesium halide structures with random phase approximation based methods

NASA Astrophysics Data System (ADS)

Nepal, Niraj K.; Ruzsinszky, Adrienn; Bates, Jefferson E.

2018-03-01

The ground state structural and energetic properties for rocksalt and cesium chloride phases of the cesium halides were explored using the random phase approximation (RPA) and beyond-RPA methods to benchmark the nonempirical SCAN meta-GGA and its empirical dispersion corrections. The importance of nonadditivity and higher-order multipole moments of dispersion in these systems is discussed. RPA generally predicts the equilibrium volume for these halides within 2.4% of the experimental value, while beyond-RPA methods utilizing the renormalized adiabatic LDA (rALDA) exchange-correlation kernel are typically within 1.8%. The zero-point vibrational energy is small and shows that the stability of these halides is purely due to electronic correlation effects. The rAPBE kernel as a correction to RPA overestimates the equilibrium volume and could not predict the correct phase ordering in the case of cesium chloride, while the rALDA kernel consistently predicted results in agreement with the experiment for all of the halides. However, due to its reasonable accuracy with lower computational cost, SCAN+rVV10 proved to be a good alternative to the RPA-like methods for describing the properties of these ionic solids.

Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes

NASA Astrophysics Data System (ADS)

Mazzuca, James W.; Haut, Nathaniel K.

2018-06-01

It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes.

PubMed

Mazzuca, James W; Haut, Nathaniel K

2018-06-14

It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

Comment on "How the huge energy of quantum vacuum gravitates to drive the slow accelerating expansion of the Universe"

NASA Astrophysics Data System (ADS)

Mazzitelli, Francisco D.; Trombetta, Leonardo G.

2018-03-01

In a recent paper [Q. Wang, Z. Zhu, and W. G. Unruh, Phys. Rev. D 95, 103504 (2017), 10.1103/PhysRevD.95.103504] it was argued that, due to the fluctuations around its mean value, vacuum energy gravitates differently from what was previously assumed. As a consequence, the Universe would accelerate with a small Hubble expansion rate, solving the cosmological constant and dark energy problems. We point out here that the results depend on the type of cutoff used to evaluate the vacuum energy. In particular, they are not valid when one uses a covariant cutoff such that the zero-point energy density is positive definite.

Self-biased magnetoelectric charge coupling in transducer of SmFe2, Pb(Zr,Ti)O3 stack, and stepped horn substrate with multi-frequency effect

NASA Astrophysics Data System (ADS)

Tang, Chengpei; Lu, Caijiang; Gao, Hongli; Fu, Guoqiang

2017-10-01

This paper presents a broadband, self-biased magnetoelectric (ME) charge coupling in a transducer comprising of a negative magnetostrictive SmFe2 plate, a piezoelectric Pb(Zr,Ti)O3 (PZT) stack, and a stepped horn substrate. By using the SmFe2 plate with a large anisotropic field, an outstanding self-biased piezomagnetic effect is realized. The horn serves as a waveguide with multiple resonances and converges vibrating energy excited by the SmFe2 plate from the wide side to the narrow side, which results in a higher vibrating magnification at the position of the PZT-stack. Then, a strong mechanical-electric coupling is realized by the use of the PZT-stack with high capacitance. Consequently, several large peaks of ME charge response with magnitudes of 1.02-18.99 nC/Oe in the 0.1-50 kHz range are observed at zero-biased magnetic field. This demonstrates that the proposed broadband self-biased structure may be useful for multifunctional devices such as low frequency AC magnetic field sensors or multi-frequency energy harvesters.

Molecular structure, vibrational spectroscopic, first order hyperpolarizability and HOMO-LUMO studies of 7-amino-8-oxo-3-vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid

NASA Astrophysics Data System (ADS)

Ramalingam, M.; Sethuraman, V.; Sundaraganesan, N.

2011-02-01

The FT-IR and FT-Raman spectra of 7-amino-8-oxo-3-vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid (7AVCA) were recorded in the region 4000-400 cm -1 and 3500-10 cm -1, respectively. Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers were carried out by ab initio HF and density functional theoretical methods invoking 6-311G(d,p) basis set. The differences between the observed and scaled wavenumber values of most of the fundamentals are very small. The electric dipole moment ( μ) and the first order hyperpolarizability ( β0) values have been computed quantum mechanically. The calculated results show that 7AVCA may have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the FT-IR and FT-Raman spectra of 7AVCA is reported. The theoretical IR and Raman spectra of 7AVCA have also been constructed. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule.

Molecular structure, vibrational spectroscopic, first order hyperpolarizability and HOMO-LUMO studies of 7-amino-8-oxo-3-vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid.

PubMed

Ramalingam, M; Sethuraman, V; Sundaraganesan, N

2011-02-01

The FT-IR and FT-Raman spectra of 7-amino-8-oxo-3-vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid (7AVCA) were recorded in the region 4000-400 cm(-1) and 3500-10 cm(-1), respectively. Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers were carried out by ab initio HF and density functional theoretical methods invoking 6-311G(d,p) basis set. The differences between the observed and scaled wavenumber values of most of the fundamentals are very small. The electric dipole moment (μ) and the first order hyperpolarizability (β0) values have been computed quantum mechanically. The calculated results show that 7AVCA may have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the FT-IR and FT-Raman spectra of 7AVCA is reported. The theoretical IR and Raman spectra of 7AVCA have also been constructed. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule. Copyright © 2010 Elsevier B.V. All rights reserved.

Calibration-quality adiabatic potential energy surfaces for H3(+) and its isotopologues.

PubMed

Pavanello, Michele; Adamowicz, Ludwik; Alijah, Alexander; Zobov, Nikolai F; Mizus, Irina I; Polyansky, Oleg L; Tennyson, Jonathan; Szidarovszky, Tamás; Császár, Attila G

2012-05-14

Calibration-quality ab initio adiabatic potential energy surfaces (PES) have been determined for all isotopologues of the molecular ion H(3)(+). The underlying Born-Oppenheimer electronic structure computations used optimized explicitly correlated shifted Gaussian functions. The surfaces include diagonal Born-Oppenheimer corrections computed from the accurate electronic wave functions. A fit to the 41,655 ab initio points is presented which gives a standard deviation better than 0.1 cm(-1) when restricted to the points up to 6000 cm(-1) above the first dissociation asymptote. Nuclear motion calculations utilizing this PES, called GLH3P, and an exact kinetic energy operator given in orthogonal internal coordinates are presented. The ro-vibrational transition frequencies for H(3)(+), H(2)D(+), and HD(2)(+) are compared with high resolution measurements. The most sophisticated and complete procedure employed to compute ro-vibrational energy levels, which makes explicit allowance for the inclusion of non-adiabatic effects, reproduces all the known ro-vibrational levels of the H(3)(+) isotopologues considered to better than 0.2 cm(-1). This represents a significant (order-of-magnitude) improvement compared to previous studies of transitions in the visible. Careful treatment of linear geometries is important for high frequency transitions and leads to new assignments for some of the previously observed lines. Prospects for further investigations of non-adiabatic effects in the H(3)(+) isotopologues are discussed. In short, the paper presents (a) an extremely accurate global potential energy surface of H(3)(+) resulting from high accuracy ab initio computations and global fit, (b) very accurate nuclear motion calculations of all available experimental line data up to 16,000 cm(-1), and (c) results suggest that we can predict accurately the lines of H(3)(+) towards dissociation and thus facilitate their experimental observation.

Calibration-quality adiabatic potential energy surfaces for H3+ and its isotopologues

NASA Astrophysics Data System (ADS)

Pavanello, Michele; Adamowicz, Ludwik; Alijah, Alexander; Zobov, Nikolai F.; Mizus, Irina I.; Polyansky, Oleg L.; Tennyson, Jonathan; Szidarovszky, Tamás; Császár, Attila G.

2012-05-01

Calibration-quality ab initio adiabatic potential energy surfaces (PES) have been determined for all isotopologues of the molecular ion H_3^+. The underlying Born-Oppenheimer electronic structure computations used optimized explicitly correlated shifted Gaussian functions. The surfaces include diagonal Born-Oppenheimer corrections computed from the accurate electronic wave functions. A fit to the 41 655 ab initio points is presented which gives a standard deviation better than 0.1 cm-1 when restricted to the points up to 6000 cm-1 above the first dissociation asymptote. Nuclear motion calculations utilizing this PES, called GLH3P, and an exact kinetic energy operator given in orthogonal internal coordinates are presented. The ro-vibrational transition frequencies for H_3^+, H2D+, and HD_2^+ are compared with high resolution measurements. The most sophisticated and complete procedure employed to compute ro-vibrational energy levels, which makes explicit allowance for the inclusion of non-adiabatic effects, reproduces all the known ro-vibrational levels of the H_3^+ isotopologues considered to better than 0.2 cm-1. This represents a significant (order-of-magnitude) improvement compared to previous studies of transitions in the visible. Careful treatment of linear geometries is important for high frequency transitions and leads to new assignments for some of the previously observed lines. Prospects for further investigations of non-adiabatic effects in the H_3^+ isotopologues are discussed. In short, the paper presents (a) an extremely accurate global potential energy surface of H_3^+ resulting from high accuracy ab initio computations and global fit, (b) very accurate nuclear motion calculations of all available experimental line data up to 16 000 cm-1, and (c) results suggest that we can predict accurately the lines of H_3^+ towards dissociation and thus facilitate their experimental observation.

Geometric Energy Derivatives at the Complete Basis Set Limit: Application to the Equilibrium Structure and Molecular Force Field of Formaldehyde.

PubMed

Morgan, W James; Matthews, Devin A; Ringholm, Magnus; Agarwal, Jay; Gong, Justin Z; Ruud, Kenneth; Allen, Wesley D; Stanton, John F; Schaefer, Henry F

2018-03-13

Geometric energy derivatives which rely on core-corrected focal-point energies extrapolated to the complete basis set (CBS) limit of coupled cluster theory with iterative and noniterative quadruple excitations, CCSDTQ and CCSDT(Q), are used as elements of molecular gradients and, in the case of CCSDT(Q), expansion coefficients of an anharmonic force field. These gradients are used to determine the CCSDTQ/CBS and CCSDT(Q)/CBS equilibrium structure of the S 0 ground state of H 2 CO where excellent agreement is observed with previous work and experimentally derived results. A fourth-order expansion about this CCSDT(Q)/CBS reference geometry using the same level of theory produces an exceptional level of agreement to spectroscopically observed vibrational band origins with a MAE of 0.57 cm -1 . Second-order vibrational perturbation theory (VPT2) and variational discrete variable representation (DVR) results are contrasted and discussed. Vibration-rotation, anharmonicity, and centrifugal distortion constants from the VPT2 analysis are reported and compared to previous work. Additionally, an initial application of a sum-over-states fourth-order vibrational perturbation theory (VPT4) formalism is employed herein, utilizing quintic and sextic derivatives obtained with a recursive algorithmic approach for response theory.

Towards zero-power ICT.

PubMed

Gammaitoni, Luca; Chiuchiú, D; Madami, M; Carlotti, G

2015-06-05

Is it possible to operate a computing device with zero energy expenditure? This question, once considered just an academic dilemma, has recently become strategic for the future of information and communication technology. In fact, in the last forty years the semiconductor industry has been driven by its ability to scale down the size of the complementary metal-oxide semiconductor-field-effect transistor, the building block of present computing devices, and to increase computing capability density up to a point where the power dissipated in heat during computation has become a serious limitation. To overcome such a limitation, since 2004 the Nanoelectronics Research Initiative has launched a grand challenge to address the fundamental limits of the physics of switches. In Europe, the European Commission has recently funded a set of projects with the aim of minimizing the energy consumption of computing. In this article we briefly review state-of-the-art zero-power computing, with special attention paid to the aspects of energy dissipation at the micro- and nanoscales.

Towards zero-power ICT

NASA Astrophysics Data System (ADS)

Gammaitoni, Luca; Chiuchiú, D.; Madami, M.; Carlotti, G.

2015-06-01

Is it possible to operate a computing device with zero energy expenditure? This question, once considered just an academic dilemma, has recently become strategic for the future of information and communication technology. In fact, in the last forty years the semiconductor industry has been driven by its ability to scale down the size of the complementary metal-oxide semiconductor-field-effect transistor, the building block of present computing devices, and to increase computing capability density up to a point where the power dissipated in heat during computation has become a serious limitation. To overcome such a limitation, since 2004 the Nanoelectronics Research Initiative has launched a grand challenge to address the fundamental limits of the physics of switches. In Europe, the European Commission has recently funded a set of projects with the aim of minimizing the energy consumption of computing. In this article we briefly review state-of-the-art zero-power computing, with special attention paid to the aspects of energy dissipation at the micro- and nanoscales.

Ab initio studies of the Rg–NO{sup +}(X{sup 1}Σ{sup +}) van der Waals complexes (Rg = He, Ne, Ar, Kr, and Xe)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orek, Cahit; Bulut, Niyazi, E-mail: jklos@umd.edu, E-mail: francois.lique@univ-lehavre.fr, E-mail: bulut-niyazi@yahoo.com; Kłos, Jacek, E-mail: jklos@umd.edu, E-mail: francois.lique@univ-lehavre.fr, E-mail: bulut-niyazi@yahoo.com

2016-05-28

We used the explicitly correlated variant of the coupled clusters method with single, double, and noniterative triple excitations [CCSD(T)-F12] to compute two-dimensional potential energy surfaces of van der Waals complexes formed by rare gas atoms (Rg) and NO{sup +}(X{sup 1}Σ{sup +}) cations. We used the correlation-consistent, triple-zeta (cc-pVTZ-F12) atomic basis sets, and for Kr and Xe rare gases, we employed corresponding pseudopotential cc-pVTZ-PP-F12 atomic basis sets. These basis sets were additionally augmented with mid-bond functions. The complexes are all of skewed T-shape type with Rg atom being closer to the N-side. Using analytical representation of the potentials, we have estimatedmore » zero-point energy corrected dissociation energies from anharmonic calculations with BOUND program and also from the harmonic approximation. The binding energies increase with the polarization of the Rg atom in series from He to Xe and are 196 cm{sup −1}, 360 cm{sup −1}, 1024 cm{sup −1}, 1434 cm{sup −1}, and 2141 cm{sup −1}, respectively. Their corresponding dissociation energies are 132 cm{sup −1}, 300 cm{sup −1}, 927 cm{sup −1}, 1320 cm{sup −1}, and 1994 cm{sup −1} for the complexes with He to Xe, respectively. We find good agreement with previous theoretical and experimental results. The harmonic vibrational frequencies were calculated for the bending and stretching modes of the Rg–NO{sup +} complexes.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadria-Vili, Yara; Bachilo, Sergei M.; Blackburn, Jeffrey L.

Photoluminescence spectra of single-walled carbon nanotubes (SWCNTs) have been recorded and analyzed for selected individual nanotubes and structurally sorted bulk samples to clarify the nature of secondary emission features. Room temperature spectra show, in addition to the main peak arising from the E 11 bright exciton, three features at lower frequency, which are identified here (in descending order of energy difference from E 11 emission) as G 1, X 1, and Y 1. The weakest (G 1) is interpreted as a vibrational satellite of E 11 involving excitation of the ~1600 cm -1 G mode. The X 1 feature, althoughmore » more intense than G 1, has a peak amplitude only ~3% of E 11. X 1 emission was found to be polarized parallel to E 11 and to be separated from that peak by 1068 cm -1 in SWCNTs with natural isotopic abundance. The separation remained unchanged for several ( n,m) species, different nanotube environments, and various levels of induced axial strain. In 13C SWCNTs, the spectral separation decreased to 1023 cm -1. The measured isotopic shift points to a phonon-assisted transition that excites the D vibration. This supports prior interpretations of the X 1 band as emission from the dark K-momentum exciton, whose energy we find to be ~230 cm -1 above E 11. The remaining sideband, Y 1, is red-shifted ~300 cm -1 from E 11 and varies in relative intensity among and within individual SWCNTs. We assign it as defect-induced emission, either from an extrinsic state or from a brightened triplet state. In contrast to single-nanotube spectra, bulk samples show asymmetric zero-phonon E 11 peaks, with widths inversely related to SWCNT diameter. As a result, an empirical expression for this dependence is presented to aid the simulation of overlapped emission spectra during quantitative fluorimetric analysis of bulk SWCNT samples.« less

Correlated phonons and the Tc-dependent dynamical phonon anomalies

NASA Astrophysics Data System (ADS)

Hakioğlu, T.; Türeci, H.

1997-11-01

Anomalously large low-temperature phonon anharmonicities can lead to static as well as dynamical changes in the low-temperature properties of the electron-phonon system. In this work, we focus our attention on the dynamically generated low-temperature correlations in an interacting electron-phonon system using a self-consistent dynamical approach in the intermediate coupling range. In the context of the model, the polaron correlations are produced by the charge-density fluctuations which are generated dynamically by the electron-phonon coupling. Conversely, the latter is influenced in the presence of the former. The purpose of this work is to examine the dynamics of this dual mechanism between the two using the illustrative Fröhlich model. In particular, the influence of the low-temperature phonon dynamics on the superconducting properties in the intermediate coupling range is investigated. The influence on the Holstein reduction factor as well as the enhancement in the zero-point fluctuations and in the electron-phonon coupling are calculated numerically. We also examine these effects in the presence of superconductivity. Within this model, the contribution of the electron-phonon interaction as one of the important elements in the mechanisms of superconductivity can reach values as high as 15-20% of the characteristic scale of the lattice vibrational energy. The second motivation of this work is to understand the nature of the Tc-dependent temperature anomalies observed in the Debye-Waller factor, dynamical pair correlations, and average atomic vibrational energies for a number of high-temperature superconductors. In our approach we do not claim nor believe that the electron-phonon interaction is the primary mechanism leading to high-temperature superconductivity. Nevertheless, our calculations suggest that the dynamically induced low-temperature phonon correlation model can account for these anomalies and illustrates their possible common origin. Finally, the relevance of incorporating these low-temperature effects into more realistic models of high-temperature superconductivity including both the charge and spin degrees and other similar ideas existing in the literature are discussed.

Photoluminescence side band spectroscopy of individual single-walled carbon nanotubes

DOE PAGES

Kadria-Vili, Yara; Bachilo, Sergei M.; Blackburn, Jeffrey L.; ...

2016-09-27

Photoluminescence spectra of single-walled carbon nanotubes (SWCNTs) have been recorded and analyzed for selected individual nanotubes and structurally sorted bulk samples to clarify the nature of secondary emission features. Room temperature spectra show, in addition to the main peak arising from the E 11 bright exciton, three features at lower frequency, which are identified here (in descending order of energy difference from E 11 emission) as G 1, X 1, and Y 1. The weakest (G 1) is interpreted as a vibrational satellite of E 11 involving excitation of the ~1600 cm -1 G mode. The X 1 feature, althoughmore » more intense than G 1, has a peak amplitude only ~3% of E 11. X 1 emission was found to be polarized parallel to E 11 and to be separated from that peak by 1068 cm -1 in SWCNTs with natural isotopic abundance. The separation remained unchanged for several ( n,m) species, different nanotube environments, and various levels of induced axial strain. In 13C SWCNTs, the spectral separation decreased to 1023 cm -1. The measured isotopic shift points to a phonon-assisted transition that excites the D vibration. This supports prior interpretations of the X 1 band as emission from the dark K-momentum exciton, whose energy we find to be ~230 cm -1 above E 11. The remaining sideband, Y 1, is red-shifted ~300 cm -1 from E 11 and varies in relative intensity among and within individual SWCNTs. We assign it as defect-induced emission, either from an extrinsic state or from a brightened triplet state. In contrast to single-nanotube spectra, bulk samples show asymmetric zero-phonon E 11 peaks, with widths inversely related to SWCNT diameter. As a result, an empirical expression for this dependence is presented to aid the simulation of overlapped emission spectra during quantitative fluorimetric analysis of bulk SWCNT samples.« less

Spring Tire

NASA Technical Reports Server (NTRS)

Asnani, Vivake M.; Benzing, Jim; Kish, Jim C.

2011-01-01

The spring tire is made from helical springs, requires no air or rubber, and consumes nearly zero energy. The tire design provides greater traction in sandy and/or rocky soil, can operate in microgravity and under harsh conditions (vastly varying temperatures), and is non-pneumatic. Like any tire, the spring tire is approximately a toroidal-shaped object intended to be mounted on a transportation wheel. Its basic function is also similar to a traditional tire, in that the spring tire contours to the surface on which it is driven to facilitate traction, and to reduce the transmission of vibration to the vehicle. The essential difference between other tires and the spring tire is the use of helical springs to support and/or distribute load. They are coiled wires that deform elastically under load with little energy loss.

Chiral zero energy modes in two-dimensional disordered Dirac semimetals

NASA Astrophysics Data System (ADS)

Liu, Lei; Yu, Yan; Wu, Hai-Bin; Zhang, Yan-Yang; Liu, Jian-Jun; Li, Shu-Shen

2018-04-01

The vacancy-induced chiral zero energy modes (CZEMs) of chiral-unitary-class (AIII) and chiral-symplectic-class (CII) two-dimensional (2 D ) disordered Dirac semimetals realized on a square bipartite lattice are investigated numerically by using the Kubo-Greenwood formula with the kernel polynomial method. The results show that, for both systems, the CZEMs exhibit the critical delocalization. The CZEM conductivity remains a robust constant (i.e., σ CZEM≈1.05 e2/h ), which is insensitive to the sample sizes, the vacancy concentrations, and the numbers of moments of Chebyshev polynomials, i.e., the dephasing strength. For both kinds of chiral systems, the CZEM conductivities are almost identical. However, they are not equal to that of graphene (i.e., 4 e2/π h ), which belongs to the chiral orthogonal class (BDI) semimetal on a 2 D hexagonal bipartite lattice. In addition, for the case that the vacancy concentrations are different in the two sublattices, the CZEM conductivity vanishes, and thus both systems exhibit localization at the Dirac point. Moreover, a band gap and a mobility gap open around zero energy. The widths of the energy gaps and mobility gaps are increasing with larger vacancy concentration difference. The width of the mobility gap is greater than that of the band gap, and a δ -function-like peak of density of states emerges at the Dirac point within the band gap, implying the existence of numerous localized states.

Ultra-sensitive probe of spectral line structure and detection of isotopic oxygen

NASA Astrophysics Data System (ADS)

Garner, Richard M.; Dharamsi, A. N.; Khan, M. Amir

2018-01-01

We discuss a new method of investigating and obtaining quantitative behavior of higher harmonic (> 2f) wavelength modulation spectroscopy (WMS) based on the signal structure. It is shown that the spectral structure of higher harmonic WMS signals, quantified by the number of zero crossings and turnings points, can have increased sensitivity to ambient conditions or line-broadening effects from changes in temperature, pressure, or optical depth. The structure of WMS signals, characterized by combinations of signal magnitude and spectral locations of turning points and zero crossings, provides a unique scale that quantifies lineshape parameters and, thus, useful in optimization of measurements obtained from multi-harmonic WMS signals. We demonstrate this by detecting weaker rotational-vibrational transitions of isotopic atmospheric oxygen (16O18O) in the near-infrared region where higher harmonic WMS signals are more sensitive contrary to their signal-to-noise ratio considerations. The proposed approach based on spectral structure provides the ability to investigate and quantify signals not only at linecenter but also in the wing region of the absorption profile. This formulation is particularly useful in tunable diode laser spectroscopy and ultra-precision laser-based sensors where absorption signal profile carries information of quantities of interest, e.g., concentration, velocity, or gas collision dynamics, etc.

Extinction cross-section suppression and active acoustic invisibility cloaking

NASA Astrophysics Data System (ADS)

Mitri, F. G.

2017-10-01

Invisibility in its canonical form requires rendering a zero extinction cross-section (or energy efficiency) from an active or a passive object. This work demonstrates the successful theoretical realization of this physical effect for an active cylindrically radiating acoustic body, undergoing periodic axisymmetric harmonic vibrations near a flat rigid boundary. Radiating, amplification and extinction cross-sections of the active source are defined. Assuming monopole and dipole modal oscillations of the circular source, conditions are found where the extinction energy efficiency factor of the active source vanishes, achieving total invisibility with minimal influence of the source size. It also takes positive or negative values, depending on its size and distance from the boundary. Moreover, the amplification energy efficiency factor is negative for the acoustically-active source. These effects also occur for higher-order modal oscillations of the active source. The results find potential applications in the development of acoustic cloaking devices and invisibility.

Bending wavefunctions for linear molecules

NASA Astrophysics Data System (ADS)

Hirano, Tsuneo; Nagashima, Umpei; Jensen, Per

2018-01-01

The bending motion of a linear triatomic molecule has two unique characteristics: the bending mode is doubly degenerate and only positive values of the bending angle, expressed by the bond angle supplement ρ bar , can be observed. The double degeneracy requires the wavefunction to be described as a two-dimensional oscillator. In the present work, we first review the conventional expressions based on two, symmetrically equivalent normal coordinates. Then we discuss an alternative expression for the bending wavefunction in terms of two geometrical coordinates, the bond angle supplement ρ bar (= π - τ ⩾ 0 , where τ is the bond angle) and the rotation angle χ (0 ⩽ χ < 2 π) describing rotation of the molecule around the molecular axis. In this formalism, defined for the (ρ bar , χ) polar-coordinate space with volume element ρ bar d ρ bar dχ , the one-dimensional wavefunction resulted through re-normalization for χ has zero amplitude at ρ bar = 0 , and the ro-vibrational average of the bending angle, i.e., the expectation value 〈 ρ bar 〉 , attains a non-zero, positive value for any ro-vibrational state including the vibrational ground state. This conclusion appears to cause some controversy since much conventional spectroscopic wisdom insists on 〈 ρ bar 〉 having the value zero.

Vibrational spectral investigation on xanthine and its derivatives—theophylline, caffeine and theobromine

NASA Astrophysics Data System (ADS)

Gunasekaran, S.; Sankari, G.; Ponnusamy, S.

2005-01-01

A normal coordinate analysis has been carried out on four compounds having a similar ring structure with different side chain substitutions, which are xanthine, caffeine, theophylline, and theobromine. Xanthine is chemically known as 2,6-dihydroxy purine. Caffeine, theophylline and theobromine are methylated xanthines. Considering the methyl groups as point mass, the number of normal modes of vibrations can be distributed as Γ vib=27 A'+12 A″ based on C s point group symmetry associated with the structures. In the present work 15 A' and 12 A″ normal modes are considered. A new set of orthonormal symmetry co-ordinates have been constructed. Wilson's F- G matrix method has been adopted for the normal coordinate analysis. A satisfactory vibrational band assignment has been made by employing the FTIR and FT Raman spectra of the compounds. The potential energy distribution is calculated with the arrived values of the force constants and hence the agreement of the frequency assignment has been checked.

Spectral and thermodynamic properties for the exciplexes of N-alkyl carbazoles with dicyanobenzenes in THF

NASA Astrophysics Data System (ADS)

Asim, Sadia; Mansha, Asim; Landgraf, Stephan; Grampp, Günter; Zahid, Muhammad; Bhatti, Haq Nawaz

2014-01-01

The exciplex emission spectra of N-ethylcarbazole with 1,2-dicyanobenzene (NEC/1,2-DCB), N-methylcarbazole with 1,2-dicyanobenzene (NMC/1,2-DCB), 1,3-dicyanobenzene (NMC/1,3-DCB), and 1,4-dicyanobenzene (NMC/1,4-DCB) are studied in tetrahydrofuran (THF) for the temperature range starting from 253 K to 334 K. Thermochromic shifts along with the spectral properties including change in peak intensities and the ratio of exciplex peak intensity to fluorophore peak intensity are studied. Effect of temperature on the energy of zero-zero transitions hνo‧, Huang-Rhys factor (S), Gauss broadening of vibronic level (σ) and the dominant high-frequency vibration (hνν) are also part of investigation. Enthalpy of exciplex formation (ΔHEX∗) calculated by the model proposed by A. Weller and the Gibb's energy of electron transfer (ΔGet∗) for all exciplex systems are also discussed in the present paper. All the exciplexes under study were observed to be dipolar in nature. The exciplex of the N-methylcarbazole/1,4-dicyanobenzene was found to be the most stable and the N-methylcarbazole/1,3-dicyanobenzene was the weakest exciplex system.

Absorption spectra of ammonia near 1 μm

NASA Astrophysics Data System (ADS)

Barton, Emma J.; Polyansky, Oleg L.; Yurchenko, Sergei. N.; Tennyson, Jonathan; Civiš, S.; Ferus, M.; Hargreaves, R.; Ovsyannikov, R. I.; Kyuberis, A. A.; Zobov, N. F.; Béguier, S.; Campargue, A.

2017-12-01

An ammonia absorption spectrum recorded at room temperature in the region 8800-10,400 cm-1 is analysed using a variational line list, BYTe, and ground state energies determined using the MARVEL procedure. BYTe is used as a starting point to initialise assignments by combination differences and the method of branches. Assignments are presented for the region 9400-9850 cm-1. 642 lines are assigned to 6 previously unobserved vibrational bands, (2v1 + 2 v42) ±, (2v1 + v31) ± and (v1 + v31 + 2 v42) ±, leading to 428 new energy levels with 208 confirmed by combination differences. A recently calculated purely ab initio NH3 PES is also used to calculate rovibrational energy levels. Comparison with assigned levels shows better agreement between observed and calculated levels than for BYTe for higher vibrational bands.

Theory of First Order Chemical Kinetics at the Critical Point of Solution.

PubMed

Baird, James K; Lang, Joshua R

2017-10-26

Liquid mixtures, which have a phase diagram exhibiting a miscibility gap ending in a critical point of solution, have been used as solvents for chemical reactions. The reaction rate in the forward direction has often been observed to slow down as a function of temperature in the critical region. Theories based upon the Gibbs free energy of reaction as the driving force for chemical change have been invoked to explain this behavior. With the assumption that the reaction is proceeding under relaxation conditions, these theories expand the free energy in a Taylor series about the position of equilibrium. Since the free energy is zero at equilibrium, the leading term in the Taylor series is proportional to the first derivative of the free energy with respect to the extent of reaction. To analyze the critical behavior of this derivative, the theories exploit the principle of critical point isomorphism, which is thought to govern all critical phenomena. They find that the derivative goes to zero in the critical region, which accounts for the slowing down observed in the reaction rate. As has been pointed out, however, most experimental rate investigations have been carried out under irreversible conditions as opposed to relaxation conditions [Shen et al. J. Phys. Chem. A 2015, 119, 8784-8791]. Below, we consider a reaction governed by first order kinetics and invoke transition state theory to take into account the irreversible conditions. We express the apparent activation energy in terms of thermodynamic derivatives evaluated under standard conditions as well as the pseudoequilibrium conditions associated with the reactant and the activated complex. We show that these derivatives approach infinity in the critical region. The apparent activation energy follows this behavior, and its divergence accounts for the slowing down of the reaction rate.

Radicals derived from acetaldehyde and vinyl alcohol.

PubMed

Estep, Marissa L; Morgan, W James; Winkles, Alexander T; Abbott, Adam S; Villegas-Escobar, Nery; Mullinax, J Wayne; Turner, Walter E; Wang, Xiao; Turney, Justin M; Schaefer, Henry F

2017-10-18

Vinyl alcohol and acetaldehyde are isoelectronic products of incomplete butanol combustion. Along with the radicals resulting from the removal of atomic hydrogen or the hydroxyl radical, these species are studied here using ab initio methods as complete as coupled cluster theory with single, double, triple, and perturbative quadruple excitations [CCSDT(Q)], with basis sets as large as cc-pV5Z. The relative energies provided herein are further refined by including corrections for relativistic effects, the frozen core approximation, and the Born-Oppenheimer approximation. The effects of anharmonic zero-point vibrational energies are also treated. The syn conformer of vinyl alcohol is predicted to be lower in energy than the anti conformer by 1.1 kcal mol -1 . The alcoholic hydrogen of syn-vinyl alcohol is found to be the easiest to remove, requiring 84.4 kcal mol -1 . Five other radicals are also carefully considered, with four conformers investigated for the 1-hydroxyvinyl radical. Beyond energetics, we have conducted an overhaul of the spectroscopic literature for these species. Our results also provide predictions for fundamental modes yet to be reported experimentally. To our knowledge, the ν 3 (3076 cm -1 ) and ν 4 (2999 cm -1 ) C-H stretches for syn-vinyl alcohol and all but one of the vibrational modes for anti-vinyl alcohol (ν 1 -ν 14 ) are yet to be observed experimentally. For the acetyl radical, ν 6 (1035 cm -1 ), ν 11 (944 cm -1 ), ν 12 (97 cm -1 ), and accounting for our changes to the assignment of the 1419.9 cm -1 experimental mode, ν 10 (1441 cm -1 ), are yet to be observed. We have predicted these unobserved fundamentals and reassigned the experimental 1419.9 cm -1 frequency in the acetyl radical to ν 4 rather than to ν 10 . Our work also strongly supports reassignment of the ν 10 and ν 11 fundamentals of the vinoxy radical. We suggest that the bands assigned to the overtones of these fundamentals were in fact combination bands. Our findings may be useful in constructing improved combustion models of butanol and in spectroscopically characterizing these molecules further.

A Time-Dependent Quantum Dynamics Study of the H2 + CH3 yields H + CH4 Reaction

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

We present a time-dependent wave-packet propagation calculation for the H2 + CH3 yields H + CH4 reaction in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probability for different initial rotational-vibrational states are presented in this study. The cumulative reaction probability (CRP) is obtained by summing over initial-state-selected reaction probability. The energy-shift approximation to account for the contribution of degrees of freedom missing in the 6D calculation is employed to obtain an approximate full-dimensional CRP. Thermal rate constant is compared with different experiment results.

Optical Gauging of Liquid and Solid Hydrogen in Zero-g Environments for Space Applications

NASA Astrophysics Data System (ADS)

Caimi, F. M.; Kocak, D. M.; Justak, J. F.

2006-04-01

Knowledge of fuel reserve levels is required for propellant management systems and power considerations in many space applications. Although methods are known for gauging fuel amounts in gravitational environments, no simple passive method is known for quantifying fuel reserves in a zero-g environment. Current ground-based methods for cryogenic liquid quantification use wire resistance measurements or point sensors, combined with pressure and temperature measurements to arrive at the desired accuracy. This paper presents an optical sensor design based on existing radiometric and integrating sphere techniques that have the potential to provide quantification in both zero-g and ground based applications. The general approach relies upon optical absorption of liquid or solid hydrogen in a vibrational overtone spectral region. The cryogen storage tank is configured as an "Integrating Sphere." Inside the tank, in a zero-g environment, the liquid and/or gaseous fuel will be free-floating and/or attached to the walls. Incident light irradiates even the smallest portion of the sphere due to the integration. The amount of light absorbed in the tank will be proportional to the amount of fuel present. Therefore, regardless of scatter, all light passed through the medium in the sphere is contained and can be quantified. This paper presents simulations for various liquid hydrogen volumetric configurations and confirms utility of the method. Initial experimental results for a liquid hydrogen analyte in non-zero-g environments are provided. Using this sensor, it is possible to achieve a 10× increase in fuel measurement accuracy which can provide an increased orbit or payload capability.

A New Approach to Identify Optimal Properties of Shunting Elements for Maximum Damping of Structural Vibration Using Piezoelectric Patches

NASA Technical Reports Server (NTRS)

Park, Junhong; Palumbo, Daniel L.

2004-01-01

The use of shunted piezoelectric patches in reducing vibration and sound radiation of structures has several advantages over passive viscoelastic elements, e.g., lower weight with increased controllability. The performance of the piezoelectric patches depends on the shunting electronics that are designed to dissipate vibration energy through a resistive element. In past efforts most of the proposed tuning methods were based on modal properties of the structure. In these cases, the tuning applies only to one mode of interest and maximum tuning is limited to invariant points when based on den Hartog's invariant points concept. In this study, a design method based on the wave propagation approach is proposed. Optimal tuning is investigated depending on the dynamic and geometric properties that include effects from boundary conditions and position of the shunted piezoelectric patch relative to the structure. Active filters are proposed as shunting electronics to implement the tuning criteria. The developed tuning methods resulted in superior capabilities in minimizing structural vibration and noise radiation compared to other tuning methods. The tuned circuits are relatively insensitive to changes in modal properties and boundary conditions, and can applied to frequency ranges in which multiple modes have effects.

Efficient FEM simulation of static and free vibration behavior of single walled boron nitride nanotubes

NASA Astrophysics Data System (ADS)

Giannopoulos, Georgios I.; Kontoni, Denise-Penelope N.; Georgantzinos, Stylianos K.

2016-08-01

This paper describes the static and free vibration behavior of single walled boron nitride nanotubes using a structural mechanics based finite element method. First, depending on the type of nanotube under investigation, its three dimensional nanostructure is developed according to the well-known corresponding positions of boron and nitride atoms as well as boron nitride bonds. Then, appropriate point masses are assigned to the atomic positions of the developed space frame. Next, these point masses are suitably interconnected with two-noded, linear, spring-like, finite elements. In order to simulate effectively the interactions observed between boron and nitride atoms within the nanotube, appropriate potential energy functions are introduced for these finite elements. In this manner, various atomistic models for both armchair and zigzag nanotubes with different aspect ratios are numerically analyzed and their effective elastic modulus as well as their natural frequencies and corresponding mode shapes are obtained. Regarding the free vibration analysis, the computed results reveal bending, breathing and axial modes of vibration depending on the nanotube size and chirality as well as the applied boundary support conditions. The longitudinal stiffness of the boron nitride nanotubes is found also sensitive to their geometric characteristics.

Reducing the cost of using collocation to compute vibrational energy levels: Results for CH2NH.

PubMed

Avila, Gustavo; Carrington, Tucker

2017-08-14

In this paper, we improve the collocation method for computing vibrational spectra that was presented in the work of Avila and Carrington, Jr. [J. Chem. Phys. 143, 214108 (2015)]. Known quadrature and collocation methods using a Smolyak grid require storing intermediate vectors with more elements than points on the Smolyak grid. This is due to the fact that grid labels are constrained among themselves and basis labels are constrained among themselves. We show that by using the so-called hierarchical basis functions, one can significantly reduce the memory required. In this paper, the intermediate vectors have only as many elements as the Smolyak grid. The ideas are tested by computing energy levels of CH 2 NH.

Energy transfer of highly vibrationally excited phenanthrene and diphenylacetylene.

PubMed

Hsu, Hsu Chen; Tsai, Ming-Tsang; Dyakov, Yuri; Ni, Chi-Kung

2011-05-14

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold phenanthrene and diphenylacetylene in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer between naphthalene and Kr, energy transfer between phenanthrene and Kr shows a larger cross-section for vibrational to translational (V → T) energy transfer, a smaller cross-section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation. These differences are further enlarged in the comparison between naphthalene and diphenylacetylene. In addition, less complex formation and significant increases in the large V → T energy transfer probabilities, termed supercollisions in diphenylacetylene and Kr collisions were observed. The differences in the energy transfer between these highly vibrationally excited molecules are attributed to the low-frequency vibrational modes, especially those vibrations with rotation-like wide-angle motions.

Numerical analysis of the vibroacoustic properties of plates with embedded grids of acoustic black holes.

PubMed

Conlon, Stephen C; Fahnline, John B; Semperlotti, Fabio

2015-01-01

The concept of an Acoustic Black Hole (ABH) has been developed and exploited as an approach for passively attenuating structural vibration. The basic principle of the ABH relies on proper tailoring of the structure geometrical properties in order to produce a gradual reduction of the flexural wave speed, theoretically approaching zero. For practical systems the idealized "zero" wave speed condition cannot be achieved so the structural areas of low wave speed are treated with surface damping layers to allow the ABH to approach the idealized dissipation level. In this work, an investigation was conducted to assess the effects that distributions of ABHs embedded in plate-like structures have on both vibration and structure radiated sound, focusing on characterizing and improving low frequency performance. Finite Element and Boundary Element models were used to assess the vibration response and radiated sound power performance of several plate configurations, comparing baseline uniform plates with embedded periodic ABH designs. The computed modal loss factors showed the importance of the ABH unit cell low order modes in the overall vibration reduction effectiveness of the embedded ABH plates at low frequencies where the free plate bending wavelengths are longer than the scale of the ABH.

Vibrations used to talk to quantum circuits

NASA Astrophysics Data System (ADS)

Cho, Adrian

2018-03-01

The budding discipline of quantum acoustics could shake up embryonic quantum computers. Such machines run by flipping quantum bits, or qubits, that can be set not only to zero or one, but, bizarrely, to zero and one at the same time. The most advanced qubits are circuits made of superconducting metal, and to control or read out a qubit, researchers make it interact with a microwave resonator—typically a strip of metal on the qubit chip or a finger-size cavity surrounding it—which rings with microwave photons like an organ pipe rings with sound. But some physicists see advantages to replacing the microwave resonator with a mechanical one that rings with quantized vibrations, or phonons. A well-designed acoustic resonator could ring longer than a microwave one does and could be far smaller, enabling researchers to produce more compact technologies. But first scientists must gain quantum control over vibrations. And several groups are on the cusp of doing that, as they reported at a recent meeting.

Energy transfer of highly vibrationally excited biphenyl.

PubMed

Hsu, Hsu Chen; Dyakov, Yuri; Ni, Chi-Kung

2010-11-07

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold biphenyl in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer of naphthalene, energy transfer of biphenyl shows more forward scattering, less complex formation, larger cross section for vibrational to translational (V→T) energy transfer, smaller cross section for translational to vibrational and rotational (T→VR) energy transfer, larger total collisional cross section, and more energy transferred from vibration to translation. Significant increase in the large V→T energy transfer probabilities, termed supercollisions, was observed. The difference in the energy transfer of highly vibrationally excited molecules between rotationally cold naphthalene and rotationally cold biphenyl is very similar to the difference in the energy transfer of highly vibrationally excited molecules between rotationally cold naphthalene and rotationally hot naphthalene. The low-frequency vibrational modes with out-of-plane motion and rotationlike wide-angle motion are attributed to make the energy transfer of biphenyl different from that of naphthalene.

Trajectory dynamics study of the Ar + CH4 dissociation reaction at high temperatures: the importance of zero-point-energy effects.

PubMed

Marques, J M C; Martínez-Núñez, E; Fernandez-Ramos, A; Vazquez, S A

2005-06-23

Large-scale classical trajectory calculations have been performed to study the reaction Ar + CH4--> CH3 +H + Ar in the temperature range 2500 < or = T/K < or = 4500. The potential energy surface used for ArCH4 is the sum of the nonbonding pairwise potentials of Hase and collaborators (J. Chem. Phys. 2001, 114, 535) that models the intermolecular interaction and the CH4 intramolecular potential of Duchovic et al. (J. Phys. Chem. 1984, 88, 1339), which has been modified to account for the H-H repulsion at small bending angles. The thermal rate coefficient has been calculated, and the zero-point energy (ZPE) of the CH3 product molecule has been taken into account in the analysis of the results; also, two approaches have been applied for discarding predissociative trajectories. In both cases, good agreement is observed between the experimental and trajectory results after imposing the ZPE of CH3. The energy-transfer parameters have also been obtained from trajectory calculations and compared with available values estimated from experiment using the master equation formalism; in general, the agreement is good.

Manipulation strategies for massive space payloads

NASA Technical Reports Server (NTRS)

Book, Wayne J.

1989-01-01

Control for the bracing strategy is being examined. It was concluded earlier that trajectory planning must be improved to best achieve the bracing motion. Very interesting results were achieved which enable the inverse dynamics of flexible arms to be calculated for linearized motion in a more efficient manner than previously published. The desired motion of the end point beginning at t=0 and ending at t=t sub f is used to calculate the required torque at the joint. The solution is separated into a causal function that is zero for t is less than 0 and an accusal function which is zero for t is greater than t sub f. A number of alternative end point trajectories were explored in terms of the peak torque required, the amount of anticipatory action, and other issues. The single link case is the immediate subject and an experimental verification of that case is being performed. Modeling with experimental verification of closed chain dynamics continues. Modeling effort has pointed out inaccuracies that result from the choice of numerical techniques used to incorporate the closed chain constraints when modeling our experimental prototype RALF (Robotic Arm Large and Flexible). Results were compared to TREETOPS, a multi body code. The experimental verification work is suggesting new ways to make comparisons with systems having structural linearity and joint and geometric nonlinearity. The generation of inertial forces was studied with a small arm that will damp the large arm's vibration.

Fault identification of rotor-bearing system based on ensemble empirical mode decomposition and self-zero space projection analysis

NASA Astrophysics Data System (ADS)

Jiang, Fan; Zhu, Zhencai; Li, Wei; Zhou, Gongbo; Chen, Guoan

2014-07-01

Accurately identifying faults in rotor-bearing systems by analyzing vibration signals, which are nonlinear and nonstationary, is challenging. To address this issue, a new approach based on ensemble empirical mode decomposition (EEMD) and self-zero space projection analysis is proposed in this paper. This method seeks to identify faults appearing in a rotor-bearing system using simple algebraic calculations and projection analyses. First, EEMD is applied to decompose the collected vibration signals into a set of intrinsic mode functions (IMFs) for features. Second, these extracted features under various mechanical health conditions are used to design a self-zero space matrix according to space projection analysis. Finally, the so-called projection indicators are calculated to identify the rotor-bearing system's faults with simple decision logic. Experiments are implemented to test the reliability and effectiveness of the proposed approach. The results show that this approach can accurately identify faults in rotor-bearing systems.

Theoretical studies of dissociative recombination

NASA Technical Reports Server (NTRS)

Guberman, S. L.

1985-01-01

The calculation of dissociative recombination rates and cross sections over a wide temperature range by theoretical quantum chemical techniques is described. Model calculations on electron capture by diatomic ions are reported which illustrate the dependence of the rates and cross sections on electron energy, electron temperature, and vibrational temperature for three model crossings of neutral and ionic potential curves. It is shown that cross sections for recombination to the lowest vibrational level of the ion can vary by several orders of magnitude depending upon the position of the neutral and ionic potential curve crossing within the turning points of the v = 1 vibrational level. A new approach for calculating electron capture widths is reported. Ab initio calculations are described for recombination of O2(+) leading to excited O atoms.

Damage assessment in a sandwich panel based on full-field vibration measurements

NASA Astrophysics Data System (ADS)

Seguel, F.; Meruane, V.

2018-03-01

Different studies have demonstrated that vibration characteristics are sensitive to debonding in composite structures. Nevertheless, one of the main restrictions of vibration measurements is the number of degrees of freedom that can be acquired simultaneously, which restricts the size of the damage that can be identified. Recent studies have shown that it is possible to use high-speed three-dimensional (3-D) digital image correlation (DIC) techniques for full-field vibration measurements. With this technique, it is possible to take measurements at thousands of points on the surface of a structure with a single snapshot. The present article investigates the application of full-field vibration measurements in the debonding assessment of an aluminium honeycomb sandwich panel. Experimental data from an aluminium honeycomb panel containing different damage scenarios is acquired by a high-speed 3-D DIC system; four methodologies to compute damage indices are evaluated: mode shape curvatures, uniform load surface, modal strain energy and gapped smoothing.

Characterizing the potential energy surface of the water dimer with DFT: failures of some popular functionals for hydrogen bonding.

PubMed

Anderson, Julie A; Tschumper, Gregory S

2006-06-08

Ten stationary points on the water dimer potential energy surface have been examined with ten density functional methods (X3LYP, B3LYP, B971, B98, MPWLYP, PBE1PBE, PBE, MPW1K, B3P86, and BHandHLYP). Geometry optimizations and vibrational frequency calculations were carried out with the TZ2P(f,d)+dif basis set. All ten of the density functionals correctly describe the relative energies of the ten stationary points. However, correctly describing the curvature of the potential energy surface is far more difficult. Only one functional (BHandHLYP) reproduces the number of imaginary frequencies from CCSD(T) calculations. The other nine density functionals fail to correctly characterize the nature of at least one of the ten (H(2)O)(2) stationary points studied here.

Cost Benefit Analysis of a Utility Scale Waste-to-Energy/Concentrating Solar Power Hybrid Facility at Fort Bliss

DTIC Science & Technology

2012-06-01

installations for Energy, Waste, and Water. This means Fort Bliss will strive to become Net Zero Energy, Net Zero Waste , and Net Zero Water in the coming...years. Net Zero Energy requires Fort Bliss to produce as much energy on-installation as it consumes annually. Net Zero Waste aims to reduce, reuse...become Net Zero Energy and Net Zero Waste by 2020. A WtE facility actually goes well beyond Fort Bliss’ Net Zero Energy mission. That mission

Modeling the archetype cysteine protease reaction using dispersion corrected density functional methods in ONIOM-type hybrid QM/MM calculations; the proteolytic reaction of papain.

PubMed

Fekete, Attila; Komáromi, István

2016-12-07

A proteolytic reaction of papain with a simple peptide model substrate N-methylacetamide has been studied. Our aim was twofold: (i) we proposed a plausible reaction mechanism with the aid of potential energy surface scans and second geometrical derivatives calculated at the stationary points, and (ii) we investigated the applicability of the dispersion corrected density functional methods in comparison with the popular hybrid generalized gradient approximations (GGA) method (B3LYP) without such a correction in the QM/MM calculations for this particular problem. In the resting state of papain the ion pair and neutral forms of the Cys-His catalytic dyad have approximately the same energy and they are separated by only a small barrier. Zero point vibrational energy correction shifted this equilibrium slightly to the neutral form. On the other hand, the electrostatic solvation free energy corrections, calculated using the Poisson-Boltzmann method for the structures sampled from molecular dynamics simulation trajectories, resulted in a more stable ion-pair form. All methods we applied predicted at least a two elementary step acylation process via a zwitterionic tetrahedral intermediate. Using dispersion corrected DFT methods the thioester S-C bond formation and the proton transfer from histidine occur in the same elementary step, although not synchronously. The proton transfer lags behind (or at least does not precede) the S-C bond formation. The predicted transition state corresponds mainly to the S-C bond formation while the proton is still on the histidine Nδ atom. In contrast, the B3LYP method using larger basis sets predicts a transition state in which the S-C bond is almost fully formed and the transition state can be mainly featured by the Nδ(histidine) to N(amid) proton transfer. Considerably lower activation energy was predicted (especially by the B3LYP method) for the next amide bond breaking elementary step of acyl-enzyme formation. Deacylation appeared to be a single elementary step process in all the methods we applied.

Saddle point localization of molecular wavefunctions.

PubMed

Mellau, Georg Ch; Kyuberis, Alexandra A; Polyansky, Oleg L; Zobov, Nikolai; Field, Robert W

2016-09-15

The quantum mechanical description of isomerization is based on bound eigenstates of the molecular potential energy surface. For the near-minimum regions there is a textbook-based relationship between the potential and eigenenergies. Here we show how the saddle point region that connects the two minima is encoded in the eigenstates of the model quartic potential and in the energy levels of the [H, C, N] potential energy surface. We model the spacing of the eigenenergies with the energy dependent classical oscillation frequency decreasing to zero at the saddle point. The eigenstates with the smallest spacing are localized at the saddle point. The analysis of the HCN ↔ HNC isomerization states shows that the eigenstates with small energy spacing relative to the effective (v1, v3, ℓ) bending potentials are highly localized in the bending coordinate at the transition state. These spectroscopically detectable states represent a chemical marker of the transition state in the eigenenergy spectrum. The method developed here provides a basis for modeling characteristic patterns in the eigenenergy spectrum of bound states.

Two methods for damping torsional vibrations in DFIG-based wind generators using power converters

NASA Astrophysics Data System (ADS)

Zhao, Zuyi; Lu, Yupu; Xie, Da; Yu, Songtao; Wu, Wangping

2017-01-01

This paper proposes novel damping control algorithms by using static synchronous compensator (STATCOM) and energy storage system (ESS) to damp torsional vibrations in doubly fed induction generator (DFIG) based wind turbine systems. It first analyses the operating characteristics of STATCOM and ESS for regulating power variations to increase grid voltage stability. Then, new control strategies for STATCOM and ESS are introduced to damp the vibrations. It is followed by illustration of their effectiveness to damp the drive train torsional vibrations of wind turbines, which can be caused by grid disturbances, such as voltage sags and frequency fluctuations. Results suggest that STATCOM is a promising technology to mitigate the torsional vibrations caused by grid voltage sags. By contrast, the ESS connected to the point of common coupling (PCC) of wind turbine systems shows even obvious advantages because of its capability of absorbing/releasing both active and reactive power. It can thus be concluded that STATCOM is useful for stabilizing power system voltage fluctuations, and ESS is more effective both in regulating PCC voltage fluctuations and damping torsional vibrations caused by grid voltage frequency fluctuations.

Effect of chiral symmetry on chaotic scattering from Majorana zero modes.

PubMed

Schomerus, H; Marciani, M; Beenakker, C W J

2015-04-24

In many of the experimental systems that may host Majorana zero modes, a so-called chiral symmetry exists that protects overlapping zero modes from splitting up. This symmetry is operative in a superconducting nanowire that is narrower than the spin-orbit scattering length, and at the Dirac point of a superconductor-topological insulator heterostructure. Here we show that chiral symmetry strongly modifies the dynamical and spectral properties of a chaotic scatterer, even if it binds only a single zero mode. These properties are quantified by the Wigner-Smith time-delay matrix Q=-iℏS^{†}dS/dE, the Hermitian energy derivative of the scattering matrix, related to the density of states by ρ=(2πℏ)^{-1}TrQ. We compute the probability distribution of Q and ρ, dependent on the number ν of Majorana zero modes, in the chiral ensembles of random-matrix theory. Chiral symmetry is essential for a significant ν dependence.