Gidopoulos, Nikitas I.; Gross, E. K. U.
2014-01-01
A novel treatment of non-adiabatic couplings is proposed. The derivation is based on a theorem by Hunter stating that the wave function of the complete system of electrons and nuclei can be written, without approximation, as a Born–Oppenheimer (BO)-type product of a nuclear wave function, X(R), and an electronic one, ΦR(r), which depends parametrically on the nuclear configuration R. From the variational principle, we deduce formally exact equations for ΦR(r) and X(R). The algebraic structure of the exact nuclear equation coincides with the corresponding one in the adiabatic approximation. The electronic equation, however, contains terms not appearing in the adiabatic case, which couple the electronic and the nuclear wave functions and account for the electron–nuclear correlation beyond the BO level. It is proposed that these terms can be incorporated using an optimized local effective potential. PMID:24516183
NASA Astrophysics Data System (ADS)
Alijah, Alexander; Kokoouline, Viatcheslav
2015-10-01
Vibrational energies and wave functions of the triplet state of the H3+ ion have been determined. In the calculations, the ground and first excited triplet electronic states are included as well as the most important part of the non-Born-Oppenheimer coupling between them. The diabatization procedure proposed by Longuet-Higgins is then applied to transform the two adiabatic ab initio potential energy surfaces of the triplet-H3+ state into a 2 × 2 diabatic matrix. The diabatization takes into account the effect of the geometrical phase due to the conical intersection between the two adiabatic potential surfaces. The results are compared to the calculation involving only the lowest adiabatic potential energy surface of the triplet-H3+ ion and neglecting the geometrical phase. The energy difference between results with and without the non-adiabatic coupling and the geometrical phase is about one wave number for the lowest vibrational levels.
NASA Astrophysics Data System (ADS)
Xavier, F. George D.; Kumar, Sanjay
2010-10-01
Ab initio global adiabatic and quasidiabatic potential energy surfaces of lowest four electronic (1-4 A3″) states of the H++O2 system have been computed in the Jacobi coordinates (R,r,γ) using Dunning's cc-pVTZ basis set at the internally contracted multireference (single and double) configuration interaction level of accuracy, which are relevant to the dynamics studies of inelastic vibrational and charge transfer processes observed in the scattering experiments. The computed equilibrium geometry parameters of the bound [HO2]+ ion in the ground electronic state and other parameters for the transition state for the isomerization process, HOO+⇌OOH+ are in good quantitative agreement with those available from the high level ab initio calculations, thus lending credence to the accuracy of the potential energy surfaces. The nonadiabatic couplings between the electronic states have been analyzed in both the adiabatic and quasidiabatic frameworks by computing the nonadiabatic coupling matrix elements and the coupling potentials, respectively. It is inferred that the dynamics of energy transfer processes in the scattering experiments carried out in the range of 9.5-23 eV would involve all the four electronic states.
Communication: Adiabatic and non-adiabatic electron-nuclear motion: Quantum and classical dynamics
NASA Astrophysics Data System (ADS)
Albert, Julian; Kaiser, Dustin; Engel, Volker
2016-05-01
Using a model for coupled electronic-nuclear motion we investigate the range from negligible to strong non-adiabatic coupling. In the adiabatic case, the quantum dynamics proceeds in a single electronic state, whereas for strong coupling a complete transition between two adiabatic electronic states takes place. It is shown that in all coupling regimes the short-time wave-packet dynamics can be described using ensembles of classical trajectories in the phase space spanned by electronic and nuclear degrees of freedom. We thus provide an example which documents that the quantum concept of non-adiabatic transitions is not necessarily needed if electronic and nuclear motion is treated on the same footing.
Engin, Selma; Sisourat, Nicolas Selles, Patricia; Taïeb, Richard; Carniato, Stéphane
2014-06-21
Raman Chirped Adiabatic Passage (RCAP) is an efficient method to climb the vibrational ladder of molecules. It was shown on the example of fixed-in-space HCl molecule that selective vibrational excitation can thus be achieved by RCAP and that population transfer can be followed by X-ray Photoelectron spectroscopy [S. Engin, N. Sisourat, P. Selles, R. Taïeb, and S. Carniato, Chem. Phys. Lett. 535, 192–195 (2012)]. Here, in a more detailed analysis of the process, we investigate the effects of highly excited electronic states and of molecular rotation on the efficiency of RCAP. Furthermore, we propose an alternative spectroscopic way to monitor the transfer by means of X-ray absorption spectra.
Adiabatic state preparation study of methylene
Veis, Libor Pittner, Jiří
2014-06-07
Quantum computers attract much attention as they promise to outperform their classical counterparts in solving certain type of problems. One of them with practical applications in quantum chemistry is simulation of complex quantum systems. An essential ingredient of efficient quantum simulation algorithms are initial guesses of the exact wave functions with high enough fidelity. As was proposed in Aspuru-Guzik et al. [Science 309, 1704 (2005)], the exact ground states can in principle be prepared by the adiabatic state preparation method. Here, we apply this approach to preparation of the lowest lying multireference singlet electronic state of methylene and numerically investigate preparation of this state at different molecular geometries. We then propose modifications that lead to speeding up the preparation process. Finally, we decompose the minimal adiabatic state preparation employing the direct mapping in terms of two-qubit interactions.
NASA Astrophysics Data System (ADS)
Kang, Dongdong; Hou, Yong; Gao, Cheng; Zeng, Jiaolong; Yuan, Jianmin
2016-05-01
In warm dense matter(WDM), the thermal motion energy of a nucleus may be comparable to its coupling energy with the neighbor nuclei and comparable to the valence electronic orbital motion energy. As the much small mass of electrons, the fluctuations of the electron orbitals are almost adiabatic dynamical changes with nuclear motion. The electronic and nuclear structure of warm and dense He and Ar are simulated by using the density functional based molecular dynamics method. The nuclear thermal motion driven adiabatic thermalization of the electron states, depression of the energy band gap and even phase transitions of electron states from insulator to metal are predicted when the nuclear thermal motion energy is comparable to the coupling energy between the neighboring atoms as well as to the valence electronic orbital motion energy. These kind of nuclear thermal motion driven adiabatic electronic states from insulator to metal phase transition occurs at much lower temperatures than the normal thermal collision excitation in low density and high temperature gases.
Cotton, Stephen J.; Miller, William H.
2013-12-21
A recently described symmetrical windowing methodology [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] for quasi-classical trajectory simulations is applied here to the Meyer-Miller [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] model for the electronic degrees of freedom in electronically non-adiabatic dynamics. Results generated using this classical approach are observed to be in very good agreement with accurate quantum mechanical results for a variety of test applications, including problems where coherence effects are significant such as the challenging asymmetric spin-boson system.
Delgado, Juan C; Selsby, Ronald G
2013-01-01
The ground state configuration of the gas phase cationic dyes pinacyanol chloride and rhodamine B are optimized with HF/6-311 + G(2d,2p) method and basis set. B3PW91/6-311 + G(2df,2p) functional and basis set is used to calculate the Mulliken atom charge distribution, total molecular energy, the dipole moment, the vertical ionization potential, the adiabatic electron affinity and the lowest excited triplet state, the last three as an energy difference between separately calculated open shell and ground states. The triplet and extra electron states are optimized to find the relaxation energy. In the ground state optimization of both dyes the chloride anion migrates to a position near the center of the chromophore. For rhodamine B the benzoidal group turns perpendicular to the chromophore plane. For both dyes, the LUMO is mostly of π character associated with the aromatic part of the molecule containing the chromophore. The highest occupied MOs consist of three almost degenerate eigenvectors involving the chloride anion coordinated with σ electrons in the molecular framework. The fourth highest MO is of π character. For both molecules in the gas phase ionization process the chloride anion loses the significant fraction of electric charge. In electron capture, the excess charge goes mainly on the dye cation. PMID:22891949
NASA Astrophysics Data System (ADS)
Yonehara, Takehiro; Takatsuka, Kazuo
2012-12-01
We develop a theory and the method of its application for chemical dynamics in systems, in which the adiabatic potential energy hyper-surfaces (PES) are densely quasi-degenerate to each other in a wide range of molecular geometry. Such adiabatic electronic states tend to couple each other through strong nonadiabatic interactions. Technically, therefore, it is often extremely hard to accurately single out the individual PES in those systems. Moreover, due to the mutual nonadiabatic couplings that may spread wide in space and due to the energy-time uncertainty relation, the notion of the isolated and well-defined potential energy surface should lose the sense. On the other hand, such dense electronic states should offer a very interesting molecular field in which chemical reactions to proceed in characteristic manners. However, to treat these systems, the standard theoretical framework of chemical reaction dynamics, which starts from the Born-Oppenheimer approximation and ends up with quantum nuclear wavepacket dynamics, is not very useful. We here explore this problem with our developed nonadiabatic electron wavepacket theory, which we call the phase-space averaging and natural branching (PSANB) method [T. Yonehara and K. Takatsuka, J. Chem. Phys. 129, 134109 (2008)], 10.1063/1.2987302, or branching-path representation, in which the packets are propagated in time along the non-Born-Oppenheimer branching paths. In this paper, after outlining the basic theory, we examine using a one-dimensional model how well the PSANB method works with such densely quasi-degenerate nonadiabatic systems. To do so, we compare the performance of PSANB with the full quantum mechanical results and those given by the fewest switches surface hopping (FSSH) method, which is known to be one of the most reliable and flexible methods to date. It turns out that the PSANB electron wavepacket approach actually yields very good results with far fewer initial sampling paths. Then we apply the
Feller, David
2016-01-01
Benchmark quality adiabatic electron affinities for a collection of atoms and small molecules were obtained with the Feller-Peterson-Dixon composite coupled cluster theory method. Prior applications of this method demonstrated its ability to accurately predict atomization energies/heats of formation for more than 170 molecules. In the current work, the 1-particle expansion involved very large correlation consistent basis sets, ranging up to aug-cc-pV9Z (aug-cc-pV10Z for H and H2), with the goal of minimizing the residual basis set truncation error that must otherwise be approximated with extrapolation formulas. The n-particle expansion begins with coupled cluster calculations through iterative single and double excitations plus a quasiperturbative treatment of "connected" triple excitations (CCSD(T)) pushed to the complete basis set limit followed by CCSDT, CCSDTQ, or CCSDTQ5 corrections. Due to the small size of the systems examined here, it was possible in many cases to extend the n-particle expansion to the full configuration interaction wave function limit. Additional, smaller corrections associated with core/valence correlation, scalar relativity, anharmonic zero point vibrational energies, and non-adiabatic effects were also included. The overall root mean square (RMS) deviation was 0.005 eV (0.12 kcal/mol). This level of agreement was comparable to what was found with molecular heats of formation. A 95% confidence level corresponds to roughly twice the RMS value or 0.01 eV. While the atomic electron affinities are known experimentally to high accuracy, the molecular values are less certain. This contributes to the difficulty of gauging the accuracy of the theoretical results. A limited number of electron affinities were determined with the explicitly correlated CCSD(T)-F12b method. After extending the VnZ-F12 orbital basis sets with additional diffuse functions, the F12b method was found to accurately reproduce the best F/F(-) value obtained with standard
NASA Astrophysics Data System (ADS)
Feller, David
2016-01-01
Benchmark quality adiabatic electron affinities for a collection of atoms and small molecules were obtained with the Feller-Peterson-Dixon composite coupled cluster theory method. Prior applications of this method demonstrated its ability to accurately predict atomization energies/heats of formation for more than 170 molecules. In the current work, the 1-particle expansion involved very large correlation consistent basis sets, ranging up to aug-cc-pV9Z (aug-cc-pV10Z for H and H2), with the goal of minimizing the residual basis set truncation error that must otherwise be approximated with extrapolation formulas. The n-particle expansion begins with coupled cluster calculations through iterative single and double excitations plus a quasiperturbative treatment of "connected" triple excitations (CCSD(T)) pushed to the complete basis set limit followed by CCSDT, CCSDTQ, or CCSDTQ5 corrections. Due to the small size of the systems examined here, it was possible in many cases to extend the n-particle expansion to the full configuration interaction wave function limit. Additional, smaller corrections associated with core/valence correlation, scalar relativity, anharmonic zero point vibrational energies, and non-adiabatic effects were also included. The overall root mean square (RMS) deviation was 0.005 eV (0.12 kcal/mol). This level of agreement was comparable to what was found with molecular heats of formation. A 95% confidence level corresponds to roughly twice the RMS value or 0.01 eV. While the atomic electron affinities are known experimentally to high accuracy, the molecular values are less certain. This contributes to the difficulty of gauging the accuracy of the theoretical results. A limited number of electron affinities were determined with the explicitly correlated CCSD(T)-F12b method. After extending the VnZ-F12 orbital basis sets with additional diffuse functions, the F12b method was found to accurately reproduce the best F/F- value obtained with standard
Geometric Adiabatic Transport in Quantum Hall States
NASA Astrophysics Data System (ADS)
Klevtsov, S.; Wiegmann, P.
2015-08-01
We argue that in addition to the Hall conductance and the nondissipative component of the viscous tensor, there exists a third independent transport coefficient, which is precisely quantized. It takes constant values along quantum Hall plateaus. We show that the new coefficient is the Chern number of a vector bundle over moduli space of surfaces of genus 2 or higher and therefore cannot change continuously along the plateau. As such, it does not transpire on a sphere or a torus. In the linear response theory, this coefficient determines intensive forces exerted on electronic fluid by adiabatic deformations of geometry and represents the effect of the gravitational anomaly. We also present the method of computing the transport coefficients for quantum Hall states.
Geometric Adiabatic Transport in Quantum Hall States.
Klevtsov, S; Wiegmann, P
2015-08-21
We argue that in addition to the Hall conductance and the nondissipative component of the viscous tensor, there exists a third independent transport coefficient, which is precisely quantized. It takes constant values along quantum Hall plateaus. We show that the new coefficient is the Chern number of a vector bundle over moduli space of surfaces of genus 2 or higher and therefore cannot change continuously along the plateau. As such, it does not transpire on a sphere or a torus. In the linear response theory, this coefficient determines intensive forces exerted on electronic fluid by adiabatic deformations of geometry and represents the effect of the gravitational anomaly. We also present the method of computing the transport coefficients for quantum Hall states. PMID:26340197
Adiabatic cooling of solar wind electrons
NASA Technical Reports Server (NTRS)
Sandbaek, Ornulf; Leer, Egil
1992-01-01
In thermally driven winds emanating from regions in the solar corona with base electron densities of n0 not less than 10 exp 8/cu cm, a substantial fraction of the heat conductive flux from the base is transfered into flow energy by the pressure gradient force. The adiabatic cooling of the electrons causes the electron temperature profile to fall off more rapidly than in heat conduction dominated flows. Alfven waves of solar origin, accelerating the basically thermally driven solar wind, lead to an increased mass flux and enhanced adiabatic cooling. The reduction in electron temperature may be significant also in the subsonic region of the flow and lead to a moderate increase of solar wind mass flux with increasing Alfven wave amplitude. In the solar wind model presented here the Alfven wave energy flux per unit mass is larger than that in models where the temperature in the subsonic flow is not reduced by the wave, and consequently the asymptotic flow speed is higher.
NASA Astrophysics Data System (ADS)
Saheer, V. C.; Kumar, Sanjay
2016-01-01
The global ground and first three excited electronic state adiabatic as well as the corresponding quasidiabatic potential energy surfaces is reported as a function of nuclear geometries in the Jacobi coordinates ( R → , r → , γ ) using Dunning's cc-pVTZ basis set at the internally contracted multi-reference (single and double) configuration interaction level of accuracy. Nonadiabatic couplings, arising out of relative motion of proton and the vibrational motion of CO, are also reported in terms of coupling potentials. The quasidiabatic potential energy surfaces and the coupling potentials have been obtained using the ab initio procedure [Simah et al., J. Chem. Phys. 111, 4523 (1999)] for the purpose of dynamics studies.
Dupuy, Nicolas; Bouaouli, Samira; Mauri, Francesco Casula, Michele; Sorella, Sandro
2015-06-07
We study the ionization energy, electron affinity, and the π → π{sup ∗} ({sup 1}L{sub a}) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the {sup 1}L{sub a} excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs. We show that this approach leads to stable energy minimization and geometry relaxation of both ground and excited states, performed consistently within the correlated QMC framework. Geometry optimization of excited states is needed to make a reliable and direct comparison with experimental adiabatic excitation energies. This is particularly important in π-conjugated and polycyclic aromatic hydrocarbons, where there is a strong interplay between low-lying energy excitations and structural modifications, playing a functional role in many photochemical processes. Anthracene is an ideal benchmark to test these effects. Its geometry relaxation energies upon electron excitation are of up to 0.3 eV in the neutral {sup 1}L{sub a} excited state, while they are of the order of 0.1 eV in electron addition and removal processes. Significant modifications of the ground state bond length alternation are revealed in the QMC excited state geometry optimizations. Our QMC study yields benchmark results for both geometries and energies, with values below chemical accuracy if compared to experiments, once zero point energy effects are taken into account.
Dupuy, Nicolas; Bouaouli, Samira; Mauri, Francesco; Sorella, Sandro; Casula, Michele
2015-06-01
We study the ionization energy, electron affinity, and the π → π(∗) ((1)La) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the (1)La excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs. We show that this approach leads to stable energy minimization and geometry relaxation of both ground and excited states, performed consistently within the correlated QMC framework. Geometry optimization of excited states is needed to make a reliable and direct comparison with experimental adiabatic excitation energies. This is particularly important in π-conjugated and polycyclic aromatic hydrocarbons, where there is a strong interplay between low-lying energy excitations and structural modifications, playing a functional role in many photochemical processes. Anthracene is an ideal benchmark to test these effects. Its geometry relaxation energies upon electron excitation are of up to 0.3 eV in the neutral (1)La excited state, while they are of the order of 0.1 eV in electron addition and removal processes. Significant modifications of the ground state bond length alternation are revealed in the QMC excited state geometry optimizations. Our QMC study yields benchmark results for both geometries and energies, with values below chemical accuracy if compared to experiments, once zero point energy effects are taken into account. PMID:26049481
NASA Astrophysics Data System (ADS)
Panda, C. D.; O'Leary, B. R.; West, A. D.; Baron, J.; Hess, P. W.; Hoffman, C.; Kirilov, E.; Overstreet, C. B.; West, E. P.; DeMille, D.; Doyle, J. M.; Gabrielse, G.
2016-05-01
Experimental searches for the electron electric-dipole moment (EDM) probe new physics beyond the standard model. The current best EDM limit was set by the ACME Collaboration [Science 343, 269 (2014), 10.1126/science.1248213], constraining time-reversal symmetry (T ) violating physics at the TeV energy scale. ACME used optical pumping to prepare a coherent superposition of ThO H3Δ1 states that have aligned electron spins. Spin precession due to the molecule's internal electric field was measured to extract the EDM. We report here on an improved method for preparing this spin-aligned state of the electron by using stimulated Raman adiabatic passage (STIRAP). We demonstrate a transfer efficiency of 75 %±5 % , representing a significant gain in signal for a next-generation EDM experiment. We discuss the particularities of implementing STIRAP in systems such as ours, where molecular ensembles with large phase-space distributions are transferred via weak molecular transitions with limited laser power and limited optical access.
NASA Astrophysics Data System (ADS)
Yan, Lingling; Qu, Yizhi; Liu, Chunhua; Wang, Jianguo; Buenker, Robert J.
2012-03-01
An ab initio multireference single- and double-excitation configuration interaction (CI) study is carried out for the ground and excited electronic states of alkali-hydride cations (LiH+, NaH+, KH+, RbH+, and CsH+). For all alkali-metal atoms, the first inner-shell and valence electrons (nine active electrons, three for Li) are considered explicitly in the ab initio self-consistent-field and CI calculations. The adiabatic potential energy curves, radial and rotational couplings are calculated and presented. Short-range (˜3 a.u.) potential wells produced by the excitation of the inner-shell electrons are found. The depths of the inner potential wells are much greater than those of the outer wells for the CsH+ system. The computed spectroscopic constants for the long-range potential well of the 2 2Σ+ state are very close to the available theoretical and experimental data. The electronic states of alkali-hydrogen cations are also compared with each other, it is found that the positions of the potential wells shift to larger internuclear distances gradually, and the depths of these potential wells become greater with increasing alkali-metal atomic number. The relationships between structures of the radial coupling matrix elements and the avoiding crossings of the potential curves are analyzed. From NaH+ to CsH+, radial coupling matrix elements display more and more complex structures due to the gradual decrease of energy separations for avoided crossings. Finally, the behavior of some rotational couplings is also shown.
Steady-state coherent transfer by adiabatic passage.
Huneke, Jan; Platero, Gloria; Kohler, Sigmund
2013-01-18
We propose steady-state electron transport based on coherent transfer by adiabatic passage (CTAP) in a linearly arranged triple quantum dot with leads attached to the outer dots. Its main feature is repeated steering of single electrons from the first dot to the last dot without relevant occupation of the middle dot. The coupling to leads enables a steady-state current, whose shot noise is significantly suppressed provided that the CTAP protocol performs properly. This represents an indication for the direct transfer between spatially separated dots and, thus, may resolve the problem of finding experimental evidence for the nonoccupation of the middle dot. PMID:23373941
Speeding up Adiabatic Quantum State Transfer by Using Dressed States
NASA Astrophysics Data System (ADS)
Baksic, Alexandre; Ribeiro, Hugo; Clerk, Aashish A.
2016-06-01
We develop new pulse schemes to significantly speed up adiabatic state transfer protocols. Our general strategy involves adding corrections to an initial control Hamiltonian that harness nonadiabatic transitions. These corrections define a set of dressed states that the system follows exactly during the state transfer. We apply this approach to stimulated Raman adiabatic passage protocols and show that a suitable choice of dressed states allows one to design fast protocols that do not require additional couplings, while simultaneously minimizing the occupancy of the "intermediate" level.
Gamallo, P; Defazio, P; Akpinar, S; Petrongolo, C
2012-08-16
We present the Born-Oppenheimer (BO) quantum mechanical (QM) dynamics of the CH decay (d) CH(X2Π) + H(2S) → C(3P) + H2(X1Σ(g)(+)) and of the H exchange reaction (e) CH(X2Π) + H′(2S) → CH′(X2Π) + H(2S) on the CH2 X̃3A″ adiabatic potential energy surface (PES) of Harding et al. (J. Phys. Chem. 1993, 97, 5472). A thorough analysis of the correlation diagram of the four lowest CH2 electronic states, as well as Renner-Teller and spin–orbit nonadiabatic test calculations on the X̃3A″, ã1A′, and b̃1A″ coupled PESs, validate the X̃3A″ BO results, confirming that these reactions occur essentially on the uncoupled X̃3A″ ground surface. We consider the CH molecule in the ground vibrational state and in the four lowest rotational states j0. Thus, we obtain initial-state resolved reaction probabilities, cross sections, and rate constants by propagating coupled-channel real wave packets and performing flux analyses. If J is the total angular momentum quantum number and K is its projection along the body-fixed z axis, CH + H gives essentially the C + H2 products via a barrierless K-inhibited insertion, CH2 resonances at low J, and large cross sections near the threshold. These cross sections decrease strongly with collision energy and depend slightly on j0. On the other hand, the small cross sections obtained for the (e) channel are nearly independent of energy. From initial-state resolved rate constants and Boltzmann populations at temperature T, we obtain QM thermal rate constants from 100 to 400 K: at 300 K, k(d) = (9.57 ± 0.96) × 10(-11) and k(e) = (1.41 ± 0.14) × 10(-11) cm(3) s(-1) for (d) and (e) reactions, respectively. The k(d) value is in good agreement with previous quasi-classical trajectory (QCT) results on the same PES, but it is larger than that observed at 297 K by a factor of 7. On the contrary, and in agreement with the small role of CH2 excited electronic states, X̃3A″ QCT and experimental rate constants agree at high
NASA Astrophysics Data System (ADS)
Mukherjee, Saikat; Adhikari, Satrajit
2014-08-01
We calculate the adiabatic potential energy surfaces (PESs) and the non-adiabatic coupling terms (NACTs) for the excited electronic states of K3 cluster by MRCI approach using MOLPRO. The NACTs are adapted with molecular symmetry to assign appropriate IREPs so that the elements of the Hamiltonian matrix are totally symmetric. We incorporate those NACTs into three-state adiabatic-to-diabatic transformation (ADT) equations to obtain ADT angles for constructing continuous, single-valued, smooth and symmetric diabatic Hamiltonian matrix, where its elements are fitted with analytic functions. Finally, we demonstrate that the dressed diabatic and adiabatic-via-dressed diabatic PECs show prominent topological effect over dressed adiabatic curves.
Classical nuclear motion coupled to electronic non-adiabatic transitions
NASA Astrophysics Data System (ADS)
Agostini, Federica; Abedi, Ali; Gross, E. K. U.
2014-12-01
Based on the exact factorization of the electron-nuclear wave function, we have recently proposed a mixed quantum-classical scheme [A. Abedi, F. Agostini, and E. K. U. Gross, Europhys. Lett. 106, 33001 (2014)] to deal with non-adiabatic processes. Here we present a comprehensive description of the formalism, including the full derivation of the equations of motion. Numerical results are presented for a model system for non-adiabatic charge transfer in order to test the performance of the method and to validate the underlying approximations.
Classical nuclear motion coupled to electronic non-adiabatic transitions
Agostini, Federica; Abedi, Ali; Gross, E. K. U.
2014-12-07
Based on the exact factorization of the electron-nuclear wave function, we have recently proposed a mixed quantum-classical scheme [A. Abedi, F. Agostini, and E. K. U. Gross, Europhys. Lett. 106, 33001 (2014)] to deal with non-adiabatic processes. Here we present a comprehensive description of the formalism, including the full derivation of the equations of motion. Numerical results are presented for a model system for non-adiabatic charge transfer in order to test the performance of the method and to validate the underlying approximations.
Semiclassical quantization of bound and quasistationary states beyond the adiabatic approximation
Benderskii, V.A.; Vetoshkin, E.V.; Kats, E.I.
2004-06-01
We examine one important (and previously overlooked) aspect of well-known crossing diabatic potentials or Landau-Zener (LZ) problem. We derive the semiclassical quantization rules for the crossing diabatic potentials with localized initial and localized or delocalized final states, in the intermediate energy region, when all four adiabatic states are coupled and should be taken into account. We found all needed connection matrices and present the following analytical results: (i) in the tunneling region, the splittings of vibrational levels are represented as a product of the splitting in the lower adiabatic potential and the nontrivial function depending on the Massey parameter; (ii) in the overbarrier region, we find specific resonances between the levels in the lower and in the upper adiabatic potentials and, in that condition, independent quantizations rules are not correct; (iii) for the delocalized final states (decay lower adiabatic potential), we describe quasistationary states and calculate the decay rate as a function of the adiabatic coupling; and (iv) for the intermediate energy regions, we calculate the energy level quantization, which can be brought into a compact form by using either adiabatic or diabatic basis set (in contrast to the previous results found in the Landau diabatic basis). Applications of the results may concern the various systems; e.g., molecules undergoing conversion of electronic states, radiationless transitions, or isomerization reactions.
Benabbas, Abdelkrim; Salna, Bridget; Sage, J. Timothy; Champion, Paul M.
2015-03-21
Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical “gating” distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working
Benabbas, Abdelkrim; Salna, Bridget; Sage, J Timothy; Champion, Paul M
2015-03-21
Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical "gating" distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working near
NASA Astrophysics Data System (ADS)
Benabbas, Abdelkrim; Salna, Bridget; Sage, J. Timothy; Champion, Paul M.
2015-03-01
Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical "gating" distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working near
NASA Astrophysics Data System (ADS)
Agostini, Federica; Abedi, Ali; Suzuki, Yasumitsu; Min, Seung Kyu; Maitra, Neepa T.; Gross, E. K. U.
2015-03-01
The Born-Oppenheimer (BO) approximation allows to visualize the coupled electron-nuclear dynamics in molecular systems as a set of nuclei moving on a single potential energy surface representing the effect of the electrons in a given eigenstate. Many interesting phenomena, however, such as vision or charge separation in organic photovoltaic materials, take place in conditions beyond its range of validity. Nevertheless, the basic construct of the adiabatic treatment, the BO potential energy surfaces, is employed to describe non-adiabatic processes and the full problem is represented in terms of adiabatic states and transitions among them in regions of strong non-adiabatic coupling. But the concept of single potential energy is lost. The alternative point of view arising in the framework of the exact factorization of the electron-nuclear wave function will be presented. A single, time-dependent, potential energy provides the force driving the nuclear motion and is adopted as starting point for the development of quantum-classical approximations to the full quantum mechanical problem.
Non-adiabatic response of relativistic radiation belt electrons to GEM magnetic storms
NASA Astrophysics Data System (ADS)
McAdams, K. L.; Reeves, G. D.
The importance of fully adiabatic effects in the relativistic radiation belt electron response to magnetic storms is poorly characterized due to many difficulties in calculating adiabatic flux response. Using the adiabatic flux model of Kim and Chan [1997a] and Los Alamos National Laboratory geosynchronous satellite data, we examine the relative timing of the adiabatic and non-adiabatic flux responses. In the three storms identified by the GEM community for in depth study, the non-adiabatic energization occurs hours earlier than the adiabatic re-energization. The adiabatic energization can account for only 10-20% of the flux increases in the first recovery stages, and only 1% of the flux increase if there is continuing activity.
Geometric Phase for Adiabatic Evolutions of General Quantum States
Wu, Biao; Liu, Jie; Niu, Qian; Singh, David J
2005-01-01
The concept of a geometric phase (Berry's phase) is generalized to the case of noneigenstates, which is applicable to both linear and nonlinear quantum systems. This is particularly important to nonlinear quantum systems, where, due to the lack of the superposition principle, the adiabatic evolution of a general state cannot be described in terms of eigenstates. For linear quantum systems, our new geometric phase reduces to a statistical average of Berry's phases. Our results are demonstrated with a nonlinear two-level model.
Adiabatic creation of atomic squeezing in dark states versus decoherences
Gong, Z. R.; Sun, C. P.; Wang Xiaoguang
2010-07-15
We study the multipartite correlations of the multiatom dark states, which are characterized by the atomic squeezing beyond the pairwise entanglement. It is shown that, in the photon storage process with atomic ensemble via the electromagnetically induced transparency (EIT) mechanism, the atomic squeezing and the pairwise entanglement can be created by adiabatically manipulating the Rabi frequency of the classical light field on the atomic ensemble. We also consider the sudden death for the atomic squeezing and the pairwise entanglement under various decoherence channels. An optimal time for generating the greatest atomic squeezing and pairwise entanglement is obtained by studying in detail the competition between the adiabatic creation of quantum correlation in the atomic ensemble and the decoherence that we describe with three typical decoherence channels.
Adiabatic perturbation theory of electronic stopping in insulators
NASA Astrophysics Data System (ADS)
Horsfield, Andrew P.; Lim, Anthony; Foulkes, W. M. C.; Correa, Alfredo A.
2016-06-01
A model able to explain the complicated structure of electronic stopping at low velocities in insulating materials is presented. It is shown to be in good agreement with results obtained from time-dependent density-functional theory for the stopping of a channeling Si atom in a Si crystal. If we define the repeat frequency f =v /λ , where λ is the periodic repeat length of the crystal along the direction the channeling atom is traveling, and v is the velocity of the channeling atom, we find that electrons experience a perturbing force that varies in time at integer multiples l of f . This enables electronic excitations at low atom velocity, but their contributions diminish rapidly with increasing values of l . The expressions for stopping power are derived using adiabatic perturbation theory for many-electron systems, and they are then specialized to the case of independent electrons. A simple model for the nonadiabatic matrix elements is described, along with the procedure for determining its parameters.
Rotation-vibrational states of H3+ and the adiabatic approximation.
Alijah, Alexander; Hinze, Juergen
2006-11-15
We discuss recent progress in the calculation and identification of rotation-vibrational states of H3+ at intermediate energies up to 13,000 cm(-1). Our calculations are based on the potential energy surface of Cencek et al. which is of sub-microhartree accuracy. As this surface includes diagonal adiabatic and relativistic corrections to the fixed nuclei electronic energies, the remaining discrepancies between our calculated and experimental data should be due to the neglect of non-adiabatic coupling to excited electronic states in the calculations. To account for this, our calculated energy values were adjusted empirically by a simple correction formula. Based on our understanding of the adiabatic approximation, we suggest two new approaches to account for the off-diagonal adiabatic correction, which should work; however, they have not been tested yet for H3+. Theoretical predictions made for the above-barrier energy region of recent experimental interest are accurate to 0.35 cm(-1) or better. PMID:17015396
Semiclassical analysis of the electron-nuclear coupling in electronic non-adiabatic processes
NASA Astrophysics Data System (ADS)
Agostini, Federica; Min, Seung Kyu; Gross, E. K. U.
2015-10-01
In the context of the exact factorization of the electron-nuclear wave function, the coupling between electrons and nuclei beyond the adiabatic regime is encoded (i) in the time-dependent vector and scalar potentials and (ii) in the electron-nuclear coupling operator. The former appear in the Schroedinger-like equation that drives the evolution of the nuclear degrees of freedom, whereas the latter is responsible for inducing non-adiabatic effects in the electronic evolution equation. As we have devoted previous studies to the analysis of the vector and scalar potentials, in this paper we focus on the properties of the electron-nuclear coupling operator, with the aim of describing a numerical procedure to approximate it within a semiclassical treatment of the nuclear dynamics.
NASA Astrophysics Data System (ADS)
Savoini, P.; Lembege, B.
2006-12-01
Test particle simulations are performed in order to analyze in details the dynamics of transmitted electrons through a supercritical strictly perpendicular collisionless shock. Recent analysis has evidenced three different behavior for the electron population: (i) adiabatic, (ii) over-adiabatic characterized by an increase of the gyrating velocity higher than that expected from the conservation of the magnetic moment and (iii) under- adiabatic characterized by a decrease of this velocity and not predicted by any existing theory. Analysis of individual time particle trajectories is performed and completed by statistics based on different upstream distributions (spherical shell and Maxwellian). The use of a Maxwellian distribution function allows us to speak in term of an electronic temperature and we observe in agreement with experimental datas that as the temperature increases (enlarged Maxwellian distribution function) the number of non-adiabatic transmitted electrons drastically decreases. In addition, our study evidenced that both non-adiabatic populations are coming from the core of the electron distribution. All combined nonstationary and nonuniformity effects have a filtering impact on the relative percentages of adiabatic and over-adiabatic populations, in contrast with under- adiabatic population which is relatively poorly affected.
Hermann, Gunter; Liu, ChunMei; Manz, Jörn; Paulus, Beate; Pérez-Torres, Jhon Fredy; Pohl, Vincent; Tremblay, Jean Christophe
2016-07-14
Recently, adiabatic attosecond charge migration (AACM) has been monitored and simulated for the first time, with application to the oriented iodoacetylene cation where AACM starts from the initial superposition of the ground state (φ0) and an electronic excited state (φ1). Here, we develop the theory for electronic fluxes during AACM in ring-shaped molecules, with application to oriented benzene prepared in the superposition of the ground and first excited singlet states. The initial state and its time evolution are analogous to coherent tunneling where φ0 and φ1 have different meanings; however, they denote the wave functions of the lowest tunneling doublet. This analogy suggests to transfer the theory of electronic fluxes during coherent tunneling to AACM, with suitable modifications which account for (i) the different time scales and (ii) the different electronic states, and which make use of (iii) the preparation of the initial state for AACM by a linearly polarized laser pulse. Application to benzene yields the multidirectional angular electronic flux with a pincer-motion type pattern during AACM: this unequivocal result confirms a previous working hypothesis. Moreover, the theory of AACM allows quantification of the electronic flux; that is, the maximum number of electrons (out of 42) which flow concertedly during AACM in benzene is 6 × 0.08 = 0.48. PMID:27046151
Stimulated Raman adiabatic passage for improved performance of a cold-atom electron and ion source
NASA Astrophysics Data System (ADS)
Sparkes, B. M.; Murphy, D.; Taylor, R. J.; Speirs, R. W.; McCulloch, A. J.; Scholten, R. E.
2016-08-01
We implement high-efficiency coherent excitation to a Rydberg state using stimulated Raman adiabatic passage in a cold-atom electron and ion source. We achieve an efficiency of 60% averaged over the laser excitation volume with a peak efficiency of 82%, a 1.6 times improvement relative to incoherent pulsed-laser excitation. Using pulsed electric field ionization of the Rydberg atoms we create electron bunches with durations of 250 ps. High-efficiency excitation will increase source brightness, crucial for ultrafast electron diffraction experiments, and coherent excitation to high-lying Rydberg states could allow for the reduction of internal bunch heating and the creation of a high-speed single-ion source.
NASA Astrophysics Data System (ADS)
Yarkony, David
2015-03-01
The construction of fit single state potential energy surfaces (PESs), analytic representations of ab initio electronic energies and energy gradients, is now well established. These single state PESs, which are essential for accurate quantum dynamics and have found wide application in more approximate quasi-classical treatments, have revolutionized adiabatic dynamics. The situation for nonadiabatic processes involving dissociative and large amplitude motion is less sanguine. In these cases, compared to single electronic state dynamics, both the electronic structure data and the representation are more challenging to determine. We describe the recent development and applications of algorithms that enable description of multiple adiabatic electronic potential energy surfaces coupled by conical intersections in their full dimensionality using coupled quasi-diabatic states. These representations are demonstrably quasi-diabatic, provide accurate representations of conical intersection seams and can smooth out the discontinuities in electronic structure energies due to changing active orbital spaces that routinely afflict global multistate representations.
Diestler, D J
2012-03-22
The Born-Oppenheimer (BO) description of electronically adiabatic molecular processes predicts a vanishing electronic flux density (j(e)),
Non-adiabatic dynamics around a conical intersection with surface-hopping coupled coherent states
NASA Astrophysics Data System (ADS)
Humeniuk, Alexander; Mitrić, Roland
2016-06-01
A surface-hopping extension of the coupled coherent states-method [D. Shalashilin and M. Child, Chem. Phys. 304, 103-120 (2004)] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schrödinger equation for the motion of the nuclei is solved in a moving basis set. The basis set is guided by classical trajectories, which can hop stochastically between different electronic potential energy surfaces. The non-adiabatic transitions are modelled by a modified version of Tully's fewest switches algorithm. The trajectories consist of Gaussians in the phase space of the nuclei (coherent states) combined with amplitudes for an electronic wave function. The time-dependent matrix elements between different coherent states determine the amplitude of each trajectory in the total multistate wave function; the diagonal matrix elements determine the hopping probabilities and gradients. In this way, both interference effects and non-adiabatic transitions can be described in a very compact fashion, leading to the exact solution if convergence with respect to the number of trajectories is achieved and the potential energy surfaces are known globally. The method is tested on a 2D model for a conical intersection [A. Ferretti, J. Chem. Phys. 104, 5517 (1996)], where a nuclear wavepacket encircles the point of degeneracy between two potential energy surfaces and interferes with itself. These interference effects are absent in classical trajectory-based molecular dynamics but can be fully incorpo rated if trajectories are replaced by surface hopping coupled coherent states.
Non-adiabatic dynamics around a conical intersection with surface-hopping coupled coherent states.
Humeniuk, Alexander; Mitrić, Roland
2016-06-21
A surface-hopping extension of the coupled coherent states-method [D. Shalashilin and M. Child, Chem. Phys. 304, 103-120 (2004)] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schrödinger equation for the motion of the nuclei is solved in a moving basis set. The basis set is guided by classical trajectories, which can hop stochastically between different electronic potential energy surfaces. The non-adiabatic transitions are modelled by a modified version of Tully's fewest switches algorithm. The trajectories consist of Gaussians in the phase space of the nuclei (coherent states) combined with amplitudes for an electronic wave function. The time-dependent matrix elements between different coherent states determine the amplitude of each trajectory in the total multistate wave function; the diagonal matrix elements determine the hopping probabilities and gradients. In this way, both interference effects and non-adiabatic transitions can be described in a very compact fashion, leading to the exact solution if convergence with respect to the number of trajectories is achieved and the potential energy surfaces are known globally. The method is tested on a 2D model for a conical intersection [A. Ferretti, J. Chem. Phys. 104, 5517 (1996)], where a nuclear wavepacket encircles the point of degeneracy between two potential energy surfaces and interferes with itself. These interference effects are absent in classical trajectory-based molecular dynamics but can be fully incorpo rated if trajectories are replaced by surface hopping coupled coherent states. PMID:27334155
Fernandez-Alberti, Sebastian; Makhov, Dmitry V; Tretiak, Sergei; Shalashilin, Dmitrii V
2016-04-21
Photoinduced dynamics of electronic and vibrational unidirectional energy transfer between meta-linked building blocks in a phenylene ethynylene dendrimer is simulated using a multiconfigurational Ehrenfest in time-dependent diabatic basis (MCE-TDDB) method, a new variant of the MCE approach developed by us for dynamics involving multiple electronic states with numerous abrupt crossings. Excited-state energies, gradients and non-adiabatic coupling terms needed for dynamics simulation are calculated on-the-fly using the Collective Electron Oscillator (CEO) approach. A comparative analysis of our results obtained using MCE-TDDB, the conventional Ehrenfest method and the surface-hopping approach with and without decoherence corrections is presented. PMID:27004611
Karpeshin, F. F.; Trzhaskovskaya, M. B.
2015-12-15
Special features of the effect of the electron shell on alpha decay that have important experimental implications are studied within the adiabatic approach. The magnitude of the effect is about several tenths of a percent or smaller, depending on the transition energy and on the atomic number. A dominant role of inner shells is shown: more than 80% of the effect is saturated by 1s electrons. This circumstance plays a crucial role for experiments, making it possible to measure this small effect by a difference method in the same storage rings via a comparison of, for example, decay probabilities in bare nuclei and heliumlike ions. The reasons behind the relative success and the applicability limits of the frozen-shell model, which has been used to calculate the effect in question for more than half a century, are analyzed. An interesting experiment aimed at studying charged alpha-particle states is proposed. This experiment will furnish unique information for testing our ideas of the interplay of nonadiabatic and adiabatic processes.
NASA Astrophysics Data System (ADS)
Savoini, Ph.; Lembège, B.; Krasnoselskikh, V.; Balikhin, M.
Test particles simulations have been performed in order to analyze quantitatively the non adiabatic heating of electrons crossing the shock front of a planar quasi-perpendicular shock. Profiles of E and B fields are issued from selfconsistent 2D full particle simulations. Results evidence the non adiabatic dynamic of a certain percentage of transmitted electrons and allow to validate the theoritical prediction of Balikhin et al. (1998). Present numerical study is extended to the quantitative statistical approach. Test particles simulations have been performed with drifted electrons crossing homogeneous shock profiles. Both cubes and spherical shell electron velocity distributions have been investigated. Relative nonadiabatic and adiabatic electron heating efficiency is discussed versus initial velocities, pitch angle and shock profile encounter by the electrons. Numerical estimates of the Lyapounov coefficient (velocity volume expansion at crossing) are deduced from simulations and will be compared with theoretical expectations.
Understanding electronically non-adiabatic relaxation dynamics in singlet fission.
Tao, Guohua
2015-01-13
Nonadiabatic relaxation of one singlet state into two triplet states is the key step in singlet fission dynamics, the understandings of which may help design next generation solar cells. In this work we perform the symmetrical quasi-classical (SQC) nonadiabatic molecular dynamics (MD) simulation [Cotton and Miller, J. Phys. Chem. A, 2013, 117, 7190; Meyer and Miller, J. Chem. Phys. 1979, 70, 3214] for a model system to study the real-time fission dynamics. The dependence of the nonadiabatic relaxation dynamics on energy levels, electronic couplings, and electronic-phonon couplings has been examined, in comparison with other analytical approximations, such as Förster theory and Marcus theory. Unlike many other methods, the SQC nondiabatic MD simulation approach is able to describe fission dynamics efficiently and accurately enough to provide microscopic insights into singlet fission. PMID:26574200
CVRQD ab initio ground-state adiabatic potential energy surfaces for the water molecule.
Barletta, Paolo; Shirin, Sergei V; Zobov, Nikolai F; Polyansky, Oleg L; Tennyson, Jonathan; Valeev, Edward F; Császár, Attila G
2006-11-28
The high accuracy ab initio adiabatic potential energy surfaces (PESs) of the ground electronic state of the water molecule, determined originally by Polyansky et al. [Science 299, 539 (2003)] and called CVRQD, are extended and carefully characterized and analyzed. The CVRQD potential energy surfaces are obtained from extrapolation to the complete basis set of nearly full configuration interaction valence-only electronic structure computations, augmented by core, relativistic, quantum electrodynamics, and diagonal Born-Oppenheimer corrections. We also report ab initio calculations of several quantities characterizing the CVRQD PESs, including equilibrium and vibrationally averaged (0 K) structures, harmonic and anharmonic force fields, harmonic vibrational frequencies, vibrational fundamentals, and zero-point energies. They can be considered as the best ab initio estimates of these quantities available today. Results of first-principles computations on the rovibrational energy levels of several isotopologues of the water molecule are also presented, based on the CVRQD PESs and the use of variational nuclear motion calculations employing an exact kinetic energy operator given in orthogonal internal coordinates. The variational nuclear motion calculations also include a simplified treatment of nonadiabatic effects. This sophisticated procedure to compute rovibrational energy levels reproduces all the known rovibrational levels of the water isotopologues considered, H(2) (16)O, H(2) (17)O, H(2) (18)O, and D(2) (16)O, to better than 1 cm(-1) on average. Finally, prospects for further improvement of the ground-state adiabatic ab initio PESs of water are discussed. PMID:17144700
The adiabatic limit of the exact factorization of the electron-nuclear wave function
NASA Astrophysics Data System (ADS)
Eich, F. G.; Agostini, Federica
2016-08-01
We propose a procedure to analyze the relation between the exact factorization of the electron-nuclear wave function and the Born-Oppenheimer approximation. We define the adiabatic limit as the limit of infinite nuclear mass. To this end, we introduce a unit system that singles out the dependence on the electron-nuclear mass ratio of each term appearing in the equations of the exact factorization. We observe how non-adiabatic effects induced by the coupling to the nuclear motion affect electronic properties and we analyze the leading term, connecting it to the classical nuclear momentum. Its dependence on the mass ratio is tested numerically on a model of proton-coupled electron transfer in different non-adiabatic regimes.
The adiabatic limit of the exact factorization of the electron-nuclear wave function.
Eich, F G; Agostini, Federica
2016-08-01
We propose a procedure to analyze the relation between the exact factorization of the electron-nuclear wave function and the Born-Oppenheimer approximation. We define the adiabatic limit as the limit of infinite nuclear mass. To this end, we introduce a unit system that singles out the dependence on the electron-nuclear mass ratio of each term appearing in the equations of the exact factorization. We observe how non-adiabatic effects induced by the coupling to the nuclear motion affect electronic properties and we analyze the leading term, connecting it to the classical nuclear momentum. Its dependence on the mass ratio is tested numerically on a model of proton-coupled electron transfer in different non-adiabatic regimes. PMID:27497542
Quantum Lattice Fluctuations in the Charge Density Wave State beyond the Adiabatic Approximation
NASA Astrophysics Data System (ADS)
Shida, Keisuke; Watanabe, Yuko; Gomi, Hiroki; Takahashi, Akira; Tomita, Norikazu
2015-12-01
We have developed a tractable numerical method in which large-amplitude quantum lattice fluctuations can be described beyond the adiabatic approximation using the coherent state representation of phonons. A many-body wave function is constructed by the superposition of direct products of non-orthogonal Slater determinants for electrons and coherent states of phonons. Both orbitals in all the Slater determinants and the amplitudes of all the coherent states are simultaneously optimized. We apply the method to the one-dimensional Su-Schrieffer-Heeger model with the on-site and nearest-neighbor-site Coulomb interactions. It is shown the lattice fluctuations in doped charge density wave (CDW) systems are described by the translational and vibrational motion of lattice solitons. Such lattice solitons induce bond alternation in the doped CDW system while the lattice becomes equidistant in the half-filled CDW system.
NASA Astrophysics Data System (ADS)
Su, Zhenpeng; Xiao, Fuliang; Zheng, Huinan; Wang, Shui
2010-10-01
Storm-time radial diffusion of radiation belt electrons with arbitrary pitch angles in a time-varying geomagnetic field is simulated based on our recently developed STEERB code. In particular, the fully adiabatic response of energetic electrons to the variation of geomagnetic field is self-consistently incorporated. Simulation results show that the outward adiabatic transport (instead of outward radial diffusion) is primarily responsible for the main phase depletion of energetic electron fluxes at large pitch angles beyond 5Re (Re is the Earth's radius). However, combined radial diffusion and adiabatic transport contributes insignificantly to the main phase depletion of energetic electron fluxes within 5Re, or the recovery phase enhancement of energetic electron fluxes in the outer radiation belt. Moreover, the simulation with both radial diffusion and adiabatic transport shows that the pitch angle distribution of energetic outer zone electrons can evolve from a rounded 90°-peaked distribution to a butterfly-shaped distribution during the main phase, and back to a rounded 90°-peaked distribution during the recovery phase. Such essential changes of pitch angle distribution may further affect the efficiency of other local loss and energization mechanisms.
Adiabatic ab initio study of the BaH(+) ion including high energy excited states.
Mejrissi, Leila; Habli, Héla; Ghalla, Houcine; Oujia, Brahim; Gadéa, Florent Xavier
2013-07-01
An adiabatic study of 1-34 (1,3)Σ(+) electronic states of barium hydride ion (BaH(+)) is presented for all states dissociating below the ionic limit Ba(2+)H(-). The 1-20 (1,3)Π and 1-12 (1,3)Δ states have been also investigated. In our approach, the valence electrons of the Ba(2+) ion described by an effective core potential (ECP) and core polarization potential (CPP) with l-dependent cutoff functions have been used. The ionic molecule BaH(+) has been treated as a two-electron system, and the full valence configuration interaction (CI) is easily achieved. The spectroscopic constants Re, De, Te, ωe, ωexe, and Be are derived. In addition, vibrational level spacing and permanent and transition dipole moments are determined and analyzed. Unusual potential shapes are found and also accidental quasidegeneracy in the vibrational spacing progression for various excited states. The (1)Σ(+) states exhibit ionic charge transfer avoided crossings series which could lead to neutralization or even H(-) formation in collisions of H(+) with Ba. PMID:23701525
NASA Astrophysics Data System (ADS)
Dorofeev, Dmitry L.; Elfimov, Sergei V.; Zon, Boris A.
2012-02-01
This paper is dedicated to the implementation of a generalized approach for calculating quantum defects in high Rydberg states of polar molecules with an account for the dipole moment of the molecular core and l uncoupling of the Rydberg electron. Adiabatic (Born-Oppenheimer) and nonadiabatic (inverse Born-Oppenheimer) regions of the spectrum are considered. The nonadiabatic case with a nonzero projection of the core momentum on the core axis is considered and is illustrated by the example of the SO molecule.
NASA Astrophysics Data System (ADS)
Hofmann, C.; Zimmermann, T.; Zielinski, A.; Landsman, A. S.
2016-04-01
The validity of the adiabatic approximation in strong field ionization under typical experimental conditions has recently become a topic of great interest. Experimental results have been inconclusive, in part, due to the uncertainty in experimental calibration of intensity. Here we turn to the time-dependent Schrödinger equation, where all the laser parameters are known exactly. We find that the centre of the electron momentum distribution (typically used for calibration of elliptically and circularly polarized light) is sensitive to non-adiabatic effects, leading to intensity shifts in experimental data that can significantly affect the interpretation of results. On the other hand, the transverse momentum spread in the plane of polarization is relatively insensitive to such effects, even in the Keldysh parameter regime approaching γ ≈ 3. This suggests the transverse momentum spread in the plane of polarization as a good alternative to the usual calibration method, particularly for experimental investigation of non-adiabatic effects using circularly polarized light.
Electronically non-adiabatic influences in surface chemistry and dynamics.
Wodtke, Alec M
2016-07-01
Electronically nonadiabatic interactions between molecules and metal surfaces are now well known. Evidence is particularly clear from studies of diatomic molecules that molecular vibration can be strongly coupled to electrons of the metal leading to efficient energy transfer between these two kinds of motion. Since molecular vibration is the same motion needed for bond breaking, it is logical to postulate that electronically nonadiabatic influences on surface chemical reaction probabilities would be strong. Still there are few if any examples where such influences have been clearly investigated. This review recounts the evidence for and against the aforementioned postulate emphasizing reacting systems that have yet to receive full attention and where electronically nonadiabatic influence of reaction probabilities might be clearly demonstrated. PMID:27152489
Non-adiabatic generation of NOON states in a Tonks-Girardeau gas
NASA Astrophysics Data System (ADS)
Schloss, James; Benseny, Albert; Gillet, Jérémie; Swain, Jacob; Busch, Thomas
2016-03-01
Adiabatic techniques can be used to control quantum states with high fidelity while exercising limited control over the parameters of a system. However, because these techniques are slow compared to other timescales in the system, they are usually not suitable for creating highly unstable states or performing time-critical processes. Both of these situations arise in quantum information processing, where entangled states may be isolated from the environment only for a short time and where quantum computers require high-fidelity operations to be performed quickly. Recently it has been shown that techniques like optimal control and shortcuts to adiabaticity can be used to prepare quantum states non-adiabatically with high fidelity. Here we present two examples of how these techniques can be used to create maximally entangled many-body NOON states in one-dimensional Tonks-Girardeau gases. Dedicated to the memory of Marvin D Girardeau.
Adiabatic many-body state preparation and information transfer in quantum dot arrays
NASA Astrophysics Data System (ADS)
Farooq, Umer; Bayat, Abolfazl; Mancini, Stefano; Bose, Sougato
2015-04-01
Quantum simulation of many-body systems are one of the most interesting tasks of quantum technology. Among them is the preparation of a many-body system in its ground state when the vanishing energy gap makes the cooling mechanisms ineffective. Adiabatic theorem, as an alternative to cooling, can be exploited for driving the many-body system to its ground state. In this paper, we study two most common disorders in quantum dot arrays, namely exchange coupling fluctuations and hyperfine interaction, in adiabatic preparation of ground state in such systems. We show that the adiabatic ground-state preparation is highly robust against those disorder effects making it a good analog simulator. Moreover, we also study the adiabatic quantum information transfer, using singlet-triplet states, across a spin chain. In contrast to ground-state preparation the transfer mechanism is highly affected by disorder and in particular, the hyperfine interaction is very destructive for the performance. This suggests that for communication tasks across such arrays adiabatic evolution is not as effective and quantum quenches could be preferable.
The adiabatic phase mixing and heating of electrons in Buneman turbulence
Che, H.; Goldstein, M. L.; Drake, J. F.; Swisdak, M.
2013-06-15
The nonlinear development of the strong Buneman instability and the associated fast electron heating in thin current layers with Ω{sub e}/ω{sub pe}<1 is explored. Phase mixing of the electrons in wave potential troughs and a rapid increase in temperature are observed during the saturation of the instability. We show that the motion of trapped electrons can be described using a Hamiltonian formalism in the adiabatic approximation. The process of separatrix crossing as electrons are trapped and de-trapped is irreversible and guarantees that the resulting electron energy gain is a true heating process.
Dawn-dusk asymmetry and adiabatic dynamic of the radiation belt electrons during magnetic storm
NASA Astrophysics Data System (ADS)
Lazutin, Leonid L.
2016-09-01
The changes of the latitudinal profiles of outer belt energetic electrons during magnetic storms are mostly explained by the precipitation into the loss cone caused by VLF and EMIC waves or by the scattering into the magnetopause. In present work, energetic electron dynamics during magnetic storm of August 29-30, 2004 we attributed at most to the adiabatic transformation of the magnetic drift trajectories and Dst effect. This conclusion was based on the analysis of dawn-dusk asymmetry of the electron latitudinal profiles measured by low altitude polar orbiter SERVIS-1 and on the coincidence of pre-storm and after-storm profiles of radiation belt electrons and protons.
Rapid Adiabatic Preparation of Injective Projected Entangled Pair States and Gibbs States
NASA Astrophysics Data System (ADS)
Ge, Yimin; Molnár, András; Cirac, J. Ignacio
2016-02-01
We propose a quantum algorithm for many-body state preparation. It is especially suited for injective projected entangled pair states and thermal states of local commuting Hamiltonians on a lattice. We show that for a uniform gap and sufficiently smooth paths, an adiabatic runtime and circuit depth of O (polylog N ) can be achieved for O (N ) spins. This is an almost exponential improvement over previous bounds. The total number of elementary gates scales as O (N p o l y l o g N ) . This is also faster than the best known upper bound of O (N2) on the mixing times of Monte Carlo Markov chain algorithms for sampling classical systems in thermal equilibrium.
Miller, William H.; Orel, Ann E.
1980-11-01
A classical interpretation of the Dirac-Van Vleck spin version of valence bond theory is used to obtain a classical model for electronic degrees of freedom within the valence bond framework. The approach is illustrated by deriving the explicit forms of the classical Hamiltonians, involving electronic and heavy particle degrees of freedom, for the H-H{sub 2}, F-H{sub 2} , and O-H{sub 2} systems. It is also shown how the initial conditions for both electronic and heavy particle degrees of freedom are chosen to carry out a classical trajectory simulation of collision processes. The attractive feature of this model is that it is as eaaily applicable to electronically non-adiabatic processes as it is to adiabatic ones.
Stark-shift-chirped rapid-adiabatic-passage technique among three states
Rangelov, A. A.; Vitanov, N. V.; Yatsenko, L. P.; Shore, B. W.; Halfmann, T.; Bergmann, K.
2005-11-15
We show that the technique of Stark-chirped rapid adiabatic passage (SCRAP), hitherto used for complete population transfer between two quantum states, offers a simple and robust method for complete population transfer amongst three states in atoms and molecules. In this case SCRAP uses three laser pulses: a strong far-off-resonant pulse modifies the transition frequencies by inducing dynamic Stark shifts and thereby creating time-dependent level crossings amongst the three diabatic states, while near-resonant and moderately strong pump and Stokes pulses, appropriately offset in time, drive the population between the initial and final states via adiabatic passage. The population transfer efficiency is robust to variations in the intensities of the lasers, as long as these intensities are sufficiently large to enforce adiabatic evolution. With suitable pulse timings the population in the (possibly decaying) intermediate state can be minimized, as with stimulated Raman adiabatic passage (STIRAP). This technique applies to one-photon as well as multiphoton transitions and it is also applicable to media exhibiting inhomogeneous broadening; these features represent clear advantages over STIRAP by overcoming the inevitable dynamical Stark shifts that accompany multiphoton transitions as well as unwanted detunings, e.g., induced by Doppler shifts.
Adiabatic path to fractional quantum Hall states of a few bosonic atoms
Popp, M.; Paredes, B.; Cirac, J.I.
2004-11-01
We propose a realistic scheme to create motionally entangled states of a few bosonic atoms. It can experimentally be realized with a gas of ultracold bosonic atoms trapped in a deep optical lattice potential. By simultaneously deforming and rotating the trapping potential on each lattice site it is feasible to adiabatically create a variety of entangled states on each lattice well. We fully address the case of N=2 and 4 atoms per well and identify a sequence of fractional quantum Hall states: the Pfaffian state, the 1/2-Laughlin quasiparticle, and the 1/2-Laughlin state. Exact knowledge of the spectrum has allowed us to design adiabatic paths to these states, with all times and parameters well within the reach of current experimental setups. We further discuss the detection of these states by measuring different properties as their density profile, angular momentum, or correlation functions.
Di Lisi, Antonio; De Siena, Silvio; Illuminati, Fabrizio; Vitali, David
2005-09-15
We introduce an efficient, quasideterministic scheme to generate maximally entangled states of two atomic ensembles. The scheme is based on quantum nondemolition measurements of total atomic populations and on adiabatic quantum feedback conditioned by the measurements outputs. The high efficiency of the scheme is tested and confirmed numerically for ideal photodetection as well as in the presence of losses.
Orel, Ann E.; Miller, William H.
1980-11-01
A recently developed classical model for electronically nonadiabatic collision processes is applied to electronic-vibrational energy transfer in a collinear atom~diatom system, A + BC(v=1) + A*+ BC(v=0), which closely resembles Br-H{sub 2}. This classical model, which treats electronic as well as heavy particle (i.e., translation, rotation, and vibration) degrees of freedom by classical mechanics, is found to describe the resonance features in this process reasonably well. The usefulness of the approach is that it allows one to extend standard Monte Carlo classical trajectory methodology to include electronically non-adiabatic processes in a dynamically consistent way,
A dynamical approach to non-adiabatic electron transfers at the bio-inorganic interface.
Zanetti-Polzi, Laura; Corni, Stefano
2016-04-21
A methodology is proposed to investigate electron transfer reactions between redox-active biomolecular systems (e.g. a protein) and inorganic surfaces. The whole system is modelled at the atomistic level using classical molecular dynamics - making an extensive sampling of the system's configurations possible - and the energies associated with the redox-active complex reduction are calculated using a hybrid quantum/classical approach along the molecular dynamics trajectory. The non-adiabaticity is introduced a posteriori using a Monte Carlo approach based on the Landau-Zener theory extended to treat a metal surface. This approach thus allows us to investigate the role of the energy fluctuations, determined by the dynamical evolution of the system, as well as the role of non-adiabaticity in affecting the kinetic rate of the electron transfer reaction. Most notably, it allows us to investigate the two contributions separately, hence achieving a detailed picture of the mechanisms that determine the rate. The analysis of the system configurations also allows us to relate the estimated electronic coupling to the structural and dynamic properties of the system. As a test case, the methodology is here applied to study the electron transfer reaction between cytochrome c and a gold surface. The results obtained explain the different electron transfer rates experimentally measured for two different concentrations of proteins on the electrode surface. PMID:27031179
Miller, William H. Cotton, Stephen J.
2015-04-07
It is noted that the recently developed symmetrical quasi-classical (SQC) treatment of the Meyer-Miller (MM) model for the simulation of electronically non-adiabatic dynamics provides a good description of detailed balance, even though the dynamics which results from the classical MM Hamiltonian is “Ehrenfest dynamics” (i.e., the force on the nuclei is an instantaneous coherent average over all electronic states). This is seen to be a consequence of the SQC windowing methodology for “processing” the results of the trajectory calculation. For a particularly simple model discussed here, this is shown to be true regardless of the choice of windowing function employed in the SQC model, and for a more realistic full classical molecular dynamics simulation, it is seen to be maintained correctly for very long time.
Shortcuts to adiabatic passage for generation of W states of distant atoms
NASA Astrophysics Data System (ADS)
Song, Kun-Huang; Chen, Ming-Feng
2016-08-01
With the help of quantum Zeno dynamics, we propose fast and noise-resistant schemes for preparing the W states in the indirectly coupled cavity systems via the inverse engineering-based Lewis-Riesenfeld invariant (IBLR). Comparing with the original adiabatic passage method, the results show that the time needed to prepare the desired state is reduced and the effects of the atomic spontaneous emission and the cavity decay on the fidelity are suppressed. Moreover, this scheme can also be generalized to generation of N-atom W states. Not only the total operation time, but also the robustness against decoherence is insensitive to the number of atoms. It proves that our scheme is useful in scalable distributed quantum information processing and contributes to the understanding of more complex systems via shortcuts to adiabatic passage based on Lewis-Riesenfeld invariants.
Quantum state engineering with flux-biased Josephson phase qubits by rapid adiabatic passages
Nie, W.; Huang, J. S.; Shi, X.; Wei, L. F.
2010-09-15
In this article, the scheme of quantum computing based on the Stark-chirped rapid adiabatic passage (SCRAP) technique [L. F. Wei, J. R. Johansson, L. X. Cen, S. Ashhab, and F. Nori, Phys. Rev. Lett. 100, 113601 (2008)] is extensively applied to implement quantum state manipulations in flux-biased Josephson phase qubits. The broken-parity symmetries of bound states in flux-biased Josephson junctions are utilized to conveniently generate the desirable Stark shifts. Then, assisted by various transition pulses, universal quantum logic gates as well as arbitrary quantum state preparations can be implemented. Compared with the usual {pi}-pulse operations widely used in experiments, the adiabatic population passages proposed here are insensitive to the details of the applied pulses and thus the desirable population transfers can be satisfyingly implemented. The experimental feasibility of the proposal is also discussed.
Effects of dephasing on quantum adiabatic pumping with nonequilibrium initial states
NASA Astrophysics Data System (ADS)
Zhou, Longwen; Tan, Da Yang; Gong, Jiangbin
2015-12-01
Thouless's quantum adiabatic pumping is of fundamental interest to condensed-matter physics. It originally considered a zero-temperature equilibrium state uniformly occupying all the bands below a Fermi surface. In light of recent direct simulations of Thouless's concept in cold-atom systems, this paper investigates the dynamics of quantum adiabatic pumping subject to dephasing for rather general initial states with nonuniform populations and possibly interband coherence. Using a theory based on pure-dephasing Lindblad evolution, we find that the pumping is contributed by two parts of different nature: a dephasing-modified geometric part weighted by initial Bloch state populations and an interband-coherence-induced part compromised by dephasing, both of them being independent of the pumping time scale. The overall pumping reflects an interplay of the band topology, initial state populations, initial state coherence, and dephasing. Theoretical results are carefully checked in a Chern insulator model coupled to a pure-dephasing environment, providing a useful starting point to understand and coherently control quantum adiabatic pumping in general situations.
Kubař, Tomáš; Elstner, Marcus
2013-04-28
In this work, a fragment-orbital density functional theory-based method is combined with two different non-adiabatic schemes for the propagation of the electronic degrees of freedom. This allows us to perform unbiased simulations of electron transfer processes in complex media, and the computational scheme is applied to the transfer of a hole in solvated DNA. It turns out that the mean-field approach, where the wave function of the hole is driven into a superposition of adiabatic states, leads to over-delocalization of the hole charge. This problem is avoided using a surface hopping scheme, resulting in a smaller rate of hole transfer. The method is highly efficient due to the on-the-fly computation of the coarse-grained DFT Hamiltonian for the nucleobases, which is coupled to the environment using a QM/MM approach. The computational efficiency and partial parallel character of the methodology make it possible to simulate electron transfer in systems of relevant biochemical size on a nanosecond time scale. Since standard non-polarizable force fields are applied in the molecular-mechanics part of the calculation, a simple scaling scheme was introduced into the electrostatic potential in order to simulate the effect of electronic polarization. It is shown that electronic polarization has an important effect on the features of charge transfer. The methodology is applied to two kinds of DNA sequences, illustrating the features of transfer along a flat energy landscape as well as over an energy barrier. The performance and relative merit of the mean-field scheme and the surface hopping for this application are discussed. PMID:23493847
Quantum state transfer between atomic ensembles trapped in separate cavities via adiabatic passage
NASA Astrophysics Data System (ADS)
Zhang, Chun-Ling; Chen, Mei-Feng
2015-07-01
We propose a new approach for quantum state transfer (QST) between atomic ensembles separately trapped in two distant cavities connected by an optical fiber via adiabatic passage. The three-level Λ-type atoms in each ensemble dispersively interact with the nonresonant classical field and cavity mode. By choosing appropriate parameters of the system, the effective Hamiltonian describes two atomic ensembles interacting with “the same cavity mode” and has a dark state. Consequently, the QST between atomic ensembles can be implemented via adiabatic passage. Numerical calculations show that the scheme is robust against moderate fluctuations of the experimental parameters. In addition, the effect of decoherence can be suppressed effectively. The idea provides a scalable way to an atomic-ensemble-based quantum network, which may be reachable with currently available technology. Project supported by the Funding (type B) from the Fujian Education Department, China (Grant No. JB13261).
NASA Astrophysics Data System (ADS)
Berriche, Hamid; Gadea, Florent Xavier
1995-12-01
The permanent dipole moments of the eight low-lying 1Σ states of the LiH molecule are calculated by an ab initio approach for both the adiabatic and the diabatic representations. The results shed light on the interplay between the ionic and the neutral states producing a direct illustration of the ionic character of the electronic wavefunction. Our results suggest that the location and the width of the avoided crossings for the potential energy curves could be experimentally derived.
Paul, Amit Kumar; Ray, Somrita; Mukhopadhyay, Debasis; Adhikari, Satrajit
2011-07-21
We perform ab initio calculation using quantum chemistry package (MOLPRO) on the excited states of Na(3) cluster and present the adiabatic PESs for the electronic states 2(2)E' and 1(2)A(1)', and the non-adiabatic coupling (NAC) terms among those states. Since the ab initio calculated NAC elements for the states 2(2)E' and 1(2)A(1)' demonstrate the numerical validity of so called "Curl Condition," such states closely form a sub-Hilbert space. For this subspace, we employ the NAC terms to solve the "adiabatic-diabatic transformation (ADT)" equations to obtain the functional form of the transformation angles and pave the way to construct the continuous and single valued diabatic potential energy surface matrix by exploiting the existing first principle based theoretical means on beyond Born-Oppenheimer treatment. Nuclear dynamics has been carried out on those diabatic surfaces to reproduce the experimental spectrum for system B of Na(3) cluster and thereby, to explore the numerical validity of the theoretical development on beyond Born-Oppenheimer approach for adiabatic to diabatic transformation. PMID:21786987
Superposition of states by adiabatic passage in N-pod systems
Amniat-Talab, M.; Saadati-Niari, M.; Nader-Ali, R.; Guerin, S.
2011-01-15
We study the stimulated Raman adiabatic passage technique in an N-pod system driven by N pulsed fields when N-2 and N-1 pulses not connected to the initial state have the same shape. We show that, for properly timed pulses, robust population transfer from an initial ground state to an arbitrary coherent superposition of the ground states can be achieved in a single step. The case of N-2 pulses of the same shape involves a geometric phase of the same type as the one appearing in tripod systems.
Filtering of matter-wave vibrational states via spatial adiabatic passage
Loiko, Yu.; Ahufinger, V.; Corbalan, R.; Mompart, J.; Birkl, G.
2011-03-15
We discuss the filtering of the vibrational states of a cold atom in an optical trap by chaining this trap with two empty ones and adiabatically controlling the tunneling. Matter-wave filtering is performed by selectively transferring the population of the highest populated vibrational state to the most distant trap while the population of the rest of the states remains in the initial trap. Analytical conditions for two-state filtering are derived and then applied to an arbitrary number of populated bound states. Realistic numerical simulations close to state-of-the-art experimental arrangements are performed by modeling the triple well with time-dependent Poeschl-Teller potentials. In addition to filtering of vibrational states, we discuss applications for quantum tomography of the initial population distribution and engineering of atomic Fock states that, eventually, could be used for tunneling-assisted evaporative cooling.
Super-heavy electron material as metallic refrigerant for adiabatic demagnetization cooling
Tokiwa, Yoshifumi; Piening, Boy; Jeevan, Hirale S.; Bud’ko, Sergey L.; Canfield, Paul C.; Gegenwart, Philipp
2016-01-01
Low-temperature refrigeration is of crucial importance in fundamental research of condensed matter physics, because the investigations of fascinating quantum phenomena, such as superconductivity, superfluidity, and quantum criticality, often require refrigeration down to very low temperatures. Currently, cryogenic refrigerators with 3He gas are widely used for cooling below 1 K. However, usage of the gas has been increasingly difficult because of the current worldwide shortage. Therefore, it is important to consider alternative methods of refrigeration. We show that a new type of refrigerant, the super-heavy electron metal YbCo2Zn20, can be used for adiabatic demagnetization refrigeration, which does not require 3He gas. This method has a number of advantages, including much better metallic thermal conductivity compared to the conventional insulating refrigerants. We also demonstrate that the cooling performance is optimized in Yb1−xScxCo2Zn20 by partial Sc substitution, with x ~ 0.19. The substitution induces chemical pressure that drives the materials to a zero-field quantum critical point. This leads to an additional enhancement of the magnetocaloric effect in low fields and low temperatures, enabling final temperatures well below 100 mK. This performance has, up to now, been restricted to insulators. For nearly a century, the same principle of using local magnetic moments has been applied for adiabatic demagnetization cooling. This study opens new possibilities of using itinerant magnetic moments for cryogen-free refrigeration. PMID:27626073
Super-heavy electron material as metallic refrigerant for adiabatic demagnetization cooling.
Tokiwa, Yoshifumi; Piening, Boy; Jeevan, Hirale S; Bud'ko, Sergey L; Canfield, Paul C; Gegenwart, Philipp
2016-09-01
Low-temperature refrigeration is of crucial importance in fundamental research of condensed matter physics, because the investigations of fascinating quantum phenomena, such as superconductivity, superfluidity, and quantum criticality, often require refrigeration down to very low temperatures. Currently, cryogenic refrigerators with (3)He gas are widely used for cooling below 1 K. However, usage of the gas has been increasingly difficult because of the current worldwide shortage. Therefore, it is important to consider alternative methods of refrigeration. We show that a new type of refrigerant, the super-heavy electron metal YbCo2Zn20, can be used for adiabatic demagnetization refrigeration, which does not require (3)He gas. This method has a number of advantages, including much better metallic thermal conductivity compared to the conventional insulating refrigerants. We also demonstrate that the cooling performance is optimized in Yb1-x Sc x Co2Zn20 by partial Sc substitution, with x ~ 0.19. The substitution induces chemical pressure that drives the materials to a zero-field quantum critical point. This leads to an additional enhancement of the magnetocaloric effect in low fields and low temperatures, enabling final temperatures well below 100 mK. This performance has, up to now, been restricted to insulators. For nearly a century, the same principle of using local magnetic moments has been applied for adiabatic demagnetization cooling. This study opens new possibilities of using itinerant magnetic moments for cryogen-free refrigeration. PMID:27626073
Borovsky, Joseph E; Denton, Michael H
2008-01-01
Using temperature and number-density measurements of the energetic-electron population from multiple spacecraft in geosynchronous orbit, the specific entropy S = T/n{sup 2/3} of the outer electron radiation belt is calculated. Then 955,527 half-hour-long data intervals are statistically analyzed. Local-time and solar-cycle variations in S are examined. The median value of the specific entropy (2.8 x 10{sup 7} eVcm{sup 2}) is much larger than the specific entropy of other particle populations in and around the magnetosphere. The evolution of the specific entropy through high-speed-stream-driven geomagnetic storms and through magnetic-cloud-driven geomagnetic storms is studied using superposed-epoch analysis. For high-speed-stream-driven storms, systematic variations in the entropy associated with electron loss and gain and with radiation-belt heating are observed in the various storm phases. For magnetic-cloud-driven storms, multiple trigger choices for the data superpositions reveal the effects of interplanetary shock arrival, sheath driving, cloud driving, and recovery phase. The specific entropy S = T/n{sup 2/3} is algebraically expressed in terms of the first and second adiabatic invariants of the electrons: this allows a relativistic expression for S in terms of T and n to be derived. For the outer electron radiation belt at geosynchronous orbit, the relativistic corrections to the specific entropy expression are -15%.
Electron distributions upstream of the Comet Halley bow shock - Evidence for adiabatic heating
NASA Technical Reports Server (NTRS)
Larson, D. E.; Anderson, K. A.; Lin, R. P.; Carlson, C. W.; Reme, H.; Glassmeier, K. H.; Neubauer, F. M.
1992-01-01
Three-dimensional plasma electron (22 eV to 30 keV) observations upstream of Comet Halley bow shock, obtained by the RPA-1 COPERNIC (Reme Plasma Analyzer - Complete Positive Ion, Electron and Ram Negative Ion Measurements near Comet Halley) experiment on the Giotto spacecraft are reported. Besides electron distributions typical of the undisturbed solar wind and backstreaming electrons observed when the magnetic field line intersects the cometary bow shock, a new type of distribution, characterized by enhanced low energy (less than 100 eV) flux which peaks at 90-deg pitch angles is found. These are most prominent when the spacecraft is on field lines which pass close to but are not connected to the bow shock. The 90-deg pitch angle electrons appear to have been adiabatically heated by the increase in the magnetic field strength resulting from the compression of the upstream solar wind plasma by the cometary mass loading. A model calculation of this effect which agrees qualitatively with the observed 90-deg flux enhancements is presented.
NASA Astrophysics Data System (ADS)
van Dishoeck, Ewine F.; van Hemert, Marc C.; Allison, A. C.; Dalgarno, A.
1984-12-01
The bound 3 2Π and repulsive 2 2Π states of OH are strongly coupled by the action of the nuclear kinetic energy operator. The process of photodissociation by absorption into the coupled 2Π states is studied theoretically. The adiabatic electronic eigenfunctions and potential energy curves of the 2 2Π and 3 2Π states are calculated using large configuration-interaction (CI) representations and the nuclear radial coupling matrix elements are obtained by numerical differentiation. The coupled equations for the nuclear wave functions of the two states are set up in an adiabatic and in a diabatic formulation and are solved by numerical integration. The electric dipole transition moments connecting the ground X 2Π state to the 2 2Π and 3 2Π states are computed from the CI wave functions and the resulting photodissociation cross sections of OH arising from absorption into the coupled 2 2Π and 3 2Π states are obtained. Two alternative sets of potential curves, coupling matrix elements, and transition moments are employed to provide an assessment of the accuracy of the results. The photodissociation cross section shows a series of resonances superimposed on a broad continuous background. The resonances are located near to the vibrational levels of the uncoupled bound diabatic potential curve. They have asymmetric Beutler-Fano profiles and vary in width from 50 cm-1 for the lowest levels to 2 cm-1 for the higher levels. The accuracy of adiabatic and diabatic approximations, carried to first order in the coupling, is explored and it is demonstrated that the diabatic approximation provides a more satisfactory representation of the photodissociation process. The discrete-continuum configuration interaction theory of Fano is applied in the diabatic formulation and the resonance structures are calculated. The discrete-continuum interaction theory yields profile parameters and level shifts which agree well with the accurate values obtained by solving the coupled
NASA Astrophysics Data System (ADS)
Trushin, Egor; Betzinger, Markus; Blügel, Stefan; Görling, Andreas
2016-08-01
An approach to calculate fundamental band gaps, ionization energies, and electron affinities of periodic electron systems is explored. Starting from total energies obtained with the help of the adiabatic-connection fluctuation-dissipation (ACFD) theorem, these physical observables are calculated according to their basic definition by differences of the total energies of the N -, (N -1 ) -, and (N +1 ) -electron system. The response functions entering the ACFD theorem are approximated here by the direct random phase approximation (dRPA). For a set of prototypical semiconductors and insulators it is shown that even with this quite drastic approximation the resulting band gaps are very close to experiment and of a similar quality to those from the computationally more involved G W approximation. By going beyond the dRPA in the future the accuracy of the calculated band gaps may be significantly improved further.
Generation of tree-type three-dimensional entangled states via adiabatic passage
NASA Astrophysics Data System (ADS)
Song, Chong; Su, Shi-Lei; Wu, Jin-Lei; Wang, Dong-Yang; Ji, Xin; Zhang, Shou
2016-06-01
We propose a scheme for generating a type of novel tree-type three-dimensional entangled state. In the scheme, an atom and two Bose-Einstein condensates (BECs) are individually trapped in three spatially separated optical cavities which are connected by two optical fibers. Because the system evolves along the dark state via adiabatic passage, the populations of the intermediate excited states of the atom and BECs are so negligible that the influence of atomic spontaneous radiation on the fidelity is restrained. In addition, because of the certain limit condition used, the cavity decay and fiber loss are efficiently suppressed. This novel three-dimensional entangled state is likely to have applications for improving quantum communication security.
Wang, Xi-guang; Guo, Guang-hua Nie, Yao-zhuang; Xia, Qing-lin; Tang, Wei; Wang, D.; Zeng, Zhong-ming
2013-12-23
We have studied the current-induced displacement of a 180° Bloch wall by means of micromagnetic simulation and analytical approach. It is found that the adiabatic spin-transfer torque can sustain a steady-state domain wall (DW) motion in the direction opposite to that of the electron flow without Walker Breakdown when a transverse microwave field is applied. This kind of motion is very sensitive to the microwave frequency and can be resonantly enhanced by exciting the domain wall thickness oscillation mode. A one-dimensional analytical model was established to account for the microwave-assisted wall motion. These findings may be helpful for reducing the critical spin-polarized current density and designing DW-based spintronic devices.
NASA Astrophysics Data System (ADS)
Ma, Song-She
2010-09-01
A scheme is proposed to generate W state of N atoms trapped in a cavity, based on adiabatic passage along dark state. Taking advantage of adiabatic passage, the atoms have no probability of being excited and thus the atomic spontaneous emission is suppressed. The scheme is simple. It does not need to adjust the interaction time accurately, and does not need to prepare the cavity field in one-photon state. Numerical simulation shows that the successful probability of the scheme increases with the increasing of the atom number.
Non-Adiabatic, Multi-State Ring-Polymer Molecular Dynamics
NASA Astrophysics Data System (ADS)
Bell, Franziska; Menzeleev, Artur; Miller, Thomas, III
2014-03-01
Ring-polymer molecular dynamics (RPMD) has been shown to be a promising method for studying mechanisms and rates in large systems which require the inclusion of quantum effects, such as zero-point energies and tunneling. Examples involve electron and/or proton transfer reactions in enzymes and artificial catalysts. However, the traditional formulation of RPMD has several shortcomings: (i) it is restricted to migrations of only one distinguishable electron, (ii) it cannot describe photophysical processes, and (iii) it cannot be used in conjunction with potential energy surfaces obtained from electronic structure methods. Here I present a parameter-free extension of the RPMD method that addresses these issues and allows for the direct simulation of non-adiabatic processes involving many-electron wavefunctions without prior assumptions of the reaction mechanism. The new approach is demonstrated to provide a quantitative description of electron-transfer reaction rates and mechanisms throughout (i) the normal and inverted regimes and (ii) the weak- and strong-coupling regimes. I would like to thank the APS for financial support in form of a New Investigator Travel Award.
Non-adiabatic resonant conversion of solar neutrinos in three generations
NASA Astrophysics Data System (ADS)
Kim, C. W.; Nussinov, S.; Sze, W. K.
1987-02-01
The survival probability of solar electron neutrinos after non-adiabatic passage through the resonance-oscillation region in the Sun is discussed for the case of three generations. A method to calculate three-generation Landau-Zener transition probabilities between adiabatic states is described. We also discuss how the Landua-Zener probability is modified in the extreme non-adiabatic case.
NASA Astrophysics Data System (ADS)
Wang, Zi; Bevan, Kirk H.
2016-01-01
In the present work, we study the effects of the electronic relaxation of semicore levels on polaron activation energies and dynamics. Within the framework of adiabatic ab initio theory, we utilize both static transition state theory and molecular dynamics methods for an in-depth study of polaronic hopping in delithiated LiFePO4 (FePO4). Our results show that electronic relaxation of semicore states is significant in FePO4, resulting in a lower activation barrier and kinetics that is one to two orders faster compared to the result of calculations that do not incorporate semicore states. In general, the results suggest that the relaxation of states far below the Fermi energy could dramatically impact the ab initio polaronic barrier estimates for many transition metal oxides and phosphates.
Tiwari, Vivek; Peters, William K.; Jonas, David M.
2013-01-01
The delocalized, anticorrelated component of pigment vibrations can drive nonadiabatic electronic energy transfer in photosynthetic light-harvesting antennas. In femtosecond experiments, this energy transfer mechanism leads to excitation of delocalized, anticorrelated vibrational wavepackets on the ground electronic state that exhibit not only 2D spectroscopic signatures attributed to electronic coherence and oscillatory quantum energy transport but also a cross-peak asymmetry not previously explained by theory. A number of antennas have electronic energy gaps matching a pigment vibrational frequency with a small vibrational coordinate change on electronic excitation. Such photosynthetic energy transfer steps resemble molecular internal conversion through a nested intermolecular funnel. PMID:23267114
Quantum state specific reactant preparation in a molecular beam by rapid adiabatic passage
Chadwick, Helen Hundt, P. Morten; Reijzen, Maarten E. van; Yoder, Bruce L.; Beck, Rainer D.
2014-01-21
Highly efficient preparation of molecules in a specific rovibrationally excited state for gas/surface reactivity measurements is achieved in a molecular beam using tunable infrared (IR) radiation from a single mode continuous wave optical parametric oscillator (cw-OPO). We demonstrate that with appropriate focusing of the IR radiation, molecules in the molecular beam crossing the fixed frequency IR field experience a Doppler tuning that can be adjusted to achieve complete population inversion of a two-level system by rapid adiabatic passage (RAP). A room temperature pyroelectric detector is used to monitor the excited fraction in the molecular beam and the population inversion is detected and quantified using IR bleaching by a second IR-OPO. The second OPO is also used for complete population transfer to an overtone or combination vibration via double resonance excitation using two spatially separated RAP processes.
Quantum state specific reactant preparation in a molecular beam by rapid adiabatic passage
NASA Astrophysics Data System (ADS)
Chadwick, Helen; Hundt, P. Morten; van Reijzen, Maarten E.; Yoder, Bruce L.; Beck, Rainer D.
2014-01-01
Highly efficient preparation of molecules in a specific rovibrationally excited state for gas/surface reactivity measurements is achieved in a molecular beam using tunable infrared (IR) radiation from a single mode continuous wave optical parametric oscillator (cw-OPO). We demonstrate that with appropriate focusing of the IR radiation, molecules in the molecular beam crossing the fixed frequency IR field experience a Doppler tuning that can be adjusted to achieve complete population inversion of a two-level system by rapid adiabatic passage (RAP). A room temperature pyroelectric detector is used to monitor the excited fraction in the molecular beam and the population inversion is detected and quantified using IR bleaching by a second IR-OPO. The second OPO is also used for complete population transfer to an overtone or combination vibration via double resonance excitation using two spatially separated RAP processes.
Quantum state specific reactant preparation in a molecular beam by rapid adiabatic passage.
Chadwick, Helen; Hundt, P Morten; van Reijzen, Maarten E; Yoder, Bruce L; Beck, Rainer D
2014-01-21
Highly efficient preparation of molecules in a specific rovibrationally excited state for gas/surface reactivity measurements is achieved in a molecular beam using tunable infrared (IR) radiation from a single mode continuous wave optical parametric oscillator (cw-OPO). We demonstrate that with appropriate focusing of the IR radiation, molecules in the molecular beam crossing the fixed frequency IR field experience a Doppler tuning that can be adjusted to achieve complete population inversion of a two-level system by rapid adiabatic passage (RAP). A room temperature pyroelectric detector is used to monitor the excited fraction in the molecular beam and the population inversion is detected and quantified using IR bleaching by a second IR-OPO. The second OPO is also used for complete population transfer to an overtone or combination vibration via double resonance excitation using two spatially separated RAP processes. PMID:25669393
NASA Astrophysics Data System (ADS)
Hadinger, G.; Tergiman, Y. S.
1986-12-01
From isotopic spectroscopic data, the internuclear distance dependence of the adiabatic corrections to the potential energy curve has been determined for the ∑ state of a diatomic molecule. Starting from an analytic inversion procedure previously described, the adiabatic corrections can be found in a straightforward way, provided that they can be considered as perturbing terms of the vibration-rotation wave equation. Application to the case of the X 1∑+ state of the lithium hydrides 6LiH, 7LiH, 6LiD, and 7LiD is carried out. The adiabatic corrections ΔUH(R) and ΔULi(R) are obtained and compared with recent results.
Asymmetry and non-adiabaticity in fragmentation of disulfide bonds upon electron capture.
Gámez, José A; Serrano-Andrés, Luis; Yáñez, Manuel
2010-08-23
Although it has been generally assumed that electron attachment to disulfide derivatives leads to a systematic and significant activation of the S-S bond, we show, by using [CH(3)SSX] (X = CH(3), NH(2), OH, F) derivatives as model compounds, that this is the case only when the X substituents have low electronegativity. Through the use of MP2, QCI and CASPT2 molecular orbital (MO) methods, we elucidate, for the first time, the mechanisms that lead to unimolecular fragmentation of disulfide derivatives after electron attachment. Our theoretical scrutiny indicates that these mechanisms are more intricate than assumed in previous studies. The most stable products, from a thermodynamic viewpoint, correspond to the release of neutral molecules; CH(4), NH(3), H(2)O, and HF. However, the barriers to reach these products depend strongly on the electronegativity of the X substituents. Only for very electronegative substituents, such as OH or F, the loss of H(2)O or HF is the most favorable process, and likely the only one observed. This is possible because of two concomitant factors, 1) the extra electron for [CH(3)SSX](-) (X = OH, F) occupies a sigma*(S-X) MO, which favors the cleavage of the S-X bond, and 2) the activation barriers associated with the hydrogen transfer process to produce H(2)O and HF are rather low. Only when the substituents are less electronegative (X = H, CH(3), NH(2)) the extra electron is located in a sigma*(S-S) orbital and the cleavage of the disulfide bridge becomes the most favorable process. The intimate mechanism associated with the S-S bond dissociation process also depends strongly on the nature of the substituent. For X = H or CH(3) the process is strictly adiabatic, while for X = NH(2) it proceeds through a conical intersection (CI) associated with the charge reorganization necessary to obtain, from a molecular anion with the extra electron delocalized in a sigma*(S-S) antibonding orbital, two fragments with the proper charge localization
NASA Astrophysics Data System (ADS)
Nunkaew, Jirakan
In this dissertation, I study the structure and dynamics of Rydberg two-electron atoms. Specifically, I study the core polarization effect of the Rydberg electron on the ground state ion of strontium and the autoionization of barium atoms in an external static field in the low field regime. The autoionization studies show that it is possible to measure the contribution to dielectronic recombination (DR) of energetically unresolved high ℓ states by measuring the recombination rate as a function of electric field. I also present the experimental observation that the ejected electrons from autoionizing states in an electric field have a directional preference that depends on the orientation of the Rydberg Stark state wavefunctions. Finally, I present the spectroscopy of the Stark autoionizing states in the low field regime using a high resolution dye-amplified diode laser.
Generalization of the cavity method for adiabatic evolution of Gibbs states
NASA Astrophysics Data System (ADS)
Zdeborová, Lenka; Krzakala, Florent
2010-06-01
Mean-field glassy systems have a complicated energy landscape and an enormous number of different Gibbs states. In this paper, we introduce a generalization of the cavity method in order to describe the adiabatic evolution of these glassy Gibbs states as an external parameter, such as the temperature, is tuned. We give a general derivation of the method and describe in details the solution of the resulting equations for the fully connected p -spin model, the XOR-satisfiability (SAT) problem and the antiferromagnetic Potts glass (coloring problem). As direct results of the states following method we present a study of very slow Monte Carlo annealings, the demonstration of the presence of temperature chaos in these systems and the identification of an easy/hard transition for simulated annealing in constraint optimization problems. We also discuss the relation between our approach and the Franz-Parisi potential, as well as with the reconstruction problem on trees in computer science. A mapping between the states following method and the physics on the Nishimori line is also presented.
NASA Technical Reports Server (NTRS)
1976-01-01
One-electron wave functions are reviewed and approximate solutions of two-electron systems are given in terms of these one-electron functions. The symmetry effects associated with electron spin are reviewed and the effects of electron exchange on energy levels of the two-electron system are given. The coupling of electronic orbital and spin angular momentum is considered next and the Lande interval rule for Russell-Saunders or LS coupling is derived. The configurations possible for various multi-electron LS couplings are enumerated (examples from the first two rows of the periodic table are given), and the meaning of the spectroscopic nomenclature is discussed, particularly with respect to the degeneracies of the electron states involved. Next the nomenclature, symmetries, and degeneracies for electron states of diatomic molecules are discussed, and some examples for N2, O2, and NO are presented. The electronic partition functions and derivative thermodynamic properties are expressed in terms of these energies and degeneracies, and examples are given for some of the simple gas species encountered in the earth's atmosphere.
Miyamoto, Yoshiyuki; Tateyama, Yoshitaka; Oyama, Norihisa; Ohno, Takahisa
2015-01-01
We examined real-time-propagation time-dependent density functional theory (rtp-TDDFT) coupled with molecular dynamics (MD), which uses single-particle representation of time-evolving wavefunctions allowing exchange of orbital characteristics between occupied and empty states making the effective Kohn-Sham Hamiltonian dependent on the potential energy surfaces (PESs). This scheme is expected to lead to mean-field average of adiabatic potential energy surfaces (PESs), and is one of Ehrenfest (mean-field) approaches. However, we demonstrate that the mean-field average can be absent in simulating photoisomerization of azobenzene and ethylene molecules. A transition from the S2 to the S1 excited state without the mean- field average was observed after examining several rtp-TDDFT-MD trajectories of a photoexcited azobenzene molecule. The subsequent trans-cis isomerization was observed in our simulation, which is consistent with experimental observation and supported by previous calculations. The absence of the mean-field average of PESs was also observed for the transition between the S1 and S0 states, indicating that the MD simulation was on a single PES. Conversely, we found no transition to the ground state (S0 state) when we performed a MD simulation of an S1 excited ethylene molecule owing to the constraint on the occupation number of each molecular orbital. Thus, we conclude that, at least for azobenzene and ethylene molecules, the rtp-TDDFT-MD is an on-the-fly simulation that can automatically see the transition among the PESs of excited states without the mean-field average unless the simulation reaches the PES of the S0 state. PMID:26658633
Miyamoto, Yoshiyuki; Tateyama, Yoshitaka; Oyama, Norihisa; Ohno, Takahisa
2015-01-01
We examined real-time-propagation time-dependent density functional theory (rtp-TDDFT) coupled with molecular dynamics (MD), which uses single-particle representation of time-evolving wavefunctions allowing exchange of orbital characteristics between occupied and empty states making the effective Kohn-Sham Hamiltonian dependent on the potential energy surfaces (PESs). This scheme is expected to lead to mean-field average of adiabatic potential energy surfaces (PESs), and is one of Ehrenfest (mean-field) approaches. However, we demonstrate that the mean-field average can be absent in simulating photoisomerization of azobenzene and ethylene molecules. A transition from the S2 to the S1 excited state without the mean- field average was observed after examining several rtp-TDDFT-MD trajectories of a photoexcited azobenzene molecule. The subsequent trans-cis isomerization was observed in our simulation, which is consistent with experimental observation and supported by previous calculations. The absence of the mean-field average of PESs was also observed for the transition between the S1 and S0 states, indicating that the MD simulation was on a single PES. Conversely, we found no transition to the ground state (S0 state) when we performed a MD simulation of an S1 excited ethylene molecule owing to the constraint on the occupation number of each molecular orbital. Thus, we conclude that, at least for azobenzene and ethylene molecules, the rtp-TDDFT-MD is an on-the-fly simulation that can automatically see the transition among the PESs of excited states without the mean-field average unless the simulation reaches the PES of the S0 state. PMID:26658633
Baranowski, M; Woźniak-Braszak, A; Jurga, K
2016-01-01
The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2MHz and 28.411MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins (1)H are polarized in the magnetic field B0 while fluorine spins (19)F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal. PMID:26705906
NASA Astrophysics Data System (ADS)
Baranowski, M.; Woźniak-Braszak, A.; Jurga, K.
2016-01-01
The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2 MHz and 28.411 MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins 1H are polarized in the magnetic field B0 while fluorine spins 19F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal.
NASA Astrophysics Data System (ADS)
Predota, Milan; Cummings, Peter T.; Chialvo, Ariel A.
The adiabatic nuclear and electronic sampling method (ANES), originally formulated as an efficient Monte Carlo algorithm for systems with fluctuating charges, is applied to the simulation of a polarizable water model with induced dipole moments. Structural, thermodynamic and dipolar properties obtained by ANES and a newer algorithm, the pair approximation for polarization interaction (PAPI), are compared with full iteration. With the best parameters, the inaccuracy of both approximate methods was found to be comparable with the uncertainty of the full iteration. The PAPI method with iteration radius equal to the second minimum of the oxygen-oxygen correlation function is, depending on the convergence tolerance, 10-15 times faster than the full iteration for 256 molecules, and yields very accurate structure and thermodynamics with deviation about 0.3%. When the iteration radius is increased to the cutoff distance, exact results are recovered at the cost of decreased efficiency. The ANES method with small nuclear displacements proved to inefficiently sample the configurational space. Simulations at low electronic temperatures with large nuclear displacements are inaccurate for up to 100 electronic moves, and increasing this number would make the simulations as slow as the full iteration. The most accurate and efficient adiabatic ANES simulations are those with infinite electronic temperature, large nuclear displacements and 1-10 electronic moves. The extra freedom of induced dipoles in the ANES method at high electronic temperatures modifies the observed dipolar properties; however, the question of whether the dielectric constant is also modified needs further consideration.
Non-adiabatic electron-proton couplings in H2 by floating Gaussian method
NASA Astrophysics Data System (ADS)
Ichikawa, Yuichi; Kato, Tsuyoshi; Yamanouchi, Kaoru
2016-08-01
Time-dependent electron-nuclear wave functions of H2 were described by the floating Gaussian method. The equations of motion for the parameters that specify the wave functions are explicitly derived. By the imaginary time propagation, the ground-state wave functions were obtained. Five high frequency components appearing in the Fourier transformed spectra of the squared inter-particle distances were ascribed to the motion of electrons, and the two lowest frequency components among the five were identified as those representing coupling of the motions of electrons and nuclei.
Collective motion of two-electron atom in hyperspherical adiabatic approximation
Mohamed, A. S.; Nikitin, S. I.
2015-03-30
This work is devoted to calculate bound states in the two-electron atoms. The separation of variables has carried out in hyper spherical coordinate system (R, θ, α). Assuming collective motion of the electrons, where the hper angle (α∼π/4) and (θ∼π). The separation of the rotational variables leads to system of differential equations with more simple form as compared with non restricted motion. Energy of doubly excited P{sup e} and D{sup 0} states are calculated semi classically by using quantization condition of Bohr -Somerfield. The results compared with previously published data.
Description of electronic excited states using electron correlation operator.
Nichols, Bryan; Rassolov, Vitaly A
2013-09-14
The electron correlation energy in a chemical system is defined as a difference between the energy of an exact energy for a given Hamiltonian, and a mean-field, or single determinant, approximation to it. A promising way to model electron correlation is through the expectation value of a linear two-electron operator for the Kohn-Sham single determinant wavefunction. For practical reasons, it is desirable for such an operator to be universal, i.e., independent of the positions and types of nuclei in a molecule. The correlation operator models the effect of electron correlation on the interaction energy in a electron pair. We choose an operator expanded in a small number of Gaussians as a model for electron correlation, and test it by computing atomic and molecular adiabatic excited states. The computations are performed within the Δ Self-Consistent Field (ΔSCF) formalism, and are compared to the time-dependent density functional theory model with popular density functionals. The simplest form of the correlation operator contains only one parameter derived from the helium atom ground state correlation energy. The correlation operator approach significantly outperforms other methods in computation of atomic excitation energies. The accuracy of molecular excitation energies computed with the correlation operator is limited by the shortcomings of the ΔSCF methodology in describing excited states. PMID:24050332
NASA Astrophysics Data System (ADS)
Cremers, C.; Degen, J.
1998-11-01
Coexistence of Jahn-Teller minima resulting from the coupling to different accepting modes within the adiabatic potential energy surface (APES) is not possible within the framework of linear vibronic coupling theory. For the lowest exited triplet state 3T1u of inorganic complexes with s2 electronic ground-state configuration, such a coexistence, due to quadratic coupling effects, is discussed. As a direct experimental evidence two vibronic progressions with different accepting modes in the emission spectra resulting from a single electronic state are observed in the emission spectra of the title compounds. The observation of vibronic finestructure in the emission spectra of [TeCl6]2- is reported for the first time.
Broadband adiabatic inversion pulses for cross polarization in wideline solid-state NMR spectroscopy
NASA Astrophysics Data System (ADS)
Harris, Kristopher J.; Lupulescu, Adonis; Lucier, Bryan E. G.; Frydman, Lucio; Schurko, Robert W.
2012-11-01
Efficient acquisition of ultra-wideline solid-state NMR powder patterns is a continuing challenge. In particular, when the breadth of the powder pattern is much larger than the cross-polarization (CP) excitation bandwidth, transfer efficiencies suffer and experimental times are greatly increased. Presented herein is a CP pulse sequence with an excitation bandwidth that is up to ten times greater than that available from a conventional spin-locked CP pulse sequence. The pulse sequence, broadband adiabatic inversion CP (BRAIN-CP), makes use of the broad, uniformly large frequency profiles of chirped inversion pulses, to provide these same characteristics to the polarization transfer process. A detailed theoretical analysis is given, providing insight into the polarization transfer process involved in BRAIN-CP. Experiments on spin-1/2 nuclei including 119Sn, 199Hg and 195Pt nuclei are presented, and the large bandwidth improvements possible with BRAIN-CP are demonstrated. Furthermore, it is shown that BRAIN-CP can be combined with broadband frequency-swept versions of the Carr-Purcell-Meiboom-Gill experiment (for instance with WURST-CPMG, or WCPMG for brevity); the combined BRAIN-CP/WCPMG experiment then provides multiplicative signal enhancements of both CP and multiple-echo acquisition over a broad frequency region.
NASA Astrophysics Data System (ADS)
Diniz, Leonardo G.; Alijah, Alexander; Adamowicz, Ludwik; Mohallem, José R.
2015-07-01
Non-adiabatic vibrational calculations performed with the accuracy of 0.2 cm-1 spanning the whole energy spectrum up to the dissociation limit for 7LiH are reported. A so far unknown v = 23 energy level is predicted. The key feature of the approach used in the calculations is a valence-bond (VB) based procedure for determining the effective masses of the two vibrating atoms, which depend on the internuclear distance, R. It is found that all LiH electrons participate in the vibrational motion. The R-dependent masses are obtained from the analysis of the simple VB two-configuration ionic-covalent representation of the electronic wave function. These findings are consistent with an interpretation of the chemical bond in LiH as a quantum mechanical superposition of one-electron ionic and covalent states.
The proximity of Mercury's spin to Cassini state 1 from adiabatic invariance
NASA Astrophysics Data System (ADS)
Peale, S. J.
2006-04-01
In determining Mercury's core structure from its rotational properties, the value of the normalized moment of inertia, C/MR, from the location of Cassini 1 is crucial. If Mercury's spin axis occupies Cassini state 1, its position defines the location of the state, where the axis is fixed in the frame precessing with the orbit. Although tidal and core-mantle dissipation drive the spin to the Cassini state with a time scale O(10) years, the spin might still be displaced from the Cassini state if the variations in the orbital elements induced by planetary perturbations, which change the position of the Cassini state, cause the spin to lag behind as it attempts to follow the state. After being brought to the state by dissipative processes, the spin axis is expected to follow the Cassini state for orbit variations with time scales long compared to the 1000 year precession period of the spin about the Cassini state because the solid angle swept out by the spin axis as it precesses is an adiabatic invariant. Short period variations in the orbital elements of small amplitude should cause displacements that are commensurate with the amplitudes of the short period terms. The exception would be if there are forcing terms in the perturbations that are nearly resonant with the 1000 year precession period. The precision of the radar and eventual spacecraft measurements of the position of Mercury's spin axis warrants a check on the likely proximity of the spin axis to the Cassini state. How confident should we be that the spin axis position defines the Cassini state sufficiently well for a precise determination of C/MR? By following simultaneously the spin position and the Cassini state position during long time scale orbital variations over past 3 million years [Quinn, T.R., Tremaine, S., Duncan, M., 1991. Astron. J. 101, 2287-2305] and short time scale variations for 20,000 years [JPL Ephemeris DE 408; Standish, E.M., private communication, 2005], we show that the spin axis
A multi-state trajectory method for non-adiabatic dynamics simulations.
Tao, Guohua
2016-03-01
A multi-state trajectory approach is proposed to describe nuclear-electron coupled dynamics in nonadiabatic simulations. In this approach, each electronic state is associated with an individual trajectory, among which electronic transition occurs. The set of these individual trajectories constitutes a multi-state trajectory, and nuclear dynamics is described by one of these individual trajectories as the system is on the corresponding state. The total nuclear-electron coupled dynamics is obtained from the ensemble average of the multi-state trajectories. A variety of benchmark systems such as the spin-boson system have been tested and the results generated using the quasi-classical version of the method show reasonably good agreement with the exact quantum calculations. Featured in a clear multi-state picture, high efficiency, and excellent numerical stability, the proposed method may have advantages in being implemented to realistic complex molecular systems, and it could be straightforwardly applied to general nonadiabatic dynamics involving multiple states. PMID:26957158
NASA Astrophysics Data System (ADS)
Haruyama, Jun; Suzuki, Takahiro; Hu, Chunping; Watanabe, Kazuyuki
2012-01-01
We present a simple and computationally efficient method to calculate excited-state nuclear forces on adiabatic potential-energy surfaces (APES) from linear-response time-dependent density-functional theory within a real-space framework. The Casida ansatz, which has been validated for computing first-order nonadiabatic couplings in previous studies, was applied to the calculation of the excited-state forces. Our method is validated by the consistency of results in the lower excited states, which reproduce well those obtained by the numerical derivative of each APES. We emphasize the usefulness of this technique by demonstrating the excited-state molecular-dynamics simulation.
NASA Astrophysics Data System (ADS)
Colonna, Nicola; de Gironcoli, Stefano
2014-03-01
We have developed an expression for the electronic correlation energy via the Adiabatic Connection Fluctuation-Dissipation Theorem (ACFDT) going beyond the Random-Phase Approximation (RPA) by including exact exchange contribution to the kernel (RPAx). Our derivation is valid and efficient for general systems. It is based on an eigenvalue decomposition of the time dependent response function of the Many Body system in the limit of vanishing coupling constant, evaluated by Density Functional Perturbation Theory. We tested the accuracy of this approximation on the homogeneous electron gas. Within RPAx, the correlation energy of the homogeneous electron gas improves significantly with respect to the RPA results up to densities of the order of rs ~ 10 . However, beyond this value, the RPAx response function becomes pathological and the approximation breaks down. We have also evaluated the dependence of the correlation energy on the spin magnetization of the system. Both RPA an RPAx are in excellent agreement with accurate Quantum Monte Carlo results.
Cotton, Stephen J; Miller, William H
2016-03-01
In a recent series of papers, it has been illustrated that a symmetrical quasi-classical (SQC) windowing model applied to the Meyer-Miller (MM) classical vibronic Hamiltonian provides an excellent description of a variety of electronically non-adiabatic benchmark model systems for which exact quantum results are available for comparison. In this paper, the SQC/MM approach is used to treat energy transfer dynamics in site-exciton models of light-harvesting complexes, and in particular, the well-known 7-state Fenna-Mathews-Olson (FMO) complex. Again, numerically "exact" results are available for comparison, here via the hierarchical equation of motion (HEOM) approach of Ishizaki and Fleming, and it is seen that the simple SQC/MM approach provides very reasonable agreement with the previous HEOM results. It is noted, however, that unlike most (if not all) simple approaches for treating these systems, because the SQC/MM approach presents a fully atomistic simulation based on classical trajectory simulation, it places no restrictions on the characteristics of the thermal baths coupled to each two-level site, e.g., bath spectral densities (SD) of any analytic functional form may be employed as well as discrete SD determined experimentally or from MD simulation (nor is there any restriction that the baths be harmonic), opening up the possibility of simulating more realistic variations on the basic site-exciton framework for describing the non-adiabatic dynamics of photosynthetic pigment complexes. PMID:26761191
A homonuclear spin-pair filter for solid-state NMR based on adiabatic-passage techniques
NASA Astrophysics Data System (ADS)
Verel, René; Baldus, Marc; Ernst, Matthias; Meier, Beat H.
1998-05-01
A filtering scheme for the selection of spin pairs (and larger spin clusters) under fast magic-angle spinning is proposed. The scheme exploits the avoided level crossing in spin pairs during an adiabatic amplitude sweep through the so-called HORROR recoupling condition. The advantages over presently used double-quantum filters are twofold. (i) The maximum theoretical filter efficiency is, due to the adiabatic variation, 100% instead of 73% as for transient methods. (ii) Since the filter does not rely on the phase-cycling properties of the double-quantum coherence, there is no need to obtain the full double-quantum intensity for all spins in the sample at one single point in time. The only important requirement is that all coupled spins pass through a two-spin state during the amplitude sweep. This makes the pulse scheme robust with respect to rf-amplitude missetting, rf-field inhomogeneity and chemical-shift offset.
Chen, Ye-Hong; Xia, Yan; Song, Jie; Chen, Qing-Qin
2015-01-01
Berry’s approach on “transitionless quantum driving” shows how to set a Hamiltonian which drives the dynamics of a system along instantaneous eigenstates of a reference Hamiltonian to reproduce the same final result of an adiabatic process in a shorter time. In this paper, motivated by transitionless quantum driving, we construct shortcuts to adiabatic passage in a three-atom system to create the Greenberger-Horne-Zeilinger states with the help of quantum Zeno dynamics and of non-resonant lasers. The influence of various decoherence processes is discussed by numerical simulation and the result proves that the scheme is fast and robust against decoherence and operational imperfection. PMID:26508283
NASA Astrophysics Data System (ADS)
Zhang, Kai; Nusran, N. M.; Slezak, B. R.; Gurudev Dutt, M. V.
2016-05-01
While it is often thought that the geometric phase is less sensitive to fluctuations in the control fields, a very general feature of adiabatic Hamiltonians is the unavoidable dynamic phase that accompanies the geometric phase. The effect of control field noise during adiabatic geometric quantum gate operations has not been probed experimentally, especially in the canonical spin qubit system that is of interest for quantum information. We present measurement of the Berry phase and carry out adiabatic geometric phase gate in a single solid-state spin qubit associated with the nitrogen-vacancy center in diamond. We manipulate the spin qubit geometrically by careful application of microwave radiation that creates an effective rotating magnetic field, and observe the resulting Berry phase signal via spin echo interferometry. Our results show that control field noise at frequencies higher than the spin echo clock frequency causes decay of the quantum phase, and degrades the fidelity of the geometric phase gate to the classical threshold after a few (∼10) operations. This occurs inspite of the geometric nature of the state preparation, due to unavoidable dynamic contributions. We have carried out systematic analysis and numerical simulations to study the effects of the control field noise and imperfect driving waveforms on the quantum phase gate.
Dynamics and spectroscopy of CH₂OO excited electronic states.
Kalinowski, Jaroslaw; Foreman, Elizabeth S; Kapnas, Kara M; Murray, Craig; Räsänen, Markku; Gerber, R Benny
2016-04-28
The excited states of the Criegee intermediate CH2OO are studied in molecular dynamics simulations using directly potentials from multi-reference perturbation theory (MR-PT2). The photoexcitation of the species is simulated, and trajectories are propagated in time on the excited state. Some of the photoexcitation events lead to direct fragmentation of the molecule, but other trajectories describe at least several vibrations in the excited state, that may terminate by relaxation to the ground electronic state. Limits on the role of non-adiabatic contributions to the process are estimated by two different simulations, one that forces surface-hopping at potential crossings, and another that ignores surface hopping altogether. The effect of non-adiabatic transitions is found to be small. Spectroscopic implications and consequences for the interpretation of experimental results are discussed. PMID:27040614
Wireless adiabatic power transfer
Rangelov, A.A.; Suchowski, H.; Silberberg, Y.; Vitanov, N.V.
2011-03-15
Research Highlights: > Efficient and robust mid-range wireless energy transfer between two coils. > The adiabatic energy transfer is analogous to adiabatic passage in quantum optics. > Wireless energy transfer is insensitive to any resonant constraints. > Wireless energy transfer is insensitive to noise in the neighborhood of the coils. - Abstract: We propose a technique for efficient mid-range wireless power transfer between two coils, by adapting the process of adiabatic passage for a coherently driven two-state quantum system to the realm of wireless energy transfer. The proposed technique is shown to be robust to noise, resonant constraints, and other interferences that exist in the neighborhood of the coils.
Topology of the Adiabatic Potential Energy Surfaces for theResonance States of the Water Anion
Haxton, Daniel J.; Rescigno, Thomas N.; McCurdy, C. William
2005-04-15
The potential energy surfaces corresponding to the long-lived fixed-nuclei electron scattering resonances of H{sub 2}O relevant to the dissociative electron attachment process are examined using a combination of ab initio scattering and bound-state calculations. These surfaces have a rich topology, characterized by three main features: a conical intersection between the {sup 2}A{sub 1} and {sup 2}B{sub 2} Feshbach resonance states; charge-transfer behavior in the OH ({sup 2}{Pi}) + H{sup -} asymptote of the {sup 2}B{sub 1} and {sup 2}A{sub 1} resonances; and an inherent double-valuedness of the surface for the {sup 2}B{sub 2} state the C{sub 2v} geometry, arising from a branch-point degeneracy with a {sup 2}B{sub 2} shape resonance. In total, eight individual seams of degeneracy among these resonances are located.
Ziegler, Tom; Krykunov, Mykhaylo; Autschbach, Jochen
2014-09-01
The random phase approximation (RPA) equation of adiabatic time dependent density functional ground state response theory (ATDDFT) has been used extensively in studies of excited states. It extracts information about excited states from frequency dependent ground state response properties and avoids, thus, in an elegant way, direct Kohn-Sham calculations on excited states in accordance with the status of DFT as a ground state theory. Thus, excitation energies can be found as resonance poles of frequency dependent ground state polarizability from the eigenvalues of the RPA equation. ATDDFT is approximate in that it makes use of a frequency independent energy kernel derived from the ground state functional. It is shown in this study that one can derive the RPA equation of ATDDFT from a purely variational approach in which stationary states above the ground state are located using our constricted variational DFT (CV-DFT) method and the ground state functional. Thus, locating stationary states above the ground state due to one-electron excitations with a ground state functional is completely equivalent to solving the RPA equation of TDDFT employing the same functional. The present study is an extension of a previous work in which we demonstrated the equivalence between ATDDFT and CV-DFT within the Tamm-Dancoff approximation. PMID:26588541
NASA Astrophysics Data System (ADS)
Subotnik, Joseph E.; Yeganeh, Sina; Cave, Robert J.; Ratner, Mark A.
2008-12-01
This article shows that, although Boys localization is usually applied to single-electron orbitals, the Boys method itself can be applied to many electron molecular states. For the two-state charge-transfer problem, we show analytically that Boys localization yields the same charge-localized diabatic states as those found by generalized Mulliken-Hush theory. We suggest that for future work in electron transfer, where systems have more than two charge centers, one may benefit by using a variant of Boys localization to construct diabatic potential energy surfaces and extract electronic coupling matrix elements. We discuss two chemical examples of Boys localization and propose a generalization of the Boys algorithm for creating diabatic states with localized spin density that should be useful for Dexter triplet-triplet energy transfer.
Romero-Redondo, C.; Garrido, E.; Barletta, P.; Kievsky, A.; Viviani, M.
2011-02-15
In this work we investigate 1+2 reactions within the framework of the hyperspherical adiabatic expansion method. With this aim two integral relations, derived from the Kohn variational principle, are used. A detailed derivation of these relations is shown. The expressions derived are general, not restricted to relative s partial waves, and with applicability in multichannel reactions. The convergence of the K matrix in terms of the adiabatic potentials is investigated. Together with a simple model case used as a test for the method, we show results for the collision of a {sup 4}He atom on a {sup 4}He{sub 2} dimer (only the elastic channel open), and for collisions involving a {sup 6}Li and two {sup 4}He atoms (two channels open).
Adame, J.; Warzel, S.
2015-11-15
In this note, we use ideas of Farhi et al. [Int. J. Quantum. Inf. 6, 503 (2008) and Quantum Inf. Comput. 11, 840 (2011)] who link a lower bound on the run time of their quantum adiabatic search algorithm to an upper bound on the energy gap above the ground-state of the generators of this algorithm. We apply these ideas to the quantum random energy model (QREM). Our main result is a simple proof of the conjectured exponential vanishing of the energy gap of the QREM.
NASA Astrophysics Data System (ADS)
Turek, Andrzej M.; Krishna, Tallapragada S. R.; Brela, Mateusz; Saltiel, Jack
2016-03-01
Fluorescence spectra of all-trans-1,6-diphenyl-1,3,5-hexatriene were measured in n-hexadecane at 99 °C by varying λexc in the 294-404 nm range. Resolution of this spectral matrix into s-trans,s-trans and s-cis,s-trans conformer fluorescence spectra yields the λexc dependence of fractional contributions which are converted to conformer specific fluorescence excitation spectra. Conformer absorption spectra obtained from the fluorescence excitation spectra are remarkably similar, but differ significantly from absorption spectra derived from a spectrothermal absorption spectral matrix measured in n-alkanes under isopolarizability conditions. The results reveal substantial conformer equilibration in the excited state. Theory is consistent with adiabatic conformer equilibration in the 21Ag state.
Single electron states in polyethylene
Wang, Y.; MacKernan, D.; Cubero, D. E-mail: n.quirke@imperial.ac.uk; Coker, D. F.; Quirke, N. E-mail: n.quirke@imperial.ac.uk
2014-04-21
We report computer simulations of an excess electron in various structural motifs of polyethylene at room temperature, including lamellar and interfacial regions between amorphous and lamellae, as well as nanometre-sized voids. Electronic properties such as density of states, mobility edges, and mobilities are computed on the different phases using a block Lanczos algorithm. Our results suggest that the electronic density of states for a heterogeneous material can be approximated by summing the single phase density of states weighted by their corresponding volume fractions. Additionally, a quantitative connection between the localized states of the excess electron and the local atomic structure is presented.
Single electron states in polyethylene
NASA Astrophysics Data System (ADS)
Wang, Y.; MacKernan, D.; Cubero, D.; Coker, D. F.; Quirke, N.
2014-04-01
We report computer simulations of an excess electron in various structural motifs of polyethylene at room temperature, including lamellar and interfacial regions between amorphous and lamellae, as well as nanometre-sized voids. Electronic properties such as density of states, mobility edges, and mobilities are computed on the different phases using a block Lanczos algorithm. Our results suggest that the electronic density of states for a heterogeneous material can be approximated by summing the single phase density of states weighted by their corresponding volume fractions. Additionally, a quantitative connection between the localized states of the excess electron and the local atomic structure is presented.
Accurate adiabatic correction in the hydrogen molecule
Pachucki, Krzysztof; Komasa, Jacek
2014-12-14
A new formalism for the accurate treatment of adiabatic effects in the hydrogen molecule is presented, in which the electronic wave function is expanded in the James-Coolidge basis functions. Systematic increase in the size of the basis set permits estimation of the accuracy. Numerical results for the adiabatic correction to the Born-Oppenheimer interaction energy reveal a relative precision of 10{sup −12} at an arbitrary internuclear distance. Such calculations have been performed for 88 internuclear distances in the range of 0 < R ⩽ 12 bohrs to construct the adiabatic correction potential and to solve the nuclear Schrödinger equation. Finally, the adiabatic correction to the dissociation energies of all rovibrational levels in H{sub 2}, HD, HT, D{sub 2}, DT, and T{sub 2} has been determined. For the ground state of H{sub 2} the estimated precision is 3 × 10{sup −7} cm{sup −1}, which is almost three orders of magnitude higher than that of the best previous result. The achieved accuracy removes the adiabatic contribution from the overall error budget of the present day theoretical predictions for the rovibrational levels.
Accurate adiabatic correction in the hydrogen molecule
NASA Astrophysics Data System (ADS)
Pachucki, Krzysztof; Komasa, Jacek
2014-12-01
A new formalism for the accurate treatment of adiabatic effects in the hydrogen molecule is presented, in which the electronic wave function is expanded in the James-Coolidge basis functions. Systematic increase in the size of the basis set permits estimation of the accuracy. Numerical results for the adiabatic correction to the Born-Oppenheimer interaction energy reveal a relative precision of 10-12 at an arbitrary internuclear distance. Such calculations have been performed for 88 internuclear distances in the range of 0 < R ⩽ 12 bohrs to construct the adiabatic correction potential and to solve the nuclear Schrödinger equation. Finally, the adiabatic correction to the dissociation energies of all rovibrational levels in H2, HD, HT, D2, DT, and T2 has been determined. For the ground state of H2 the estimated precision is 3 × 10-7 cm-1, which is almost three orders of magnitude higher than that of the best previous result. The achieved accuracy removes the adiabatic contribution from the overall error budget of the present day theoretical predictions for the rovibrational levels.
Parallelizable adiabatic gate teleportation
NASA Astrophysics Data System (ADS)
Nakago, Kosuke; Hajdušek, Michal; Nakayama, Shojun; Murao, Mio
2015-12-01
To investigate how a temporally ordered gate sequence can be parallelized in adiabatic implementations of quantum computation, we modify adiabatic gate teleportation, a model of quantum computation proposed by Bacon and Flammia [Phys. Rev. Lett. 103, 120504 (2009), 10.1103/PhysRevLett.103.120504], to a form deterministically simulating parallelized gate teleportation, which is achievable only by postselection. We introduce a twisted Heisenberg-type interaction Hamiltonian, a Heisenberg-type spin interaction where the coordinates of the second qubit are twisted according to a unitary gate. We develop parallelizable adiabatic gate teleportation (PAGT) where a sequence of unitary gates is performed in a single step of the adiabatic process. In PAGT, numeric calculations suggest the necessary time for the adiabatic evolution implementing a sequence of L unitary gates increases at most as O (L5) . However, we show that it has the interesting property that it can map the temporal order of gates to the spatial order of interactions specified by the final Hamiltonian. Using this property, we present a controlled-PAGT scheme to manipulate the order of gates by a control qubit. In the controlled-PAGT scheme, two differently ordered sequential unitary gates F G and G F are coherently performed depending on the state of a control qubit by simultaneously applying the twisted Heisenberg-type interaction Hamiltonians implementing unitary gates F and G . We investigate why the twisted Heisenberg-type interaction Hamiltonian allows PAGT. We show that the twisted Heisenberg-type interaction Hamiltonian has an ability to perform a transposed unitary gate by just modifying the space ordering of the final Hamiltonian implementing a unitary gate in adiabatic gate teleportation. The dynamics generated by the time-reversed Hamiltonian represented by the transposed unitary gate enables deterministic simulation of a postselected event of parallelized gate teleportation in adiabatic
Quantum and classical non-adiabatic dynamics of Li_{2}^{+}Ne photodissociation
NASA Astrophysics Data System (ADS)
Pouilly, Brigitte; Monnerville, Maurice; Zanuttini, David; Gervais, Benoît
2015-01-01
The 3D photodissociation dynamics of Li2+Ne system is investigated by quantum calculations using the multi-configuration time-dependent Hartree (MCTDH) method and by classical simulations with the trajectory surface hopping (TSH) approach. Six electronic states of A’ symmetry and two states of A” symmetry are involved in the process. Couplings in the excitation region and two conical intersections in the vicinity of the Franck-Condon zone control the non-adiabatic nuclear dynamics. A diabatic representation including all the states and the couplings is determined. Diabatic and adiabatic populations calculated for initial excitation to pure diabatic and adiabatic states lead to a clear understanding of the mechanisms governing the non-adiabatic photodissociation process. The classical and quantum photodissociation cross-sections for absorption in two adiabatic states of the A’ symmetry are calculated. A remarkable agreement between quantum and classical results is obtained regarding the populations and the absorption cross-sections.
Transition from the adiabatic to the sudden limit in core-electron photoemission
NASA Astrophysics Data System (ADS)
Hedin, Lars; Michiels, John; Inglesfield, John
1998-12-01
Experimental results for core-electron photoemission Jk(ω) are often compared with the one-electron spectral function Ac(ɛk-ω), where ω is the photon energy, ɛk is the photoelectron energy, and the optical transition matrix elements are taken as constant. Since Jk(ω) is nonzero only for ɛk>0, we must actually compare it with Ac(ɛk-ω)θ(ɛk). For metals Ac(ω) is known to have a quasiparticle (QP) peak with an asymmetric power-law [theories of Mahan, Nozières, de Dominicis, Langreth, and others (MND)] singularity due to low-energy particle-hole excitations. The QP peak starts at the core-electron energy ɛc, and is followed by an extended satellite (shakeup) structure at smaller ω. For photon energies ω just above threshold, ωth=-ɛc, Ac(ɛk-ω)θ(ɛk) as a function of ɛk (ω constant) is cut just behind the quasiparticle peak, and neither the tail of the MND line nor the plasmon satellites are present. The sudden (high-energy) limit is given by a convolution of Ac(ω) and a loss function, i.e., by the Berglund-Spicer two-step expression. Thus Ac(ω) alone does not give the correct photoelectron spectrum, neither at low nor at high energies. We present an extension of the quantum-mechanical (QM) models developed earlier by Inglesfield, and by Bardyszewski and Hedin to calculate Jk(ω). It includes recoil and damping, as well as shakeup effects and extrinsic losses, is exact in the high-energy limit, and allows calculations of Jk(ω) including the MND line and multiple plasmon losses. The model, which involves electrons coupled to quasibosons, is motivated by detailed arguments. As an illustration we have made quantitative calculations for a semi-infinite jellium with the density of aluminum metal and an embedded atom. The coupling functions (fluctuation potentials) between the electron and the quasibosons are related to the random-phase-approximation dielectric function, and different levels of approximations are evaluated numerically. The differences
NASA Astrophysics Data System (ADS)
Kłos, Jacek; Alexander, Millard H.; Kumar, Praveen; Poirier, Bill; Jiang, Bin; Guo, Hua
2016-05-01
We report new and more accurate adiabatic potential energy surfaces (PESs) for the ground X˜ 1A1 and electronically excited C˜ 1B2(21A') states of the SO2 molecule. Ab initio points are calculated using the explicitly correlated internally contracted multi-reference configuration interaction (icMRCI-F12) method. A second less accurate PES for the ground X ˜ state is also calculated using an explicitly correlated single-reference coupled-cluster method with single, double, and non-iterative triple excitations [CCSD(T)-F12]. With these new three-dimensional PESs, we determine energies of the vibrational bound states and compare these values to existing literature data and experiment.
Adiabatically implementing quantum gates
Sun, Jie; Lu, Songfeng Liu, Fang
2014-06-14
We show that, through the approach of quantum adiabatic evolution, all of the usual quantum gates can be implemented efficiently, yielding running time of order O(1). This may be considered as a useful alternative to the standard quantum computing approach, which involves quantum gates transforming quantum states during the computing process.
Spatial adiabatic passage: a review of recent progress
NASA Astrophysics Data System (ADS)
Menchon-Enrich, R.; Benseny, A.; Ahufinger, V.; Greentree, A. D.; Busch, Th; Mompart, J.
2016-07-01
Adiabatic techniques are known to allow for engineering quantum states with high fidelity. This requirement is currently of large interest, as applications in quantum information require the preparation and manipulation of quantum states with minimal errors. Here we review recent progress on developing techniques for the preparation of spatial states through adiabatic passage, particularly focusing on three state systems. These techniques can be applied to matter waves in external potentials, such as cold atoms or electrons, and to classical waves in waveguides, such as light or sound.
Spatial adiabatic passage: a review of recent progress.
Menchon-Enrich, R; Benseny, A; Ahufinger, V; Greentree, A D; Busch, Th; Mompart, J
2016-07-01
Adiabatic techniques are known to allow for engineering quantum states with high fidelity. This requirement is currently of large interest, as applications in quantum information require the preparation and manipulation of quantum states with minimal errors. Here we review recent progress on developing techniques for the preparation of spatial states through adiabatic passage, particularly focusing on three state systems. These techniques can be applied to matter waves in external potentials, such as cold atoms or electrons, and to classical waves in waveguides, such as light or sound. PMID:27245462
Dou, Wenjie; Subotnik, Joseph E
2016-08-01
We present a very general form of electronic friction as present when a molecule with multiple orbitals hybridizes with a metal electrode. To develop this picture of friction, we embed the quantum-classical Liouville equation (QCLE) within a classical master equation (CME). Thus, this article extends our previous work analyzing the case of one electronic level, as we may now treat the case of multiple levels and many electronic molecular states. We show that, in the adiabatic limit, where electron transitions are much faster than nuclear motion, the QCLE-CME reduces to a Fokker-Planck equation, such that nuclei feel an average force as well as friction and a random force-as caused by their interaction with the metallic electrons. Finally, we show numerically and analytically that our frictional results agree with other published results calculated using non-equilibrium Green's functions. Numerical recipes for solving this QCLE-CME will be provided in a subsequent paper. PMID:27497534
NASA Astrophysics Data System (ADS)
Dou, Wenjie; Subotnik, Joseph E.
2016-08-01
We present a very general form of electronic friction as present when a molecule with multiple orbitals hybridizes with a metal electrode. To develop this picture of friction, we embed the quantum-classical Liouville equation (QCLE) within a classical master equation (CME). Thus, this article extends our previous work analyzing the case of one electronic level, as we may now treat the case of multiple levels and many electronic molecular states. We show that, in the adiabatic limit, where electron transitions are much faster than nuclear motion, the QCLE-CME reduces to a Fokker-Planck equation, such that nuclei feel an average force as well as friction and a random force—as caused by their interaction with the metallic electrons. Finally, we show numerically and analytically that our frictional results agree with other published results calculated using non-equilibrium Green's functions. Numerical recipes for solving this QCLE-CME will be provided in a subsequent paper.
Electron correlations in solid state physics
Freericks, J.K.
1991-04-01
Exactly solvable models of electron correlations in solid state physics are presented. These models include the spinless Falicov- Kimball model, the t-t{prime}-J model, and the Hubbard model. The spinless Falicov-Kimball model is analyzed in one-dimension. Perturbation theory and numerical techniques are employed to determine the phase diagram at zero temperature. A fractal structure is found where the ground-state changes (discontinuously) at each rational electron filling. The t-t{prime}-J model (strongly interacting limit of a Hubbard model) is studied on eight-site small clusters in the simple-cubic, body-centered-cubic, face-centered-cubic, and square lattices. Symmetry is used to simplify the problem and determine the exact many-body wavefunctions. Ground states are found that exhibit magnetic order or heavy-fermionic character. Attempts to extrapolate to the thermodynamic limit are also made. The Hubbard model is examined on an eight-site square-lattice cluster in the presence of and in the absence of a magnetic field'' that couples only to orbital motion. A new magnetic phase is discovered for the ordinary Hubbard model at half-filling. In the magnetic field'' case, it is found that the strongly frustrated Heisenberg model may be studied from adiabatic continuation of a tight-binding model (from weak to strong coupling) at one point. The full symmetries of the Hamiltonian are utilized to make the exact diagonalization feasibile. Finally, the presence of hidden'' extra symmetry for finite size clusters with periodic boundary conditions is analyzed for a variety of clusters. Moderately sized systems allow nonrigid transformations that map a lattice onto itself preserving its neighbor structure; similar operations are not present in smaller or larger systems. The additional symmetry requires particular representations of the space group to stick together explaining many puzzling degeneracies found in exact diagonalization studies.
NASA Astrophysics Data System (ADS)
Li, Dafa
2016-05-01
The adiabatic theorem was proposed about 90 years ago and has played an important role in quantum physics. The quantitative adiabatic condition constructed from eigenstates and eigenvalues of a Hamiltonian is a traditional tool to estimate adiabaticity and has proven to be the necessary and sufficient condition for adiabaticity. However, recently the condition has become a controversial subject. In this paper, we list some expressions to estimate the validity of the adiabatic approximation. We show that the quantitative adiabatic condition is invalid for the adiabatic approximation via the Euclidean distance between the adiabatic state and the evolution state. Furthermore, we deduce general necessary and sufficient conditions for the validity of the adiabatic approximation by different definitions.
Zhou, Linsen; Xie, Daiqian E-mail: hguo@unm.edu; Guo, Hua E-mail: hguo@unm.edu
2015-03-28
A detailed quantum mechanical characterization of the photodissociation dynamics of H{sub 2}O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X{sup ~}/A{sup ~}) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X{sup ~}, v = 0) exhibit very different characteristics. The A′ states, produced mostly via the B{sup ~}→X{sup ~} conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B{sup ~}→A{sup ~} Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X{sup ~}) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B{sup ~}→X{sup ~} non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(A{sup ~}) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.
NASA Astrophysics Data System (ADS)
Zhou, Linsen; Xie, Daiqian; Guo, Hua
2015-03-01
A detailed quantum mechanical characterization of the photodissociation dynamics of H2O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH( X ˜ / A ˜ ) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH( X ˜ , v = 0) exhibit very different characteristics. The A' states, produced mostly via the B ˜ → X ˜ conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B ˜ → A ˜ Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH( X ˜ ) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B ˜ → X ˜ non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH( A ˜ ) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.
Zhou, Linsen; Xie, Daiqian; Guo, Hua
2015-03-28
A detailed quantum mechanical characterization of the photodissociation dynamics of H2O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X̃/Ã) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X̃, v = 0) exhibit very different characteristics. The A' states, produced mostly via the B̃→X̃ conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B̃→Ã Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X̃) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B̃→X̃ non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(Ã) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces. PMID:25833589
Transitionless driving on adiabatic search algorithm
Oh, Sangchul; Kais, Sabre
2014-12-14
We study quantum dynamics of the adiabatic search algorithm with the equivalent two-level system. Its adiabatic and non-adiabatic evolution is studied and visualized as trajectories of Bloch vectors on a Bloch sphere. We find the change in the non-adiabatic transition probability from exponential decay for the short running time to inverse-square decay in asymptotic running time. The scaling of the critical running time is expressed in terms of the Lambert W function. We derive the transitionless driving Hamiltonian for the adiabatic search algorithm, which makes a quantum state follow the adiabatic path. We demonstrate that a uniform transitionless driving Hamiltonian, approximate to the exact time-dependent driving Hamiltonian, can alter the non-adiabatic transition probability from the inverse square decay to the inverse fourth power decay with the running time. This may open up a new but simple way of speeding up adiabatic quantum dynamics.
Transitionless driving on adiabatic search algorithm
NASA Astrophysics Data System (ADS)
Oh, Sangchul; Kais, Sabre
2014-12-01
We study quantum dynamics of the adiabatic search algorithm with the equivalent two-level system. Its adiabatic and non-adiabatic evolution is studied and visualized as trajectories of Bloch vectors on a Bloch sphere. We find the change in the non-adiabatic transition probability from exponential decay for the short running time to inverse-square decay in asymptotic running time. The scaling of the critical running time is expressed in terms of the Lambert W function. We derive the transitionless driving Hamiltonian for the adiabatic search algorithm, which makes a quantum state follow the adiabatic path. We demonstrate that a uniform transitionless driving Hamiltonian, approximate to the exact time-dependent driving Hamiltonian, can alter the non-adiabatic transition probability from the inverse square decay to the inverse fourth power decay with the running time. This may open up a new but simple way of speeding up adiabatic quantum dynamics.
Transitionless driving on adiabatic search algorithm.
Oh, Sangchul; Kais, Sabre
2014-12-14
We study quantum dynamics of the adiabatic search algorithm with the equivalent two-level system. Its adiabatic and non-adiabatic evolution is studied and visualized as trajectories of Bloch vectors on a Bloch sphere. We find the change in the non-adiabatic transition probability from exponential decay for the short running time to inverse-square decay in asymptotic running time. The scaling of the critical running time is expressed in terms of the Lambert W function. We derive the transitionless driving Hamiltonian for the adiabatic search algorithm, which makes a quantum state follow the adiabatic path. We demonstrate that a uniform transitionless driving Hamiltonian, approximate to the exact time-dependent driving Hamiltonian, can alter the non-adiabatic transition probability from the inverse square decay to the inverse fourth power decay with the running time. This may open up a new but simple way of speeding up adiabatic quantum dynamics. PMID:25494733
Adiabatic tracking of a state: a new route to nonequilibrium physics.
Moliner, M; Schmitteckert, P
2013-09-20
We present a novel numerical approach to track the response of a quantum system to an external perturbation that is progressively switched on. The method is applied, within the framework of the density matrix renormalization group technique, to track current-carrying states of interacting fermions in one dimension and in the presence of an Aharonov-Bohm magnetic flux. This protocol allows us to access highly excited states. We also discuss the connection with the entanglement entropy of these excited states. PMID:24093238
Excited states of a hydrated electron and aqueous chloride by computer simulation
NASA Astrophysics Data System (ADS)
Borgis, Daniel; Staib, Arnulf
1994-12-01
Results of adiabatic molecular dynamics simulations for a hydrated electron and the aqueous chloride anion are reported. A novel technical feature is the efficient representation of solute electronic wavefunctions in terms of floating spherical Gaussian orbitals. The simulations account for the coupling of the excess electron to the solvent electronic polarization in an explicit and self-consistent fashion. The computed electronic ground state absorption spectrum for e(-)/H2O and the charge-transfer-to-solvent spectra for Cl(-)/H2O are analyzed. The energetic aspects of the models and the short time solute electronic dynamics are discussed.
Deng, Shihu; Kong, Xiangyu; Zhang, GuanXin; Yang, Yan; Zheng, Weijun; Sun, Zhenrong; Zhang, De-Qing; Wang, Xue B.
2014-06-19
The first excited state of the model green fluorescence protein (GFP) chromophore anion (S1) and its energy level against the electron-detached neutral radical, D0 state are crucial in determining the photophysics and the photo-induced dynamics of GFP. Extensive experimental and theoretical studies, particularly several very recent gas phase investigations concluded that S1 is a bound state in the Franck-Condon vertical region with respect to D0. However, what remains unknown and challenging is if S1 is bound adiabatically, primarily due to lack of accurate experimental measurements, as well as due to close proximity in energy for these two states that even sophisticated high-level ab initio calculations can’t reliably predict. Here, we report a negative ion photoelectron spectroscopy study on the model GFP chromophore anion, the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI–). Despite the considerable size and low symmetry of the molecule, well resolved vibrational structures were obtained with the 0–0 transition being the most intense peak. The adiabatic (ADE) and vertical detachment energy (VDE) therefore are determined, both to be 2.73 ± 0.01 eV, indicating the detached D0 state is 0.16 eV higher in energy than the photon excited S1 state. The accurate ADE and VDE values and the well-resolved photoelectron spectra reported here provide much needed, robust benchmarks for future theoretical investigations.
NASA Astrophysics Data System (ADS)
Wu, Jin-Lei; Song, Chong; Xu, Jing; Yu, Lin; Ji, Xin; Zhang, Shou
2016-06-01
An efficient scheme is proposed for generating n-qubit Greenberger-Horne-Zeilinger states of n superconducting qubits separated by (n-1 ) coplanar waveguide resonators capacitively via adiabatic passage with the help of quantum Zeno dynamics in one step. In the scheme, it is not necessary to precisely control the time of the whole operation and the Rabi frequencies of classical fields because of the introduction of adiabatic passage. The numerical simulations for three-qubit Greenberger-Horne-Zeilinger state show that the scheme is insensitive to the dissipation of the resonators and the energy relaxation of the superconducting qubits. The three-qubit Greenberger-Horne-Zeilinger state can be deterministically generated with comparatively high fidelity in the current experimental conditions, though the scheme is somewhat sensitive to the dephasing of superconducting qubits.
Interchain electron states in polyethylene
NASA Astrophysics Data System (ADS)
Serra, S.; Tosatti, E.; Iarlori, S.; Scandolo, S.; Santoro, G.
2000-08-01
We present a theoretical study of the nature of the lowest empty conduction-band states in crystalline polyethylene (PE), conducted through density-functional electronic structure calculations. Results reveal that the wave function of the conduction-band edge is of interchain character, as opposed to the intrachain character of all the filled valence-band states. Thus, while a hole added to neutral PE will mainly belong to the PE chain backbone bonds, an added electron in PE will mostly reside between the chains, and far from the existing bonds. Moreover, the added electron state charge centroid is predicted to move further out from the chain backbone towards the low-density interstitial region, if and when the chains are pried apart. This suggests that injected electrons will naturally flow to low-density regions inside real PE, and that the experimentally established propensity of PE to expel electrons out of the bulk, should be directly related to the interchain nature of the conduction states.
A diabatic representation of the two lowest electronic states of Li{sub 3}
Ghassemi, Elham Nour; Larson, Jonas; Institut für Theoretische Physik, Universität zu Köln, Köln De-50937 ; Larson, Åsa
2014-04-21
Using the Multi-Reference Configuration Interaction method, the adiabatic potential energy surfaces of Li{sub 3} are computed. The two lowest electronic states are bound and exhibit a conical intersection. By fitting the calculated potential energy surfaces to the cubic E ⊗ ε Jahn-Teller model we extract the effective Jahn-Teller parameters corresponding to Li{sub 3}. These are used to set up the transformation matrix which transforms from the adiabatic to a diabatic representation. This diabatization method gives a Hamiltonian for Li{sub 3} which is free from singular non-adiabatic couplings and should be accurate for large internuclear distances, and it thereby allows for bound dynamics in the vicinity of the conical intersection to be explored.
Equation of state in relativistic magnetohydrodynamics: variable versus constant adiabatic index
NASA Astrophysics Data System (ADS)
Mignone, A.; McKinney, Jonathan C.
2007-07-01
The role of the equation of state (EoS) for a perfectly conducting, relativistic magnetized fluid is the main subject of this work. The ideal constant Γ-law EoS, commonly adopted in a wide range of astrophysical applications, is compared with a more realistic EoS that better approximates the single-specie relativistic gas. The paper focuses on three different topics. First, the influence of a more realistic EoS on the propagation of fast magnetosonic shocks is investigated. This calls into question the validity of the constant Γ-law EoS in problems where the temperature of the gas substantially changes across hydromagnetic waves. Secondly, we present a new inversion scheme to recover primitive variables (such as rest-mass density and pressure) from conservative ones that allows for a general EoS and avoids catastrophic numerical cancellations in the non-relativistic and ultrarelativistic limits. Finally, selected numerical tests of astrophysical relevance (including magnetized accretion flows around Kerr black holes) are compared using different equations of state. Our main conclusion is that the choice of a realistic EoS can considerably bear upon the solution when transitions from cold to hot gas (or vice versa) are present. Under these circumstances, a polytropic EoS can significantly endanger the solution.
Cotton, Stephen J; Miller, William H
2015-12-17
A recent series of papers has shown that a symmetrical quasi-classical (SQC) windowing procedure applied to the Meyer-Miller (MM) classical vibronic Hamiltonian provides a very good treatment of electronically nonadiabatic processes in a variety of benchmark model systems, including systems that exhibit strong quantum coherence effects and some which other approximate approaches have difficulty in describing correctly. In this paper, a different classical electronic Hamiltonian for the treatment of electronically nonadiabatic processes is proposed (and "quantized" via the SQC windowing approach), which maps the dynamics of F coupled electronic states to a set of F spin-(1)/2 degrees of freedom (DOF), similar to the Fermionic spin model described by Miller and White (J. Chem. Phys. 1986, 84, 5059). It is noted that this spin-mapping (SM) Hamiltonian is an exact Hamiltonian if treated as a quantum mechanical (QM) operator-and thus QM'ly equivalent to the MM Hamiltonian-but that an analytically distinct classical analogue is obtained by replacing the QM spin-operators with their classical counterparts. Due to their analytic differences, a practical comparison is then made between the MM and SM Hamiltonians (when quantized with the SQC technique) by applying the latter to many of the same benchmark test problems successfully treated in our recent work with the SQC/MM model. We find that for every benchmark problem the MM model provides (slightly) better agreement with the correct quantum nonadiabatic transition probabilities than does the new SM model. This is despite the fact that one might expect, a priori, a more natural description of electronic state populations (occupied versus unoccupied) to be provided by DOF with only two states, i.e., spin-(1)/2 DOF, rather than by harmonic oscillator DOF which have an infinite manifold of states (though only two of these are ever occupied). PMID:26299361
Adiabatic potential-energy curves of long-range Rydberg molecules: Two-electron R -matrix approach
NASA Astrophysics Data System (ADS)
Tarana, Michal; Čurík, Roman
2016-01-01
We introduce a computational method developed for study of long-range molecular Rydberg states of such systems that can be approximated by two electrons in a model potential of the atomic cores. Only diatomic molecules are considered. The method is based on a two-electron R -matrix approach inside a sphere centered on one of the atoms. The wave function is then connected to a Coulomb region outside the sphere via a multichannel version of the Coulomb Green's function. This approach is put into a test by its application to a study of Rydberg states of the hydrogen molecule for internuclear distances R from 20 to 400 bohrs and energies corresponding to n from 3 to 22. The results are compared with previous quantum chemical calculations (lower quantum numbers n ) and computations based on contact-potential models (higher quantum numbers n ).
Golibrzuch, Kai; Shirhatti, Pranav R.; Kandratsenka, Alexander; Wodtke, Alec M.; Bartels, Christof; Max Planck Institute for Biophysical Chemistry, Göttingen 37077 ; Rahinov, Igor; Auerbach, Daniel J.; Max Planck Institute for Biophysical Chemistry, Göttingen 37077; Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106
2014-01-28
We present a combined experimental and theoretical study of NO(v = 3 → 3, 2, 1) scattering from a Au(111) surface at incidence translational energies ranging from 0.1 to 1.2 eV. Experimentally, molecular beam–surface scattering is combined with vibrational overtone pumping and quantum-state selective detection of the recoiling molecules. Theoretically, we employ a recently developed first-principles approach, which employs an Independent Electron Surface Hopping (IESH) algorithm to model the nonadiabatic dynamics on a Newns-Anderson Hamiltonian derived from density functional theory. This approach has been successful when compared to previously reported NO/Au scattering data. The experiments presented here show that vibrational relaxation probabilities increase with incidence energy of translation. The theoretical simulations incorrectly predict high relaxation probabilities at low incidence translational energy. We show that this behavior originates from trajectories exhibiting multiple bounces at the surface, associated with deeper penetration and favored (N-down) molecular orientation, resulting in a higher average number of electronic hops and thus stronger vibrational relaxation. The experimentally observed narrow angular distributions suggest that mainly single-bounce collisions are important. Restricting the simulations by selecting only single-bounce trajectories improves agreement with experiment. The multiple bounce artifacts discovered in this work are also present in simulations employing electronic friction and even for electronically adiabatic simulations, meaning they are not a direct result of the IESH algorithm. This work demonstrates how even subtle errors in the adiabatic interaction potential, especially those that influence the interaction time of the molecule with the surface, can lead to an incorrect description of electronically nonadiabatic vibrational energy transfer in molecule-surface collisions.
NASA Astrophysics Data System (ADS)
Chen, Wei-Chun; Wang, Yih-Wen; Shu, Chi-Min
2016-06-01
Use of adiabatic calorimetry to characterise thermal runaway of Li-ion cells is a crucial technique in battery safety testing. Various states of charge (SoC) of Li-ion cells were investigated to ascertain their thermal runaway features using a Vent Sizing Package 2 (VSP2) adiabatic calorimeter. To evaluate the thermal runaway characteristics, the temperature-pressure-time trajectories of commercial cylindrical cells were tested, and it was found that cells at a SoC of greater than 50% were subject to thermal explosion at elevated temperatures. Calorimetry data from various 18650 Li-ion cells with different SoC were used to calculate the thermal explosion energies and chemical kinetics; furthermore, a novel self-heating model based on a pseudo-zero-order reaction that follows the Arrhenius equation was found to be applicable for studying the exothermic reaction of a charged cell.
NASA Astrophysics Data System (ADS)
Liang, H.; Ashour-Abdalla, M.; Richard, R. L.; Schriver, D.; El-Alaoui, M.; Walker, R. J.
2013-12-01
We investigate the spatial evolution of energetic electron distribution functions in the near-Earth plasma sheet associated with earthward propagating dipolarization fronts by using in situ observations as well as magnetohydrodynamic (MHD) and large scale kinetic (LSK) simulations. We have investigated two substorms, one on February 15, 2008 and the other on August 15, 2001. The February 15 event was observed by one of the THEMIS spacecraft at X_{GSM} -10RE, while the August 15 event was observed by Cluster at X -18RE. Both the MHD and LSK simulation results are compared to these spacecraft observations. Earthward propagating dipolarization fronts are found in both the observations and the MHD simulations, which exhibit very different magnetotail configurations, with contrasting flows, magnetic reconnection configuration, and plasma sheet structure. Electron LSK simulations were performed by using the time-varying magnetic and electric fields from the global MHD simulations. For the February 15, 2008 event, the electrons were launched near X = -20 RE with a thermal energy of 1 keV and for August 15, 2001 event, they were launched at 4 keV near X = -22 RE. These electrons undergo both non-adiabatic acceleration near the magnetotail reconnection region and adiabatic acceleration as they propagate earthward from the launch region. We compute the electron distribution functions parallel and perpendicular to the magnetic field at different locations between X = -18 RE and X = -10 RE in the plasma sheet. We find that for the February 15, 2008 event, reconnection is localized with a narrow region of high-speed flows ( 300 km/s). For this event the distribution functions show mainly f(v_perp) > f(v_par) ("par" and "perp" correspond to parallel and perpendicular to magnetic field). On August 15, 2001, there is a neutral line extending across the tail with relatively low-speed flows ( 100 km/s). For this event the distribution functions show mainly f(v_par) > f(v_perp). The
Nonadiabatic quantum Liouville and master equations in the adiabatic basis
Jang, Seogjoo
2012-12-14
A compact form of nonadiabatic molecular Hamiltonian in the basis of adiabatic electronic states and nuclear position states is presented. The Hamiltonian, which includes both the first and the second derivative couplings, is Hermitian and thus leads to a standard expression for the quantum Liouville equation for the density operator. With the application of a projection operator technique, a quantum master equation for the diagonal components of the density operator is derived. Under the assumption that nuclear states are much more short ranged compared to electronic states and assuming no singularity, a semi-adiabatic approximation is invoked, which results in expressions for the nonadiabatic molecular Hamiltonian and the quantum Liouville equation that are much more amenable to advanced quantum dynamics calculation. The semi-adiabatic approximation is also applied to a resonance energy transfer system consisting of a donor and an acceptor interacting via Coulomb terms, and explicit detailed expressions for exciton-bath Hamiltonian including all the non-adiabatic terms are derived.
The molecular symmetry adapted non - adiabatic coupling terms and diabatic Hamiltonian matrix
NASA Astrophysics Data System (ADS)
Mukherjee, Saikat; Bandyopadhyay, Sudip; Paul, Amit Kumar; Adhikari, Satrajit
2013-04-01
We calculate the adiabatic Potential Energy Surfaces (PESs) and the Non - Adiabatic Coupling Terms (NACTs) for the excited electronic states (22 E' and 12 A'1) of Na3 cluster at the MRCI level by using ab initio quantum chemistry package (MOLPRO), where the NACTs are adapted with Molecular Symmetry (MS) by employing appropriate Irreducible Representations (IREPs). Such terms are incorporated into the Adiabatic to Diabatic Transformation (ADT) equations to obtain the ADT angles to construct the continuous, single - valued, symmetric and smooth 3 × 3 diabatic Hamiltonian matrix.
Zhao, Li; Zhou, Pan-Wang; Zhao, Guang-Jiu
2016-07-28
The trans-urocanic acid, a UV chromophore in the epidermis of human skin, was found to exhibit a wavelength dependent isomerization property. The isomerization quantum yield to cis-urocanic is greatest when being excited to the S1 state, whereas exciting the molecule to the S2 state causes almost no isomerization. The comparative photochemical behavior of the trans-urocanic on the S1 and S2 states continues to be the subject of intense research effort. This study is concerned with the unique photo-behavior of this interesting molecule on the S2 state. Combining the on-the-fly surface hopping dynamics simulations and static electronic structure calculations, three decay channels were observed following excitation to the S2 state. An overwhelming majority of the molecules decay to the S1 state through a planar or pucker characterized minimum energy conical intersection (MECI), and then decay to the ground state along a relaxation coordinate driven by a pucker deformation of the ring. A very small fraction of molecules decay to the S1 state by a MECI characterized by a twisting motion around the CC double bond, which continues to drive the molecule to deactivate to the ground state. The latter channel is related with the photoisomerization process, whereas the former one will only generate the original trans-form products. The present work provides a novel S2 state decay mechanism of this molecule, which offers useful information to explain the wavelength dependent isomerization behavior. PMID:27475370
NASA Astrophysics Data System (ADS)
Zhao, Li; Zhou, Pan-Wang; Zhao, Guang-Jiu
2016-07-01
The trans-urocanic acid, a UV chromophore in the epidermis of human skin, was found to exhibit a wavelength dependent isomerization property. The isomerization quantum yield to cis-urocanic is greatest when being excited to the S1 state, whereas exciting the molecule to the S2 state causes almost no isomerization. The comparative photochemical behavior of the trans-urocanic on the S1 and S2 states continues to be the subject of intense research effort. This study is concerned with the unique photo-behavior of this interesting molecule on the S2 state. Combining the on-the-fly surface hopping dynamics simulations and static electronic structure calculations, three decay channels were observed following excitation to the S2 state. An overwhelming majority of the molecules decay to the S1 state through a planar or pucker characterized minimum energy conical intersection (MECI), and then decay to the ground state along a relaxation coordinate driven by a pucker deformation of the ring. A very small fraction of molecules decay to the S1 state by a MECI characterized by a twisting motion around the CC double bond, which continues to drive the molecule to deactivate to the ground state. The latter channel is related with the photoisomerization process, whereas the former one will only generate the original trans-form products. The present work provides a novel S2 state decay mechanism of this molecule, which offers useful information to explain the wavelength dependent isomerization behavior.
NASA Astrophysics Data System (ADS)
Engel, D.; Klews, M.; Wunner, G.
2009-02-01
We have developed a new method for the fast computation of wavelengths and oscillator strengths for medium-Z atoms and ions, up to iron, at neutron star magnetic field strengths. The method is a parallelized Hartree-Fock approach in adiabatic approximation based on finite-element and B-spline techniques. It turns out that typically 15-20 finite elements are sufficient to calculate energies to within a relative accuracy of 10-5 in 4 or 5 iteration steps using B-splines of 6th order, with parallelization speed-ups of 20 on a 26-processor machine. Results have been obtained for the energies of the ground states and excited levels and for the transition strengths of astrophysically relevant atoms and ions in the range Z=2…26 in different ionization stages. Catalogue identifier: AECC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AECC_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 3845 No. of bytes in distributed program, including test data, etc.: 27 989 Distribution format: tar.gz Programming language: MPI/Fortran 95 and Python Computer: Cluster of 1-26 HP Compaq dc5750 Operating system: Fedora 7 Has the code been vectorised or parallelized?: Yes RAM: 1 GByte Classification: 2.1 External routines: MPI/GFortran, LAPACK, PyLab/Matplotlib Nature of problem: Calculations of synthetic spectra [1] of strongly magnetized neutron stars are bedevilled by the lack of data for atoms in intense magnetic fields. While the behaviour of hydrogen and helium has been investigated in detail (see, e.g., [2]), complete and reliable data for heavier elements, in particular iron, are still missing. Since neutron stars are formed by the collapse of the iron cores of massive stars, it may be assumed that their atmospheres contain an iron plasma. Our objective is to fill the gap
NASA Astrophysics Data System (ADS)
Froese, Robert D. J.; Morokuma, Keiji
1996-12-01
The recently proposed integrated MO + MO (IMOMO) and MO + MM (IMOMM) methods have been applied to excited states of large molecules, i.e., the adiabatic triplet excitation energies of cyclic alkenes and enones. The IMOMO methods with G2MS as High level and HF or MP2 as Low level agree well with pure MO benchmarks and experiments. The substituent shifts have been discussed in the IMOMO analysis. The geometries of a testosterone derivative with more than 50 atoms were optimized for the lower triplet excited states with the IMOMM(HF:MM3) method and their energies were calculated using IMOMO and IMOMM methods.
The properties of LiH in its ground and first excited electronic state
NASA Astrophysics Data System (ADS)
Bishop, David M.; Cheung, Lap M.
1983-09-01
With the aid of recently produced potential curves for the X 1Σ+ and A 1Σ+ states of lithium hydride, the rovibronic energies of 7LiH have been calculated. From these energies the standard spectroscopic constants have been evaluated. The effect on these constants of inclusion of adiabatic corrections (for diagonal nuclear motion) in the potential curves is discussed. The expectation values of certain powers of the electronic coordinates are also tabulated.
Kittell, Aaron W.; Camenisch, Theodore G.; Ratke, Joseph J.; Sidabras, Jason W.; Hyde, James S.
2011-01-01
A continuous wave (CW) electron paramagnetic resonance (EPR) spectrum is typically displayed as the first harmonic response to the application of 100 kHz magnetic field modulation, which is used to enhance sensitivity by reducing the level of 1/f noise. However, magnetic field modulation of any amplitude causes spectral broadening and sacrifices EPR spectral intensity by at least a factor of two. In the work presented here, a CW rapid-scan spectroscopic technique that avoids these compromises and also provides a means of avoiding 1/f noise is developed. This technique, termed non-adiabatic rapid sweep (NARS) EPR, consists of repetitively sweeping the polarizing magnetic field in a linear manner over a spectral fragment with a small coil at a repetition rate that is sufficiently high that receiver noise, microwave phase noise, and environmental microphonics, each of which has 1/f characteristics, are overcome. Nevertheless, the rate of sweep is sufficiently slow that adiabatic responses are avoided and the spin system is always close to thermal equilibrium. The repetitively acquired spectra from the spectral fragment are averaged. Under these conditions, undistorted pure absorption spectra are obtained without broadening or loss of signal intensity. A digital filter such as a moving average is applied to remove high frequency noise, which is approximately equivalent in bandwidth to use of an integrating time constant in conventional field modulation with lock-in detection. Nitroxide spectra at L- and X-band are presented. PMID:21741868
Patrick, Christopher E. Thygesen, Kristian S.
2015-09-14
We present calculations of the correlation energies of crystalline solids and isolated systems within the adiabatic-connection fluctuation-dissipation formulation of density-functional theory. We perform a quantitative comparison of a set of model exchange-correlation kernels originally derived for the homogeneous electron gas (HEG), including the recently introduced renormalized adiabatic local-density approximation (rALDA) and also kernels which (a) satisfy known exact limits of the HEG, (b) carry a frequency dependence, or (c) display a 1/k{sup 2} divergence for small wavevectors. After generalizing the kernels to inhomogeneous systems through a reciprocal-space averaging procedure, we calculate the lattice constants and bulk moduli of a test set of 10 solids consisting of tetrahedrally bonded semiconductors (C, Si, SiC), ionic compounds (MgO, LiCl, LiF), and metals (Al, Na, Cu, Pd). We also consider the atomization energy of the H{sub 2} molecule. We compare the results calculated with different kernels to those obtained from the random-phase approximation (RPA) and to experimental measurements. We demonstrate that the model kernels correct the RPA’s tendency to overestimate the magnitude of the correlation energy whilst maintaining a high-accuracy description of structural properties.
[Bond selective chemistry beyond the adiabatic approximation
Butler, L.J.
1993-02-28
The adiabatic Born-Oppenheimer potential energy surface approximation is not valid for reaction of a wide variety of energetic materials and organic fuels; coupling between electronic states of reacting species plays a key role in determining the selectivity of the chemical reactions induced. This research program initially studies this coupling in (1) selective C-Br bond fission in 1,3- bromoiodopropane, (2) C-S:S-H bond fission branching in CH[sub 3]SH, and (3) competition between bond fission channels and H[sub 2] elimination in CH[sub 3]NH[sub 2].
Bond selective chemistry beyond the adiabatic approximation
Butler, L.J.
1993-12-01
One of the most important challenges in chemistry is to develop predictive ability for the branching between energetically allowed chemical reaction pathways. Such predictive capability, coupled with a fundamental understanding of the important molecular interactions, is essential to the development and utilization of new fuels and the design of efficient combustion processes. Existing transition state and exact quantum theories successfully predict the branching between available product channels for systems in which each reaction coordinate can be adequately described by different paths along a single adiabatic potential energy surface. In particular, unimolecular dissociation following thermal, infrared multiphoton, or overtone excitation in the ground state yields a branching between energetically allowed product channels which can be successfully predicted by the application of statistical theories, i.e. the weakest bond breaks. (The predictions are particularly good for competing reactions in which when there is no saddle point along the reaction coordinates, as in simple bond fission reactions.) The predicted lack of bond selectivity results from the assumption of rapid internal vibrational energy redistribution and the implicit use of a single adiabatic Born-Oppenheimer potential energy surface for the reaction. However, the adiabatic approximation is not valid for the reaction of a wide variety of energetic materials and organic fuels; coupling between the electronic states of the reacting species play a a key role in determining the selectivity of the chemical reactions induced. The work described below investigated the central role played by coupling between electronic states in polyatomic molecules in determining the selective branching between energetically allowed fragmentation pathways in two key systems.
NASA Astrophysics Data System (ADS)
Engel, D.; Klews, M.; Wunner, G.
2009-02-01
We have developed a new method for the fast computation of wavelengths and oscillator strengths for medium-Z atoms and ions, up to iron, at neutron star magnetic field strengths. The method is a parallelized Hartree-Fock approach in adiabatic approximation based on finite-element and B-spline techniques. It turns out that typically 15-20 finite elements are sufficient to calculate energies to within a relative accuracy of 10-5 in 4 or 5 iteration steps using B-splines of 6th order, with parallelization speed-ups of 20 on a 26-processor machine. Results have been obtained for the energies of the ground states and excited levels and for the transition strengths of astrophysically relevant atoms and ions in the range Z=2…26 in different ionization stages. Catalogue identifier: AECC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AECC_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 3845 No. of bytes in distributed program, including test data, etc.: 27 989 Distribution format: tar.gz Programming language: MPI/Fortran 95 and Python Computer: Cluster of 1-26 HP Compaq dc5750 Operating system: Fedora 7 Has the code been vectorised or parallelized?: Yes RAM: 1 GByte Classification: 2.1 External routines: MPI/GFortran, LAPACK, PyLab/Matplotlib Nature of problem: Calculations of synthetic spectra [1] of strongly magnetized neutron stars are bedevilled by the lack of data for atoms in intense magnetic fields. While the behaviour of hydrogen and helium has been investigated in detail (see, e.g., [2]), complete and reliable data for heavier elements, in particular iron, are still missing. Since neutron stars are formed by the collapse of the iron cores of massive stars, it may be assumed that their atmospheres contain an iron plasma. Our objective is to fill the gap
Wu, Guorong; Neville, Simon P.; Worth, Graham A.; Schalk, Oliver; Sekikawa, Taro; Ashfold, Michael N. R.; Stolow, Albert
2015-02-21
The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole’s electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A{sub 2}(πσ{sup ∗}) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A{sub 1}(ππ{sup ∗}) and B{sub 2}(ππ{sup ∗}) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole’s electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B{sub 1}(πσ{sup ∗}) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B{sub 1}(πσ{sup ∗}) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A{sub 2}(πσ{sup ∗}) state.
Ab initio study on electronically excited states of lithium isocyanide, LiNC
NASA Astrophysics Data System (ADS)
Yasumatsu, Hisato; Jeung, Gwang-Hi
2014-01-01
The electronically excited states of the lithium isocyanide molecule, LiNC, were studied by means of ab initio calculations. The bonding nature of LiNC up to ˜10 eV is discussed on the basis of the potential energy surfaces according to the interaction between the ion-pair and covalent states. The ion-pair states are described by Coulomb attractive interaction in the long distance range, while the covalent ones are almost repulsive or bound with a very shallow potential dent. These two states interact each other to form adiabatic potential energy surfaces with non-monotonic change in the potential energy with the internuclear distance.
NASA Technical Reports Server (NTRS)
Goodrich, C. C.; Scudder, J. D.
1984-01-01
The adiabatic energy gain of electrons in the stationary electric and magnetic field structure of collisionless shock waves was examined analytically in reference to conditions of the earth's bow shock. The study was performed to characterize the behavior of electrons interacting with the cross-shock potential. A normal incidence frame (NIF) was adopted in order to calculate the reversible energy change across a time stationary shock, and comparisons were made with predictions made by the de Hoffman-Teller (HT) model (1950). The electron energy gain, about 20-50 eV, is demonstrated to be consistent with a 200-500 eV potential jump in the bow shock quasi-perpendicular geometry. The electrons lose energy working against the solar wind motional electric field. The reversible energy process is close to that modeled by HT, which predicts that the motional electric field vanishes and the electron energy gain from the electric potential is equated to the ion energy loss to the potential.
Time-dependent and time-independent approaches to study effects of degenerate electronic states
NASA Astrophysics Data System (ADS)
Baer, Michael; Yahalom, Asher; Englman, Robert
1998-10-01
Two types of phases are discussed in this article: (1) The topological phase as introduced by Berry [Proc. R. Soc. London, Ser. A 392, 45(1984)] and Aharonov and Anandan [Phys. Rev. Lett. 58, 1593 (1987)] and (2) the Longuet-Higgins phase [Proc. R. Soc. London, Ser. A 344, 147 (1975)]. The two types of phases have a common origin, namely the multivaluedness of the electronic adiabatic basis, a phenomenon associated with the existence of a degeneracy in configuration space. It will be shown, by studying an electronic model Hamiltonian that arises from a two-state approximation to the Mathieu equation, that the two phases differ from each other substantially, coinciding only in the adiabatic limit upon completion of a cycle.
Ab initio spectroscopic characterization of borane, BH, in its X1Σ+ electronic state.
Koput, Jacek
2015-11-15
The accurate potential energy and electric dipole moment functions of borane, BH, in its X1Σ+ electronic state have been determined from ab initio calculations using the multireference averaged coupled-pair functional method in conjunction with the correlation-consistent core-valence basis sets up to septuple-zeta quality. The higher-order electron correlation, scalar relativistic, adiabatic, and nonadiabatic effects were discussed. Vibration-rotation energy levels of the (11)BH, (11)BD, (10)BH, and (10)BD isotopologues were predicted to near "spectroscopic" accuracy. For the main isotopologue (11)BH, the adiabatic dissociation energy D0 and the effective equilibrium internuclear distance r(e) were predicted to be 28,469 ± 10 cm(-1) and 1.23214 ± 0.0001 Å, respectively. PMID:26444679
Kotelnikov, A I; Ortega, J M; Medvedev, E S; Psikha, B L; Garcia, D; Mathis, P
2002-05-15
The broad set of nonexponential electron transfer (ET) kinetics in reaction centers (RC) from Rhodopseudomonas sulfoviridis in temperature range 297-40 K are described within a mixed adiabatic/nonadiabatic model. The key point of the model is the combination of Sumi-Marcus and Rips-Jortner approaches which can be represented by the separate contributions of temperature-independent vibrational (v) and temperature-dependent diffusive (d) coordinates to the preexponential factor, to the free energy of reaction DeltaG=DeltaG(v)+DeltaG(d)(T) and to the reorganization energy lambda=lambda(v)+lambda(d)(T). The broad distribution of protein dielectric relaxation times along the diffusive coordinate is considered within the Davidson-Cole formalism. PMID:12009432
Conical intersections between X2A1 and A2B2 electronic states of NO
NASA Astrophysics Data System (ADS)
Sardar, Subhankar; Mukherjee, Saikat; Paul, Amit Kumar; Adhikari, Satrajit
2013-04-01
We explore both the general symmetry-allowed accidental (SAA) conical intersections (CIs) and Renner-Teller (RT) interactions prevailed between the ground (X2A1) and first excited (A2B2) electronic states of NO in the configuration space of normal mode coordinates. Global ab initio potential-energy surfaces and Non Adiabatic Coupling Term (NACT) between those states are reported. For each of the three pairs of normal mode (Q1,Q2,Q3), calculated NACT show singularity at different positions, which are used to calculate Adiabatic-to-Diabatic Transformation (ADT) angles and thereby, the diagonal elements of ADT matrix display (i) sign change for odd number of SAA CI (s) and (ii) no sign change for even number of SAA CIs as well as Renner-Teller interactions. Similar to Jahn-Teller CI, the existence of SAA CIs are, further, confirmed by Longuet-Higgins' phase change.
Zanon-Willette, Thomas; Clercq, Emeric de; Arimondo, Ennio
2011-12-15
Exact and asymptotic line shape expressions are derived from the semiclassical density matrix representation describing a set of closed three-level {Lambda} atomic or molecular states including decoherences, relaxation rates, and light shifts. An accurate analysis of the exact steady-state dark-resonance profile describing the Autler-Townes doublet, the electromagnetically induced transparency or coherent population trapping resonance, and the Fano-Feshbach line shape leads to the linewidth expression of the two-photon Raman transition and frequency shifts associated to the clock transition. From an adiabatic analysis of the dynamical optical Bloch equations in the weak field limit, a pumping time required to efficiently trap a large number of atoms into a coherent superposition of long-lived states is established. For a highly asymmetrical configuration with different decay channels, a strong two-photon resonance based on a lower states population inversion is established when the driving continuous-wave laser fields are greatly unbalanced. When time separated resonant two-photon pulses are applied in the adiabatic pulsed regime for atomic or molecular clock engineering, where the first pulse is long enough to reach a coherent steady-state preparation and the second pulse is very short to avoid repumping into a new dark state, dark-resonance fringes mixing continuous-wave line shape properties and coherent Ramsey oscillations are created. Those fringes allow interrogation schemes bypassing the power broadening effect. Frequency shifts affecting the central clock fringe computed from asymptotic profiles and related to the Raman decoherence process exhibit nonlinear shapes with the three-level observable used for quantum measurement. We point out that different observables experience different shifts on the lower-state clock transition.
NASA Astrophysics Data System (ADS)
Ladner, D. R.; Martinez-Galarce, D. S.; McCammon, D.
2006-04-01
An X-ray detection instrument to be flown on a sounding rocket experiment (the Advanced Technology Solar Spectroscopic Imager - ATSSI) for solar physics observations is being developed by the Lockheed Martin Solar and Astrophysics Laboratory (LMSAL). The detector is a novel class of microcalorimeter, a superconducting Transition-Edge Sensor (TES), that coupled with associated SQUID and feedback electronics requires high temperature stability at ~70 mK to resolve the energy of absorbed X-ray photons emitted from the solar corona. The cooling system incorporates an existing Adiabatic Demagnetization Refrigerator (ADR) developed at the University of Wisconsin (UW), which was previously flown to study the diffuse cosmic X-ray background. The Si thermistor detectors for that project required 130 K shielded JFET electronic components that are much less sensitive to the external field of the ADR solenoid than are the 1st (~70 mK) and 2nd (~2 K) SQUID stages used with TESs for solar observations. Modification of the Wisconsin ADR design, including TES focal plane and electronics re-positioning, therefore requires a tradeoff between the existing ADR solenoid nulling coil geometry and a low mass passive solenoid shield, while preserving the vibration isolation features of the existing design. We have developed models to accurately compute the magnetic field with and without shielding or nulling coils at critical locations to guide the re-design of the detector subsystem. The models and their application are described.
Adiabatic evolution of an irreversible two level system
Kvitsinsky, A.; Putterman, S. )
1991-05-01
The adiabatic dynamics of a two level atom with spontaneous decay is studied. The existence of a complex adiabatic phase shift is established: The real part being the usual Berry's phase. A closed-form expression for this phase and the adiabatic transition amplitudes is obtained. Incorporation of a finite preparation time for the initial state yields a new asymptotic form for the adiabatic transition amplitudes which is significantly different from the standard Landau--Zener--Dykhne formula.
On a Nonlinear Model in Adiabatic Evolutions
NASA Astrophysics Data System (ADS)
Sun, Jie; Lu, Song-Feng
2016-08-01
In this paper, we study a kind of nonlinear model of adiabatic evolution in quantum search problem. As will be seen here, for this problem, there always exists a possibility that this nonlinear model can successfully solve the problem, while the linear model can not. Also in the same setting, when the overlap between the initial state and the final stare is sufficiently large, a simple linear adiabatic evolution can achieve O(1) time efficiency, but infinite time complexity for the nonlinear model of adiabatic evolution is needed. This tells us, it is not always a wise choice to use nonlinear interpolations in adiabatic algorithms. Sometimes, simple linear adiabatic evolutions may be sufficient for using. Supported by the National Natural Science Foundation of China under Grant Nos. 61402188 and 61173050. The first author also gratefully acknowledges the support from the China Postdoctoral Science Foundation under Grant No. 2014M552041
Kittell, Aaron W.; Hustedt, Eric J.; Hyde, James S.
2014-01-01
Site-directed spin-labeling electron paramagnetic resonance (SDSL EPR) provides insight into the local structure and motion of a spin probe strategically attached to a molecule. When a second spin is introduced to the system, macromolecular information can be obtained through measurement of inter-spin distances either by continuous wave (CW) or pulsed electron double resonance (ELDOR) techniques. If both methodologies are considered, inter-spin distances of 8 to 80 Å can be experimentally determined. However, there exists a region at the upper limit of the conventional X-band (9.5 GHz) CW technique and the lower limit of the four-pulse double electron-electron resonance (DEER) experiment where neither method is particularly reliable. The work presented here utilizes L-band (1.9 GHz) in combination with non-adiabatic rapid sweep (NARS) EPR to address this opportunity by increasing the upper limit of the CW technique. Because L-band linewidths are three to seven times narrower than those at X-band, dipolar broadenings that are small relative to the X-band inhomogeneous linewidth become observable, but the signal loss due to the frequency dependence of the Boltzmann factor, has made L-band especially challenging. NARS has been shown to increase sensitivity by a factor of five, and overcomes much of this loss, making L-band distance determination more feasible [1]. Two different systems are presented and distances of 18–30 Å have been experimentally determined at physiologically relevant temperatures. Measurements are in excellent agreement with a helical model and values determined by DEER. PMID:22750251
Degenerate adiabatic perturbation theory: Foundations and applications
NASA Astrophysics Data System (ADS)
Rigolin, Gustavo; Ortiz, Gerardo
2014-08-01
We present details and expand on the framework leading to the recently introduced degenerate adiabatic perturbation theory [Phys. Rev. Lett. 104, 170406 (2010), 10.1103/PhysRevLett.104.170406], and on the formulation of the degenerate adiabatic theorem, along with its necessary and sufficient conditions [given in Phys. Rev. A 85, 062111 (2012), 10.1103/PhysRevA.85.062111]. We start with the adiabatic approximation for degenerate Hamiltonians that paves the way to a clear and rigorous statement of the associated degenerate adiabatic theorem, where the non-Abelian geometric phase (Wilczek-Zee phase) plays a central role to its quantitative formulation. We then describe the degenerate adiabatic perturbation theory, whose zeroth-order term is the degenerate adiabatic approximation, in its full generality. The parameter in the perturbative power-series expansion of the time-dependent wave function is directly associated to the inverse of the time it takes to drive the system from its initial to its final state. With the aid of the degenerate adiabatic perturbation theory we obtain rigorous necessary and sufficient conditions for the validity of the adiabatic theorem of quantum mechanics. Finally, to illustrate the power and wide scope of the methodology, we apply the framework to a degenerate Hamiltonian, whose closed-form time-dependent wave function is derived exactly, and also to other nonexactly solvable Hamiltonians whose solutions are numerically computed.
Benzonitrile: Electron affinity, excited states, and anion solvation
NASA Astrophysics Data System (ADS)
Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei
2015-10-01
We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.
Theoretical studies of electronically excited states
Besley, Nicholas A.
2014-10-06
Time-dependent density functional theory is the most widely used quantum chemical method for studying molecules in electronically excited states. However, excited states can also be computed within Kohn-Sham density functional theory by exploiting methods that converge the self-consistent field equations to give excited state solutions. The usefulness of single reference self-consistent field based approaches for studying excited states is demonstrated by considering the calculation of several types of spectroscopy including the infrared spectroscopy of molecules in an electronically excited state, the rovibrational spectrum of the NO-Ar complex, core electron binding energies and the emission spectroscopy of BODIPY in water.
NASA Astrophysics Data System (ADS)
Li, L.
2013-12-01
By removing the influences of 'magnetopause shadowing' (r0>6.6RE) and geomagnetic activities, we investigated statistically the responses of magnetic field and relativistic (>0.5MeV) electrons at geosynchronous orbit to 201 interplanetary perturbations during 6 years from 2003 (solar maximum) to 2008 (solar minimum). The statistical results indicate that during geomagnetically quiet times (HSYM ≥-30nT, and AE<200nT), ~47.3% changes in the geosynchronous magnetic field and relativistic electron fluxes are caused by the combined actions of the enhancement of solar wind dynamic pressure (Pd) and the southward turning of interplanetary magnetic field (IMF) (ΔPd>0.4 nPa, and IMF Bz<0 nT), and only ~18.4% changes are due to single dynamic pressure increase (ΔPd >0.4 nPa, but IMF Bz>0 nT), and ~34.3% changes are due to single southward turning of IMF (IMF Bz<0 nT, but |ΔPd|<0.4 nPa). Although the responses of magnetic field and relativistic electrons to the southward turning of IMF are weaker than their responses to the dynamic pressure increase, the southward turning of IMF can cause the dawn-dusk asymmetric perturbations that the magnetic field and the relativistic electrons tend to increase on the dawnside (LT~00:00-12:00) but decrease on the duskside (LT~13:00-23:00). Furthermore, the variation of relativistic electron fluxes is adiabatically controlled by the magnitude and elevation angle changes of magnetic field during the single IMF southward turnings. However, the variation of relativistic electron fluxes is independent of the change in magnetic field in some compression regions during the enhancement of solar wind dynamic pressure (including the single pressure increases and the combined external perturbations), indicating that nonadiabatic dynamic processes of relativistic electrons occur there. Acknowledgments. This work is supported by NSFC (grants 41074119 and 40604018). Liuyuan Li is grateful to the staffs working for the data from GOES 8-12 satellites
Nonadiabtic electron dynamics in densely quasidegenerate states in highly excited boron cluster
NASA Astrophysics Data System (ADS)
Yonehara, Takehiro; Takatsuka, Kazuo
2016-04-01
Following the previous study on nonadiabatic reaction dynamics including boron clusters [T. Yonehara and K. Takatsuka, J. Chem. Phys. 137, 22A520 (2012)], we explore deep into highly excited electronic states of the singlet boron cluster (B12) to find the characteristic features of the densely quasi-degenerate electronic state manifold, which undergo very frequent nonadiabatic transitions and thereby intensive electronic state mixing among very many of the relevant states. So much so, isolating the individual adiabatic states and tracking the expected potential energy surfaces both lose the physical sense. This domain of molecular situation is far beyond the realm of the Born-Oppenheimer approximation. To survey such a violent electronic state-mixing, we apply a method of nonadiabatic electron wavepacket dynamics, the semiclassical Ehrenfest method. We have tracked those electron wavepackets and found the electronic state mixing looks like an ultrafast diffusion in the Hilbert space, which results in huge fluctuation. Furthermore, due to such a violent mixing, the quantum phases associated with the electronic states are swiftly randomized, and consequently the coherence among the electronic states are lost quickly. Besides, these highly excited states are mostly of highly poly-radical nature, even in the spin singlet manifold and the number of radicals amounts up to 10 electrons in the sense of unpaired electrons. Thus the electronic states are summarized to be poly-radical and decoherent with huge fluctuation in shorter time scales of vibrational motions. The present numerical study sets a theoretical foundation for unknown molecular properties and chemical reactivity of such densely quasi-degenerate chemical species.
Nonadiabtic electron dynamics in densely quasidegenerate states in highly excited boron cluster.
Yonehara, Takehiro; Takatsuka, Kazuo
2016-04-28
Following the previous study on nonadiabatic reaction dynamics including boron clusters [T. Yonehara and K. Takatsuka, J. Chem. Phys. 137, 22A520 (2012)], we explore deep into highly excited electronic states of the singlet boron cluster (B12) to find the characteristic features of the densely quasi-degenerate electronic state manifold, which undergo very frequent nonadiabatic transitions and thereby intensive electronic state mixing among very many of the relevant states. So much so, isolating the individual adiabatic states and tracking the expected potential energy surfaces both lose the physical sense. This domain of molecular situation is far beyond the realm of the Born-Oppenheimer approximation. To survey such a violent electronic state-mixing, we apply a method of nonadiabatic electron wavepacket dynamics, the semiclassical Ehrenfest method. We have tracked those electron wavepackets and found the electronic state mixing looks like an ultrafast diffusion in the Hilbert space, which results in huge fluctuation. Furthermore, due to such a violent mixing, the quantum phases associated with the electronic states are swiftly randomized, and consequently the coherence among the electronic states are lost quickly. Besides, these highly excited states are mostly of highly poly-radical nature, even in the spin singlet manifold and the number of radicals amounts up to 10 electrons in the sense of unpaired electrons. Thus the electronic states are summarized to be poly-radical and decoherent with huge fluctuation in shorter time scales of vibrational motions. The present numerical study sets a theoretical foundation for unknown molecular properties and chemical reactivity of such densely quasi-degenerate chemical species. PMID:27131547
NASA Astrophysics Data System (ADS)
Allouche, A. R.; Aubert-Frécon, M.
2011-07-01
A theoretical investigation of the electronic structure of the NaK molecule including spin-orbit effects has been performed for the 34 Ω(+/-) states dissociating adiabatically into the limits up to Na(3s2S1/2) + K(3d2D3/2) from both an ab initio approach and a long-range model. Equilibrium distances, transition energies, harmonic frequencies as well as depths of wells and heights of humps are reported for all the states. Formulas for calculating the long-range energies for all the 0+/-, 1, 2, and 3 states under investigation are also displayed. They are expressed in terms of the Cn (n = 6,8, …) long-range coefficients and exchange integrals for the 2S+1Λ(+) parent states, available from literature. As present data could help experimentalists we make available extensive tables of energy values versus internuclear distances in our database at the web address: http://www-lasim.univ-lyon1.fr/spip.php?rubrique99.
Studies in Chaotic adiabatic dynamics
Jarzynski, C.
1994-01-01
Chaotic adiabatic dynamics refers to the study of systems exhibiting chaotic evolution under slowly time-dependent equations of motion. In this dissertation the author restricts his attention to Hamiltonian chaotic adiabatic systems. The results presented are organized around a central theme, namely, that the energies of such systems evolve diffusively. He begins with a general analysis, in which he motivates and derives a Fokker-Planck equation governing this process of energy diffusion. He applies this equation to study the {open_quotes}goodness{close_quotes} of an adiabatic invariant associated with chaotic motion. This formalism is then applied to two specific examples. The first is that of a gas of noninteracting point particles inside a hard container that deforms slowly with time. Both the two- and three-dimensional cases are considered. The results are discussed in the context of the Wall Formula for one-body dissipation in nuclear physics, and it is shown that such a gas approaches, asymptotically with time, an exponential velocity distribution. The second example involves the Fermi mechanism for the acceleration of cosmic rays. Explicit evolution equations are obtained for the distribution of cosmic ray energies within this model, and the steady-state energy distribution that arises when this equation is modified to account for the injection and removal of cosmic rays is discussed. Finally, the author re-examines the multiple-time-scale approach as applied to the study of phase space evolution under a chaotic adiabatic Hamiltonian. This leads to a more rigorous derivation of the above-mentioned Fokker-Planck equation, and also to a new term which has relevance to the problem of chaotic adiabatic reaction forces (the forces acting on slow, heavy degrees of freedom due to their coupling to light, fast chaotic degrees).
Olsen, Seth
2015-01-28
This paper reviews basic results from a theory of the a priori classical probabilities (weights) in state-averaged complete active space self-consistent field (SA-CASSCF) models. It addresses how the classical probabilities limit the invariance of the self-consistency condition to transformations of the complete active space configuration interaction (CAS-CI) problem. Such transformations are of interest for choosing representations of the SA-CASSCF solution that are diabatic with respect to some interaction. I achieve the known result that a SA-CASSCF can be self-consistently transformed only within degenerate subspaces of the CAS-CI ensemble density matrix. For uniformly distributed (“microcanonical”) SA-CASSCF ensembles, self-consistency is invariant to any unitary CAS-CI transformation that acts locally on the ensemble support. Most SA-CASSCF applications in current literature are microcanonical. A problem with microcanonical SA-CASSCF models for problems with “more diabatic than adiabatic” states is described. The problem is that not all diabatic energies and couplings are self-consistently resolvable. A canonical-ensemble SA-CASSCF strategy is proposed to solve the problem. For canonical-ensemble SA-CASSCF, the equilibrated ensemble is a Boltzmann density matrix parametrized by its own CAS-CI Hamiltonian and a Lagrange multiplier acting as an inverse “temperature,” unrelated to the physical temperature. Like the convergence criterion for microcanonical-ensemble SA-CASSCF, the equilibration condition for canonical-ensemble SA-CASSCF is invariant to transformations that act locally on the ensemble CAS-CI density matrix. The advantage of a canonical-ensemble description is that more adiabatic states can be included in the support of the ensemble without running into convergence problems. The constraint on the dimensionality of the problem is relieved by the introduction of an energy constraint. The method is illustrated with a complete active space
Anomalous confined electron states in graphene superlattices
Anh Le, H.; Chien Nguyen, D.; Nam Do, V.
2014-07-07
We show that periodic scalar potentials can induce the localization of some electronic states in graphene. Particularly, localized states are found at energies outside the potential variation range and embedded in the continuum spectrum of delocalized ones. The picture of the connection of wave functions with typical symmetries defined in relevant-edge nanoribbons is employed to explain the formation of the electronic structure and to characterize/classify eigen-states in graphene superlattices.
Adiabatic Compression of Oxygen: Real Fluid Temperatures
NASA Technical Reports Server (NTRS)
Barragan, Michelle; Wilson, D. Bruce; Stoltzfus, Joel M.
2000-01-01
The adiabatic compression of oxygen has been identified as an ignition source for systems operating in enriched oxygen atmospheres. Current practice is to evaluate the temperature rise on compression by treating oxygen as an ideal gas with constant heat capacity. This paper establishes the appropriate thermodynamic analysis for the common occurrence of adiabatic compression of oxygen and in the process defines a satisfactory equation of state (EOS) for oxygen. It uses that EOS to model adiabatic compression as isentropic compression and calculates final temperatures for this system using current approaches for comparison.
Stimulated Raman adiabatic passage through permanent dipole moment transitions
Niu Yingyu; Wang Rong; Qiu Minghui
2010-04-15
The rovibrational dynamics of stimulated Raman adiabatic passage (STIRAP) through permanent dipole moment transitions are investigated theoretically using a time-dependent quantum wave packet method for the ground electronic state of an HF molecule. The two basic STIRAP processes, {Lambda} and ladder systems, are simulated. The calculated results show that nearly 100% of the population can be transferred to the target state. Besides the interested transitions, the pulses can induce other transitions which affect the dynamics of STIRAP. The final populations of the initial and target states depend on delay time.
Schio, Luca; Alagia, Michele; Dias, Antonio A; Falcinelli, Stefano; Zhaunerchyk, Vitali; Lee, Edmond P F; Mok, Daniel K W; Dyke, John M; Stranges, Stefano
2016-07-14
In this work, hydrogen peroxide has been studied with threshold photoelectron (TPE) spectroscopy and photoelectron (PE) spectroscopy. The TPE spectrum has been recorded in the 10.0-21.0 eV ionization energy region, and the PE spectrum has been recorded at 21.22 eV photon energy. Five bands have been observed which have been assigned on the basis of UCCSD(T)-F12/VQZ-F12 and IP-EOM CCSD calculations. Vibrational structure has only been resolved in the TPE spectrum of the first band, associated with the X̃(2)Bg H2O2(+) ← X̃(1)A H2O2 ionization, on its low energy side. This structure is assigned with the help of harmonic Franck-Condon factor calculations that use the UCCSD(T)-F12a/VQZ-F12 computed adiabatic ionization energy (AIE), and UCCSD(T)-F12a/VQZ-F12 computed equilibrium geometric parameters and harmonic vibrational frequencies for the H2O2 X̃(1)A state and the H2O2(+) X̃(2)Bg state. These calculations show that the main vibrational structure on the leading edge of the first TPE band is in the O-O stretching mode (ω3) and the HOOH deformation mode (ω4), and comparison of the simulated spectrum to the experimental spectrum gives the first AIE of H2O2 as (10.685 ± 0.005) eV and ω4 = (850 ± 30) and ω3 = (1340 ± 30) cm(-1) in the X̃(2)Bg state of H2O2(+). Contributions from ionization of vibrationally excited levels in the torsion mode have been identified in the TPE spectrum of the first band and the need for a vibrationally resolved TPE spectrum from vibrationally cooled molecules, as well as higher level Franck-Condon factors than performed in this work, is emphasized. PMID:27045948
Ozone absorption spectroscopy in search of low-lying electronic states
NASA Technical Reports Server (NTRS)
Anderson, S. M.; Mauersberger, K.
1995-01-01
A spectrometer capable of detecting ozone absorption features 9 orders of magnitude weaker than the Hartley band has been employed to investigate the molecule's near-infrared absorption spectrum. At this sensitivity a wealth of information on the low-lying electronically excited states often believed to play a role in atmospheric chemistry is available in the form of vibrational and rotational structure. We have analyzed these spectra using a combination of digital filtering and isotope substitution and find evidence for three electronically excited states below 1.5 eV. The lowest of these states is metastable, bound by approximately 0.1 eV and probably the (3)A2 rather than the (3)B2 state. Its adiabatic electronic energy is 1.24 +/- 0.01 eV, slightly above the dissociation energy of the ground state. Two higher states, at 1.29 +/- 0.03 and 1.48 +/- 0.03 eV are identified as the (3)B2 and the (3)B1, respectively. Combined with other recent theoretical and experimental data on the low-lying electronic states of ozone, these results imply that these are, in fact, the lowest three excited states; that is, there are no electronically excited states of ozone lying below the energy of O(3P) + O2((3)Sigma(-), v = 0). Some of the implications for atmospheric chemistry are considered.
Vura-Weis, Josh; Newton, M. D.; Wasielewski, Michael R; Subotnik, J.E.
2010-12-09
A common strategy to calculate electronic coupling matrix elements for charge or energy transfer is to take the adiabatic states generated by electronic structure computations and rotate them to form localized diabatic states. In this paper, we show that, for intermolecular transfer of singlet electronic excitation, usually we cannot fully localize the electronic excitations in this way. Instead, we calculate putative initial and final states with small excitation tails caused by weak interactions with high energy excited states in the electronic manifold. These tails do not lead to substantial changes in the total diabatic coupling between states, but they do lead to a different partitioning of the total coupling between Coulomb (Förster), exchange (Dexter), and one-electron components. The tails may be reduced by using a multistate diabatic model or eliminated entirely by truncation (denoted as “chopping”). Without more information, we are unable to conclude with certainty whether the observed diabatic tails are a physical reality or a computational artifact. This research suggests that decomposition of the diabatic coupling between chromophores into Coulomb, exchange, and one-electron components may depend strongly on the number of states considered, and such results should be treated with caution.
Borovkov, V I; Beregovaya, I V; Shchegoleva, L N; Potashov, P A; Bagryansky, V A; Molin, Y N
2012-09-14
Paramagnetic spin-lattice relaxation (SLR) in radical cations (RCs) of the cycloalkane series in liquid solution was studied and analyzed from the point of view of the correlation between the relaxation rate and the structure of the adiabatic potential energy surface (PES) of the RCs. SLR rates in the RCs formed in x-ray irradiated n-hexane solutions of the cycloalkanes studied were measured with the method of time-resolved magnetic field effect in the recombination fluorescence of spin-correlated radical ion pairs. Temperature and, for some cycloalkanes, magnetic field dependences of the relaxation rate were determined. It was found that the conventional Redfield theory of the paramagnetic relaxation as applied to the results on cyclohexane RC, gave a value of about 0.2 ps for the correlation time of the perturbation together with an unrealistically high value of 0.1 T in field units for the matrix element of the relaxation transition. The PES structure was obtained with the DFT quantum-chemical calculations. It was found that for all of the cycloalkanes RCs considered, including low symmetric alkyl-substituted ones, the adiabatic PESes were surfaces of pseudorotation due to avoided crossing. In the RCs studied, a correlation between the SLR rate and the calculated barrier height to the pseudorotation was revealed. For RCs with a higher relaxation rate, the apparent activation energies for the SLR were similar to the calculated heights of the barrier. To rationalize the data obtained it was assumed that the vibronic states degeneracy, which is specific for Jahn-Teller active cyclohexane RC, was approximately kept in the RCs of substituted cycloalkanes for the vibronic states with the energies above and close to the barrier height to the pseudorotation. It was proposed that the effective spin-lattice relaxation in a radical with nearly degenerate low-lying vibronic states originated from stochastic crossings of the vibronic levels that occur due to fluctuations of
Adiabatically driven Brownian pumps.
Rozenbaum, Viktor M; Makhnovskii, Yurii A; Shapochkina, Irina V; Sheu, Sheh-Yi; Yang, Dah-Yen; Lin, Sheng Hsien
2013-07-01
We investigate a Brownian pump which, being powered by a flashing ratchet mechanism, produces net particle transport through a membrane. The extension of the Parrondo's approach developed for reversible Brownian motors [Parrondo, Phys. Rev. E 57, 7297 (1998)] to adiabatically driven pumps is given. We demonstrate that the pumping mechanism becomes especially efficient when the time variation of the potential occurs adiabatically fast or adiabatically slow, in perfect analogy with adiabatically driven Brownian motors which exhibit high efficiency [Rozenbaum et al., Phys. Rev. E 85, 041116 (2012)]. At the same time, the efficiency of the pumping mechanism is shown to be less than that of Brownian motors due to fluctuations of the number of particles in the membrane. PMID:23944411
NASA Astrophysics Data System (ADS)
Zhu, Xiaolei; Yarkony, David R.
2016-01-01
We have recently introduced a diabatization scheme, which simultaneously fits and diabatizes adiabatic ab initio electronic wave functions, Zhu and Yarkony J. Chem. Phys. 140, 024112 (2014). The algorithm uses derivative couplings in the defining equations for the diabatic Hamiltonian, Hd, and fits all its matrix elements simultaneously to adiabatic state data. This procedure ultimately provides an accurate, quantifiably diabatic, representation of the adiabatic electronic structure data. However, optimizing the large number of nonlinear parameters in the basis functions and adjusting the number and kind of basis functions from which the fit is built, which provide the essential flexibility, has proved challenging. In this work, we introduce a procedure that combines adiabatic state and diabatic state data to efficiently optimize the nonlinear parameters and basis function expansion. Further, we consider using direct properties based diabatizations to initialize the fitting procedure. To address this issue, we introduce a systematic method for eliminating the debilitating (diabolical) singularities in the defining equations of properties based diabatizations. We exploit the observation that if approximate diabatic data are available, the commonly used approach of fitting each matrix element of Hd individually provides a starting point (seed) from which convergence of the full Hd construction algorithm is rapid. The optimization of nonlinear parameters and basis functions and the elimination of debilitating singularities are, respectively, illustrated using the 1,2,3,41A states of phenol and the 1,21A states of NH3, states which are coupled by conical intersections.
Nearly free electron states in MXenes
NASA Astrophysics Data System (ADS)
Khazaei, Mohammad; Ranjbar, Ahmad; Ghorbani-Asl, Mahdi; Arai, Masao; Sasaki, Taizo; Liang, Yunye; Yunoki, Seiji
2016-05-01
Using a set of first-principles calculations, we studied the electronic structures of two-dimensional transition metal carbides and nitrides, so called MXenes, functionalized with F, O, and OH. Our projected band structures and electron localization function analyses reveal the existence of nearly free electron (NFE) states in a variety of MXenes. The NFE states are spatially located just outside the atomic structure of MXenes and are extended parallel to the surfaces. Moreover, we found that the OH-terminated MXenes offer the NFE states energetically close to the Fermi level. In particular, the NFE states in some of the OH-terminated MXenes, such as T i2C (OH) 2,Z r2C (OH) 2,Z r2N (OH) 2,H f2C (OH) 2,H f2N (OH) 2,N b2C (OH) 2 , and T a2C (OH) 2 , are partially occupied. This is in remarkable contrast to graphene, graphane, and Mo S2 , in which their NFE states are located far above the Fermi level and thus they are unoccupied. As a prototype of such systems, we investigated the electron transport properties of H f2C (OH) 2 and found that the NFE states in H f2C (OH) 2 provide almost perfect transmission channels without nuclear scattering for electron transport. Our results indicate that these systems might find applications in nanoelectronic devices. Our findings provide new insights into the unique electronic band structures of MXenes.
Fermionic thermocoherent state: Efficiency of electron transport
NASA Astrophysics Data System (ADS)
Karmakar, Anirban; Gangopadhyay, Gautam
2016-02-01
On the basis of the fermionic coherent state of Cahill and Glauber [Phys. Rev. A 59, 1538 (1999)], 10.1103/PhysRevA.59.1538, we have introduced here the fermionic thermocoherent state in terms of the quasiprobability distribution which shows the appropriate thermal and coherent limits as in the bosonic case or the Glauber-Lachs state. It is shown that the fermionic thermocoherent state can be realized as a displaced thermal state of fermions. Its relation with the fermionic displaced number state and the fermion-added coherent state are explored in the spirit of the bosonic case. We have investigated the nature of the average current and the suppression of noise due to the thermocoherent character of the source. The theory is applied to the problem of electronic conduction. A modification of the Landauer conductance formula is suggested which reflects the role of nonzero coherence of the source in electron transport.
General conditions for quantum adiabatic evolution
Comparat, Daniel
2009-07-15
Adiabaticity occurs when, during its evolution, a physical system remains in the instantaneous eigenstate of the Hamiltonian. Unfortunately, existing results, such as the quantum adiabatic theorem based on a slow down evolution [H({epsilon}t),{epsilon}{yields}0], are insufficient to describe an evolution driven by the Hamiltonian H(t) itself. Here we derive general criteria and exact bounds, for the state and its phase, ensuring an adiabatic evolution for any Hamiltonian H(t). As a corollary, we demonstrate that the commonly used condition of a slow Hamiltonian variation rate, compared to the spectral gap, is indeed sufficient to ensure adiabaticity but only when the Hamiltonian is real and nonoscillating (for instance, containing exponential or polynomial but no sinusoidal functions)
On the Role of Prior Probability in Adiabatic Quantum Algorithms
NASA Astrophysics Data System (ADS)
Sun, Jie; Lu, Songfeng; Yang, Liping
2016-03-01
In this paper, we study the role of prior probability on the efficiency of quantum local adiabatic search algorithm. The following aspects for prior probability are found here: firstly, only the probabilities of marked states affect the running time of the adiabatic evolution; secondly, the prior probability can be used for improving the efficiency of the adiabatic algorithm; thirdly, like the usual quantum adiabatic evolution, the running time for the case of multiple solution states where the number of marked elements are smaller enough than the size of the set assigned that contains them can be significantly bigger than that of the case where the assigned set only contains all the marked states.
Intense steady state electron beam generator
Hershcovitch, Ady; Kovarik, Vincent J.; Prelec, Krsto
1990-01-01
An intense, steady state, low emittance electron beam generator is formed by operating a hollow cathode discharge plasma source at critical levels in combination with an extraction electrode and a target electrode that are operable to extract a beam of fast primary electrons from the plasma source through a negatively biased grid that is critically operated to repel bulk electrons toward the plasma source while allowing the fast primary electrons to move toward the target in the desired beam that can be successfully transported for relatively large distances, such as one or more meters away from the plasma source.
Intense steady state electron beam generator
Hershcovitch, A.; Kovarik, V.J.; Prelec, K.
1990-07-17
An intense, steady state, low emittance electron beam generator is formed by operating a hollow cathode discharge plasma source at critical levels in combination with an extraction electrode and a target electrode that are operable to extract a beam of fast primary electrons from the plasma source through a negatively biased grid that is critically operated to repel bulk electrons toward the plasma source while allowing the fast primary electrons to move toward the target in the desired beam that can be successfully transported for relatively large distances, such as one or more meters away from the plasma source. 2 figs.
Adiabaticity in open quantum systems
NASA Astrophysics Data System (ADS)
Venuti, Lorenzo Campos; Albash, Tameem; Lidar, Daniel A.; Zanardi, Paolo
2016-03-01
We provide a rigorous generalization of the quantum adiabatic theorem for open systems described by a Markovian master equation with time-dependent Liouvillian L (t ) . We focus on the finite system case relevant for adiabatic quantum computing and quantum annealing. Adiabaticity is defined in terms of closeness to the instantaneous steady state. While the general result is conceptually similar to the closed-system case, there are important differences. Namely, a system initialized in the zero-eigenvalue eigenspace of L (t ) will remain in this eigenspace with a deviation that is inversely proportional to the total evolution time T . In the case of a finite number of level crossings, the scaling becomes T-η with an exponent η that we relate to the rate of the gap closing. For master equations that describe relaxation to thermal equilibrium, we show that the evolution time T should be long compared to the corresponding minimum inverse gap squared of L (t ) . Our results are illustrated with several examples.
Protecting and accelerating adiabatic passage with time-delayed pulse sequences.
Sampedro, Pablo; Chang, Bo Y; Sola, Ignacio R
2016-05-21
Using numerical simulations of two-photon electronic absorption with femtosecond pulses in Na2 we show that: (i) it is possible to avoid the characteristic saturation or dumped Rabi oscillations in the yield of absorption by time-delaying the laser pulses; (ii) it is possible to accelerate the onset of adiabatic passage by using the vibrational coherence starting in a wave packet; and (iii) it is possible to prepare the initial wave packet in order to achieve full state-selective transitions with broadband pulses. The findings can be used, for instance, to achieve ultrafast adiabatic passage by light-induced potentials and understand its intrinsic robustness. PMID:27125342
NASA Astrophysics Data System (ADS)
Straasø, Lasse A.; Shankar, Ravi; Tan, Kong Ooi; Hellwagner, Johannes; Meier, Beat H.; Hansen, Michael Ryan; Nielsen, Niels Chr.; Vosegaard, Thomas; Ernst, Matthias; Nielsen, Anders B.
2016-07-01
The homonuclear radio-frequency driven recoupling (RFDR) experiment is commonly used in solid-state NMR spectroscopy to gain insight into the structure of biological samples due to its ease of implementation, stability towards fluctuations/missetting of radio-frequency (rf) field strength, and in general low rf requirements. A theoretical operator-based Floquet description is presented to appreciate the effect of having a temporal displacement of the π-pulses in the RFDR experiment. From this description, we demonstrate improved transfer efficiency for the RFDR experiment by generating an adiabatic passage through the zero-quantum recoupling condition. We have compared the performances of RFDR and the improved sequence to mediate efficient 13CO to 13Cα polarization transfer for uniformly 13C,15N-labeled glycine and for the fibril forming peptide SNNFGAILSS (one-letter amino acid codes) uniformly 13C,15N-labeled at the FGAIL residues. Using numerically optimized sweeps, we get experimental gains of approximately 20% for glycine where numerical simulations predict an improvement of 25% relative to the standard implementation. For the fibril forming peptide, using the same sweep parameters as found for glycine, we have gains in the order of 10%-20% depending on the spectral regions of interest.
Complete state-resolved non-adiabatic dynamics of the O((3)P) + D2 → OD(X(2)Π) + D reaction.
Lahankar, Sridhar A; Zhang, Jianming; Minton, Timothy K; McKendrick, Kenneth G
2014-09-01
The first quantum-state-resolved distributions over the full range of available product levels are reported for any isotopic variant of the elementary reaction of O((3)P) with molecular hydrogen. A laser-detonation source was used to produce a hyperthermal oxygen-atom beam, which allowed for sufficient collision energy to surmount the reaction barrier. This beam was crossed by a supersonic beam of D2. The nascent OD products were detected by laser-induced fluorescence. OD rotational distributions in vibrational states v' = 0, 1, and 2 at a collision energy of 25 kcal mol(-1) are reported, together with distributions for the dominant product vibrational level, v'= 0, at lower collision energies of 20 and 15 kcal mol(-1). The OD product is highly rotationally excited, to a degree that declines as expected for the higher vibrational levels or for reductions in the collision energy. The measured rovibrational distributions at the highest collision energy are in excellent agreement with previous theoretical predictions based on quantum scattering calculations on the triplet potential energy surfaces developed by Rogers et al. (J. Phys. Chem. A 2000, 104, 2308-2325). However, no significant OD spin-orbit preference was observed, in contrast to the predictions of most existing theoretical models of the non-adiabatic dynamics based on the widely used reduced-dimensional four-state model of Hoffmann and Schatz (J. Chem. Phys. 2000, 113, 9456-9465). Furthermore, a clear observed preference for OD Π(A') Λ-doublet levels is not consistent with a simple extrapolation of the calculated relative reaction cross sections on intermediate surfaces of (3)A' and (3)A″ symmetry. PMID:25084139
Two electronic states in spherical quantum nanolayer
NASA Astrophysics Data System (ADS)
Aghekyan, N. G.; Kazaryan, E. M.; Kostanyan, A. A.; Sarkisyan, H. A.
2010-10-01
In this paper two electronic states in spherical quantum nanolayer are discussed. The Coulomb interaction between the electrons is discussed as perturbation. For confinement potential of the nanolayer the three-dimensional radial analog of Smorodinsky-Winternitz potential is considered. The problem is discussed within the frameworks of Russell-Saunders coupling scheme, thus, the spin-orbit interaction is considered weak. Therefore the eigenfunctions of the system is represented as a multiplication of its coordinate wave function and spin wave function. For this system the analogue of helium atom theory is represented. The eigenfunctions and energy states are obtained for one and two electron cases in the spherical quantum nanolayer. For the spherical nanolayer the dependence of perturbation energy, unperturbed system energy and the total energy for the ground state upon the inner radius is represented when the outer radius is fixed.
Effects of steady state adiabatic convection on the configuration of the near-earth plasma sheet, 2
Linhi Hau )
1991-04-01
The author has constructed two new two-dimensional equilibrium magnetic field models for the Earth's magnetotail, in which flux tubes have nearly constant pV{sup 5/3} between the outer boundary of the Alfven layers and 36 R{sub E} geocentric distance. These models, corresponding to different values of pV{sup 5/3}, are constructed for magnetospheres with rectangular magnetopauses and nonflaring tails. These results thus confirm the speculation made in his earlier paper (Hau et al., 1989) that, within the limit of ideal MHD, there exists a family of steady convection solutions, corresponding to various degrees of magnetotail inflation. Like the previous steady state solutions, each of these models also exhibits a broad minimum in equatorial magnetic field strength B{sub ze} tailward of the inner edge region between 10 and 20 R{sub E}. However, these new steady state magnetic field models possess higher values of flux tube content pV{sup 5/3} and thus have more stretched tail configurations and smaller minimum values of B{sub ze} than those in the original model. For a model that has B{sub ze}/B{sub lobe}{approximately}0.15 at 36 R{sub E}, which is close to observed averages, the ratio B{sub ze}/B{sub lobe} is about 0.029 at 13 R{sub E}.
Floating electron states in covalent semiconductors.
Matsushita, Yu-ichiro; Furuya, Shinnosuke; Oshiyama, Atsushi
2012-06-15
We report first-principles electronic-structure calculations that clarify the floating nature of electron states in covalent semiconductors. It is found that wave functions of several conduction- and valence-band states, including the conduction-band minima, do not distribute near atomic sites, as was taken for granted, but float in interstitial channels in most semiconductors. The directions and shapes of the interstitial channels depend on the crystal symmetry so that mysterious variation of the energy gaps in SiC polymorphs is naturally explained by considering the floating nature. PMID:23004300
Adiabatic cooling of antiprotons.
Gabrielse, G; Kolthammer, W S; McConnell, R; Richerme, P; Kalra, R; Novitski, E; Grzonka, D; Oelert, W; Sefzick, T; Zielinski, M; Fitzakerley, D; George, M C; Hessels, E A; Storry, C H; Weel, M; Müllers, A; Walz, J
2011-02-18
Adiabatic cooling is shown to be a simple and effective method to cool many charged particles in a trap to very low temperatures. Up to 3×10(6) p are cooled to 3.5 K-10(3) times more cold p and a 3 times lower p temperature than previously reported. A second cooling method cools p plasmas via the synchrotron radiation of embedded e(-) (with many fewer e(-) than p in preparation for adiabatic cooling. No p are lost during either process-a significant advantage for rare particles. PMID:21405511
Adiabatic Cooling of Antiprotons
Gabrielse, G.; Kolthammer, W. S.; McConnell, R.; Richerme, P.; Kalra, R.; Novitski, E.; Oelert, W.; Grzonka, D.; Sefzick, T.; Zielinski, M.; Fitzakerley, D.; George, M. C.; Hessels, E. A.; Storry, C. H.; Weel, M.; Muellers, A.; Walz, J.
2011-02-18
Adiabatic cooling is shown to be a simple and effective method to cool many charged particles in a trap to very low temperatures. Up to 3x10{sup 6} p are cooled to 3.5 K--10{sup 3} times more cold p and a 3 times lower p temperature than previously reported. A second cooling method cools p plasmas via the synchrotron radiation of embedded e{sup -} (with many fewer e{sup -} than p) in preparation for adiabatic cooling. No p are lost during either process--a significant advantage for rare particles.
Electronically excited states of PANH anions.
Theis, Mallory L; Candian, Alessandra; Tielens, Alexander G G M; Lee, Timothy J; Fortenberry, Ryan C
2015-06-14
The singly deprotonated anion derivatives of nitrogenated polycyclic aromatic hydrocarbons (PANHs) are investigated for their electronically excited state properties. These include single deprotonation of the two unique arrangements of quinoline producing fourteen different isomers. This same procedure is also undertaken for single deprotonation of the three nitrogenation isomers of acridine and the three of pyrenidine. It is shown quantum chemically that the quinoline-class of PANH anion derivatives can only produce a candidate dipole-bound excited state each, a state defined as the interaction of an extra electron with the dipole moment of the corresponding neutral. However, the acridine- and pyrenidine-classes possess valence excited states as well as the possible dipole-bound excited states where the latter is only possible if the dipole moment is sufficiently large to retain the extra electron; the valence excitation is independent of the radical dipolar strength. As a result, the theoretical vertically computed electronic spectra of deprotonated PANH anion derivatives is fairly rich in the 1.5 eV to 2.5 eV range significantly opening the possibilities for these molecules to be applied to longer wavelength studies of visible and near-IR spectroscopy. Lastly, the study of these systems is also enhanced by the inclusion of informed orbital arrangements in a simply constructed basis set that is shown to be more complete and efficient than standard atom-centered functions. PMID:25975430
Electronics: State of the Art No. 2.
ERIC Educational Resources Information Center
Gosling, W.
1979-01-01
Reviewed is a brief history of electronics technology, from the early beginnings of vacuum devices to development of solid state devices, silicon fabrication in the use of transistors, and integrated circuits. Educational needs at the university or polytechnic level are discussed. (CS)
Ouyang, Wenjun; Dou, Wenjie; Subotnik, Joseph E.
2015-02-28
We investigate the incorporation of the surface-leaking (SL) algorithm into Tully’s fewest-switches surface hopping (FSSH) algorithm to simulate some electronic relaxation induced by an electronic bath in conjunction with some electronic transitions between discrete states. The resulting SL-FSSH algorithm is benchmarked against exact quantum scattering calculations for three one-dimensional model problems. The results show excellent agreement between SL-FSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SL-FSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SL-FSSH, especially the wide band approximation. Considering the easiness of implementation and the low computational cost, we expect this method to be useful in studying processes involving both a continuum of electronic states (where electronic dynamics are probabilistic) and processes involving only a few electronic states (where non-adiabatic processes cannot ignore short-time coherence)
Entanglement and adiabatic quantum computation
NASA Astrophysics Data System (ADS)
Ahrensmeier, D.
2006-06-01
Adiabatic quantum computation provides an alternative approach to quantum computation using a time-dependent Hamiltonian. The time evolution of entanglement during the adiabatic quantum search algorithm is studied, and its relevance as a resource is discussed.
Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo
White, Alexander J.; Gorshkov, Vyacheslav N.; Tretiak, Sergei; Mozyrsky, Dmitry
2015-07-07
Non-adiabatic dynamics, where systems non-radiatively transition between electronic states, plays a crucial role in many photo-physical processes, such as fluorescence, phosphorescence, and photoisomerization. Methods for the simulation of non-adiabatic dynamics are typically either numerically impractical, highly complex, or based on approximations which can result in failure for even simple systems. Recently, the Semiclassical Monte Carlo (SCMC) approach was developed in an attempt to combine the accuracy of rigorous semiclassical methods with the efficiency and simplicity of widely used surface hopping methods. However, while SCMC was found to be more efficient than other semiclassical methods, it is not yet as efficientmore » as is needed to be used for large molecular systems. Here, we have developed two new methods: the accelerated-SCMC and the accelerated-SCMC with re-Gaussianization, which reduce the cost of the SCMC algorithm up to two orders of magnitude for certain systems. In many cases shown here, the new procedures are nearly as efficient as the commonly used surface hopping schemes, with little to no loss of accuracy. This implies that these modified SCMC algorithms will be of practical numerical solutions for simulating non-adiabatic dynamics in realistic molecular systems.« less
Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo
White, Alexander J.; Gorshkov, Vyacheslav N.; Tretiak, Sergei; Mozyrsky, Dmitry
2015-07-07
Non-adiabatic dynamics, where systems non-radiatively transition between electronic states, plays a crucial role in many photo-physical processes, such as fluorescence, phosphorescence, and photoisomerization. Methods for the simulation of non-adiabatic dynamics are typically either numerically impractical, highly complex, or based on approximations which can result in failure for even simple systems. Recently, the Semiclassical Monte Carlo (SCMC) approach was developed in an attempt to combine the accuracy of rigorous semiclassical methods with the efficiency and simplicity of widely used surface hopping methods. However, while SCMC was found to be more efficient than other semiclassical methods, it is not yet as efficient as is needed to be used for large molecular systems. Here, we have developed two new methods: the accelerated-SCMC and the accelerated-SCMC with re-Gaussianization, which reduce the cost of the SCMC algorithm up to two orders of magnitude for certain systems. In many cases shown here, the new procedures are nearly as efficient as the commonly used surface hopping schemes, with little to no loss of accuracy. This implies that these modified SCMC algorithms will be of practical numerical solutions for simulating non-adiabatic dynamics in realistic molecular systems.
Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo
White, Alexander J.; Gorshkov, Vyacheslav N.; Tretiak, Sergei; Mozyrsky, Dmitry
2015-07-07
Non-adiabatic dynamics, where systems non-radiatively transition between electronic states, plays a crucial role in many photo-physical processes, such as fluorescence, phosphorescence, and photoisomerization. Methods for the simulation of non-adiabatic dynamics are typically either numerically impractical, highly complex, or based on approximations which can result in failure for even simple systems. Recently, the Semiclassical Monte Carlo (SCMC) approach was developed in an attempt to combine the accuracy of rigorous semiclassical methods with the efficiency and simplicity of widely used surface hopping methods. However, while SCMC was found to be more efficient than other semiclassical methods, it is not yet as efficient as is needed to be used for large molecular systems. Here, we have developed two new methods: the accelerated-SCMC and the accelerated-SCMC with re-Gaussianization, which reduce the cost of the SCMC algorithm up to two orders of magnitude for certain systems. In most cases shown here, the new procedures are nearly as efficient as the commonly used surface hopping schemes, with little to no loss of accuracy. This implies that these modified SCMC algorithms will be of practical numerical solutions for simulating non-adiabatic dynamics in realistic molecular systems.
Graph isomorphism and adiabatic quantum computing
NASA Astrophysics Data System (ADS)
Gaitan, Frank; Clark, Lane
2014-02-01
In the graph isomorphism (GI) problem two N-vertex graphs G and G' are given and the task is to determine whether there exists a permutation of the vertices of G that preserves adjacency and transforms G →G'. If yes, then G and G' are said to be isomorphic; otherwise they are nonisomorphic. The GI problem is an important problem in computer science and is thought to be of comparable difficulty to integer factorization. In this paper we present a quantum algorithm that solves arbitrary instances of GI and which also provides an approach to determining all automorphisms of a given graph. We show how the GI problem can be converted to a combinatorial optimization problem that can be solved using adiabatic quantum evolution. We numerically simulate the algorithm's quantum dynamics and show that it correctly (i) distinguishes nonisomorphic graphs; (ii) recognizes isomorphic graphs and determines the permutation(s) that connect them; and (iii) finds the automorphism group of a given graph G. We then discuss the GI quantum algorithm's experimental implementation, and close by showing how it can be leveraged to give a quantum algorithm that solves arbitrary instances of the NP-complete subgraph isomorphism problem. The computational complexity of an adiabatic quantum algorithm is largely determined by the minimum energy gap Δ (N) separating the ground and first-excited states in the limit of large problem size N ≫1. Calculating Δ (N) in this limit is a fundamental open problem in adiabatic quantum computing, and so it is not possible to determine the computational complexity of adiabatic quantum algorithms in general, nor consequently, of the specific adiabatic quantum algorithms presented here. Adiabatic quantum computing has been shown to be equivalent to the circuit model of quantum computing, and so development of adiabatic quantum algorithms continues to be of great interest.
Unoccupied electronic states in adsorbate systems
NASA Astrophysics Data System (ADS)
Bertel, E.
1991-11-01
Experimental work on unoccupied electronic states in adsorbate systems on metallic substrates is reviewed with emphasis on recent developments. The first part is devoted to molecular adsorbates. Weakly chemisorbed hydrocarbons are briefly discussed. An exhaustive inverse photoemission (IPE) study of the CO bond to the transition metals Ni, Pb, and Pt is presented. Adsorbed NO is taken as an example to demonstrate the persisting discrepancies in the interpretation of IPE spectra. Atomic adsorbates are discussed in the second part. The quantum well state model is applied to interpret the surface states in reconstructing and non-reconstructing adsorption systems of alkali metals and hydrogen. A recent controversy on the unoccupied electronic states of the Cu(110)/O p(2×1) surface is critically reviewed. The quantum well state model is then compared to tight binding and local-density-functional calculations of the unoccupied bands and the deficiencies of the various approaches are pointed out. Finally, the relation between the surface state model and more chemically oriented models of surface bonding is briefly discussed.
Ultrafast hydrogen migration in acetylene cation driven by non-adiabatic effects.
Madjet, Mohamed El-Amine; Li, Zheng; Vendrell, Oriol
2013-03-01
Non-adiabatic dynamics of the acetylene cation is investigated using mixed quantum-classical dynamics based on trajectory surface hopping. To describe the non-adiabatic effects, two surface hopping methods are used, namely, Tully's fewest switches and Landau-Zener surface hopping. Similarities and differences between the results based on those two methods are discussed. We find that the photoionization of acetylene into the first excited state A(2)Σg(+) drives the molecule from the linear structure to a trans-bent structure. Through a conical intersection the acetylene cation can relax back to either the ground state of acetylene or vinylidene. We conclude that hydrogen migration always takes place after non-radiative electronic relaxation to the ground state of the monocation. Based on the analysis of correlation functions we identify coherent oscillations between acetylene and vinylidene with a period of about 70 fs after the electronic relaxation. PMID:23485298
Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions.
Menzeleev, Artur R; Bell, Franziska; Miller, Thomas F
2014-02-14
We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force. PMID:24527896
Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions
Menzeleev, Artur R.; Bell, Franziska; Miller, Thomas F.
2014-02-14
We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force.
ab Initio Diabatic energies and dipole moments of the electronic states of RbLi molecule.
Dardouri, Riadh; Habli, Héla; Oujia, Brahim; Gadéa, Florent Xavier
2013-09-15
For all states dissociating below the ionic limit Li(-) Rb(+) , we perform a diabatic study for (1) Σ(+) electronic states dissociating into Rb (5s, 5p, 4d, 6s, 6p, 5d, 7s, 4f) + Li (2s, 2p, 3s). Furthermore, we present the diabatic results for the 1-11 (3) σ, 1-8 (1,3) Π, and 1-4 (1,3) Δ states. The present calculations on the RbLi molecule are complementary to previous theoretical work on this system, including recently observed electronic states that had not been calculated previously. The calculations rely on ab-initio pseudopotential, core polarization potential operators for the core-valence correlation and full valence configuration interaction approaches, combined to an efficient diabatization procedure. For the low-lying states, diabatic potentials and permanent dipole moments are analyzed, revealing the strong imprint of the ionic state in the (1) Σ(+) adiabatic states. The transition dipole moment is used to evaluate the radiative lifetimes of the vibrational levels trapped in the 2 (1) Σ(+) excited states for the first time. In addition to the bound-bound contribution, the bound-free term has been evaluated using the Franck-Condon approximation and also exactly added to the total radiative lifetime. PMID:23804208
Adiabatic topological quantum computing
NASA Astrophysics Data System (ADS)
Cesare, Chris; Landahl, Andrew J.; Bacon, Dave; Flammia, Steven T.; Neels, Alice
2015-07-01
Topological quantum computing promises error-resistant quantum computation without active error correction. However, there is a worry that during the process of executing quantum gates by braiding anyons around each other, extra anyonic excitations will be created that will disorder the encoded quantum information. Here, we explore this question in detail by studying adiabatic code deformations on Hamiltonians based on topological codes, notably Kitaev's surface codes and the more recently discovered color codes. We develop protocols that enable universal quantum computing by adiabatic evolution in a way that keeps the energy gap of the system constant with respect to the computation size and introduces only simple local Hamiltonian interactions. This allows one to perform holonomic quantum computing with these topological quantum computing systems. The tools we develop allow one to go beyond numerical simulations and understand these processes analytically.
Complete population inversion of Bose particles by an adiabatic cycle
NASA Astrophysics Data System (ADS)
Tanaka, Atushi; Cheon, Taksu
2016-04-01
We show that an adiabatic cycle excites Bose particles confined in a one-dimensional box. During the adiabatic cycle, a wall described by a δ-shaped potential is applied and its strength and position are slowly varied. When the system is initially prepared in the ground state, namely, in the zero-temperature equilibrium state, the adiabatic cycle brings all Bosons into the first excited one-particle state, leaving the system in a nonequilibrium state. The absorbed energy during the cycle is proportional to the number of Bosons.
Adiabatic Hyperspherical Analysis of Realistic Nuclear Potentials
NASA Astrophysics Data System (ADS)
Daily, K. M.; Kievsky, Alejandro; Greene, Chris H.
2015-12-01
Using the hyperspherical adiabatic method with the realistic nuclear potentials Argonne V14, Argonne V18, and Argonne V18 with the Urbana IX three-body potential, we calculate the adiabatic potentials and the triton bound state energies. We find that a discrete variable representation with the slow variable discretization method along the hyperradial degree of freedom results in energies consistent with the literature. However, using a Laguerre basis results in missing energy, even when extrapolated to an infinite number of basis functions and channels. We do not include the isospin T = 3/2 contribution in our analysis.
Anderson localization makes adiabatic quantum optimization fail
Altshuler, Boris; Krovi, Hari; Roland, Jérémie
2010-01-01
Understanding NP-complete problems is a central topic in computer science (NP stands for nondeterministic polynomial time). This is why adiabatic quantum optimization has attracted so much attention, as it provided a new approach to tackle NP-complete problems using a quantum computer. The efficiency of this approach is limited by small spectral gaps between the ground and excited states of the quantum computer’s Hamiltonian. We show that the statistics of the gaps can be analyzed in a novel way, borrowed from the study of quantum disordered systems in statistical mechanics. It turns out that due to a phenomenon similar to Anderson localization, exponentially small gaps appear close to the end of the adiabatic algorithm for large random instances of NP-complete problems. This implies that unfortunately, adiabatic quantum optimization fails: The system gets trapped in one of the numerous local minima. PMID:20616043
A theoretical study on low-lying electronic states and spectroscopic properties of PH
NASA Astrophysics Data System (ADS)
Gao, Yufeng; Gao, Tao
2014-01-01
The low-lying electronic states (X3∑-, a1Δ, b1Σ+, A3Π, c1Π and 5∑-) of the PH species correlating with the first three dissociation channels have been investigated at the MRCI + Q/aug-cc-PV5Z level of theory. Accurate adiabatic potential energy curves and spectroscopic constants (Te, Re, ωeχe, ωe, Be, De) of these electronic states have been reported. Effect of the spin-orbit coupling on the A3Π and 5∑- states of the PH has been calculated, which lead to the spin-orbit-induced predissociation of the A3Π state. Electronic transition moment, Einstein coefficients and Franck-Condon factors for the A3Π - X3∑- system have been calculated. Dipole moment functions (μe) and radiative lifetime (τv‧) for the A3Π state has also been determined. The radiative lifetime for A3Π - X3∑- transition is computed and compared with the available data.
Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.
2015-06-21
The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.
NASA Astrophysics Data System (ADS)
Grebenshchikov, Sergy Yu.
2013-06-01
The absorption spectrum of CO2 in the wavelength range 120-160 nm is analyzed by means of quantum mechanical calculations performed using vibronically coupled potential energy surfaces of five singlet valence electronic states and the coordinate dependent transition dipole moment vectors. The thermally averaged spectrum, calculated for T = 190 K via Boltzmann averaging of optical transitions from many initial rotational states, accurately reproduces the experimental spectral envelope, consisting of a low and a high energy band, the positions of the absorption maxima, their FWHMs, peak intensities, and frequencies of diffuse structures in each band. Contributions of the vibronic interactions due to Renner-Teller coupling, conical intersections, and the Herzberg-Teller effect are isolated and the calculated bands are assigned in terms of adiabatic electronic states. Finally, diffuse structures in the calculated bands are vibronically assigned using wave functions of the underlying resonance states. It is demonstrated that the main progressions in the high energy band correspond to consecutive excitations of the pseudorotational motion along the closed loop of the CI seam, and progressions differ in the number of nodes along the radial mode perpendicular to the closed seam. Irregularity of the diffuse peaks in the low energy band is interpreted as a manifestation of the carbene-type "cyclic" OCO minimum.
NASA Astrophysics Data System (ADS)
Akopyan, M. E.; Baturo, V. V.; Lukashov, S. S.; Poretsky, S. A.; Pravilov, A. M.
2012-06-01
The stepwise two-step two-color and three-step three-color laser excitation schemes are used for selective population of rovibronic levels of the first-tier ion-pair E0_g^ + and D0_u^ + states of molecular iodine and studies of non-adiabatic transitions to the D and E states induced by collisions with M = I2(X) and H2O. Collection and analysis of the luminescence after excitation of the vE = 8, 13 and vD = 13, 18 vibronic levels of the E and D states in the pure iodine vapor and the gas-phase mixtures with H2O provide rate constants for the non-adiabatic transitions to the D and E state induced by collisions with these molecules. Vibrational distributions for the I2(E,v_E {longleftrArr} limits^M D,v_D ) collision-induced non-adiabatic transitions (CINATs) are obtained. Rather strong λ _{lum}^{max } ≈ 3400 Å luminescence band is observed in the I2 + H2O mixtures, whereas its intensity is ˜100 times less in pure iodine vapor. Radiative lifetimes and quenching rate constants of the I2(E,vE = 8, 13 and D,vD = 13, 18) vibronic state are also determined. Rate constants of the I2(E,v_E stackrel {I_2 (X)} { to 30pt {rArrfill}} D,v_D ), vE = 8-54, CINATs are measured again and compared with those obtained earlier. New data confirm resonance characters of the CINATs found in our laboratory about 10 years ago. Possible reasons of differences between rate constant values obtained in this and earlier works are discussed. It is shown, in particular, that differences in rate constants of non-resonant CINATs are due to admixture of water vapor in iodine.
Cotton, Stephen J.; Igumenshchev, Kirill; Miller, William H.
2014-08-28
It has recently been shown [S. J. Cotton and W. H. Miller, J. Chem. Phys. 139, 234112 (2013)] that a symmetrical windowing quasi-classical (SQC) approach [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] applied to the Meyer-Miller model [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] for the electronic degrees of freedom in electronically non-adiabatic dynamics is capable of quantitatively reproducing quantum mechanical results for a variety of test applications, including cases where “quantum” coherence effects are significant. Here we apply this same SQC methodology, within a flux-side correlation function framework, to calculate thermal rate constants corresponding to several proposed models of electron transfer processes [P. Huo, T. F. Miller III, and D. F. Coker, J. Chem. Phys. 139, 151103 (2013); A. R. Menzeleev, N. Ananth, and T. F. Miller III, J. Chem. Phys. 135, 074106 (2011)]. Good quantitative agreement with Marcus Theory is obtained over several orders of magnitude variation in non-adiabatic coupling. Moreover, the “inverted regime” in thermal rate constants (with increasing bias) known from Marcus Theory is also reproduced with good accuracy by this very simple classical approach. The SQC treatment is also applied to a recent model of photoinduced proton coupled electron transfer [C. Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, J. Chem. Phys. 131, 154502 (2009)] and population decay of the photoexcited donor state is found to be in reasonable agreement with results calculated via reduced density matrix theory.
NASA Astrophysics Data System (ADS)
Mai, Sebastian; Marquetand, Philipp; González, Leticia
2014-05-01
The importance of triplet states in the photorelaxation dynamics of SO2 is studied by mixed quantum-classical dynamics simulations. Using the SHARC method, standing for Surface Hopping including ARbitrary Couplings, intersystem crossing (ISC) processes caused by spin-orbit coupling are found occurring on an ultrafast time scale (few 100 fs) and thus competing with internal conversion. While in the singlet-only dynamics only oscillatory population transfer between the 1B1 and 1A2 states is observed, in the dynamics including singlet and triplet states we find additionally continuous ISC to the 3B2 state and to a smaller extent to the 3B1/3A2 coupled states. The populations obtained from the dynamics are discussed with respect to the overall nuclear motion and in the light of recent TRPEPICO studies [I. Wilkinson, A. E. Boguslavskiy, J. Mikosch, D. M. Villeneuve, H.-J. Wörner, M. Spanner, S. Patchkovskii, and A. Stolow, "Excited state dynamics in SO2. I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy," J. Chem. Phys. 140, 204301 (2014)].
Newton, M.D.; Vura-Weis, J.; Wasielewski, M.R.; Subotnik, J.E.
2010-10-19
A common strategy to calculate electronic coupling matrix elements for charge or energy transfer is to take the adiabatic states generated by electronic structure computations and rotate them to form localized diabatic states. In this paper, we show that, for intermolecular transfer of singlet electronic excitation, usually we cannot fully localize the electronic excitations in this way. Instead, we calculate putative initial and final states with small excitation tails caused by weak interactions with high energy excited states in the electronic manifold. These tails do not lead to substantial changes in the total diabatic coupling between states, but they do lead to a different partitioning of the total coupling between Coulomb (Forster), exchange (Dexter), and one-electron components. The tails may be reduced by using a multistate diabatic model or eliminated entirely by truncation (denoted as 'chopping'). Without more information, we are unable to conclude with certainty whether the observed diabatic tails are a physical reality or a computational artifact. This research suggests that decomposition of the diabatic coupling between chromophores into Coulomb, exchange, and one-electron components may depend strongly on the number of states considered, and such results should be treated with caution.
NASA Astrophysics Data System (ADS)
Voityuk, Alexander A.
2006-02-01
Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽda=(E2-E1)μ12/Rda+(2E3-E1-E2)2μ13μ23/Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model.
Bazzani, A.; Turchetti, G.; Benedetti, C.; Rambaldi, S.; Servizi, G.
2005-06-08
In a high intensity circular accelerator the synchrotron dynamics introduces a slow modulation in the betatronic tune due to the space-charge tune depression. When the transverse motion is non-linear due to the presence of multipolar effects, resonance islands move in the phase space and change their amplitude. This effect introduces the trapping and detrapping phenomenon and a slow diffusion in the phase space. We apply the neo-adiabatic theory to describe this diffusion mechanism that can contribute to halo formation.
Shortcut to adiabatic gate teleportation
NASA Astrophysics Data System (ADS)
Santos, Alan C.; Silva, Raphael D.; Sarandy, Marcelo S.
2016-01-01
We introduce a shortcut to the adiabatic gate teleportation model of quantum computation. More specifically, we determine fast local counterdiabatic Hamiltonians able to implement teleportation as a universal computational primitive. In this scenario, we provide the counterdiabatic driving for arbitrary n -qubit gates, which allows to achieve universality through a variety of gate sets. Remarkably, our approach maps the superadiabatic Hamiltonian HSA for an arbitrary n -qubit gate teleportation into the implementation of a rotated superadiabatic dynamics of an n -qubit state teleportation. This result is rather general, with the speed of the evolution only dictated by the quantum speed limit. In particular, we analyze the energetic cost for different Hamiltonian interpolations in the context of the energy-time complementarity.
NASA Astrophysics Data System (ADS)
Cave, Robert J.; Stanton, John F.
2016-02-01
We present a simple quasi-diabatization scheme applicable to spectroscopic studies that can be applied using any wavefunction for which one-electron properties and transition properties can be calculated. The method is based on rotation of a pair (or set) of adiabatic states to minimize the difference between the given transition property at a reference geometry of high symmetry (where the quasi-diabatic states and adiabatic states coincide) and points of lower symmetry where quasi-diabatic quantities are desired. Compared to other quasi-diabatization techniques, the method requires no special coding, facilitates direct comparison between quasi-diabatic quantities calculated using different types of wavefunctions, and is free of any selection of configurations in the definition of the quasi-diabatic states. On the other hand, the method appears to be sensitive to multi-state issues, unlike recent methods we have developed that use a configurational definition of quasi-diabatic states. Results are presented and compared with two other recently developed quasi-diabatization techniques.
Dephasing effects on stimulated Raman adiabatic passage in tripod configurations
Lazarou, C.; Vitanov, N. V.
2010-09-15
We present an analytic description of the effects of dephasing processes on stimulated Raman adiabatic passage in a tripod quantum system. To this end, we develop an effective two-level model. Our analysis makes use of the adiabatic approximation in the weak dephasing regime. An effective master equation for a two-level system formed by two dark states is derived, where analytic solutions are obtained by utilizing the Demkov-Kunike model. From these, it is found that the fidelity for the final coherent superposition state decreases exponentially for increasing dephasing rates. Depending on the pulse ordering and for adiabatic evolution, the pulse delay can have an inverse effect.
Adiabatic Quantum Simulation of Quantum Chemistry
Babbush, Ryan; Love, Peter J.; Aspuru-Guzik, Alán
2014-01-01
We show how to apply the quantum adiabatic algorithm directly to the quantum computation of molecular properties. We describe a procedure to map electronic structure Hamiltonians to 2-body qubit Hamiltonians with a small set of physically realizable couplings. By combining the Bravyi-Kitaev construction to map fermions to qubits with perturbative gadgets to reduce the Hamiltonian to 2-body, we obtain precision requirements on the coupling strengths and a number of ancilla qubits that scale polynomially in the problem size. Hence our mapping is efficient. The required set of controllable interactions includes only two types of interaction beyond the Ising interactions required to apply the quantum adiabatic algorithm to combinatorial optimization problems. Our mapping may also be of interest to chemists directly as it defines a dictionary from electronic structure to spin Hamiltonians with physical interactions. PMID:25308187
On the Electronically Excited States of Uracil
Epifanovsky, Evgeny; Kowalski, Karol; Fan, Peng-Dong; Valiev, Marat; Matsika, Spiridoula; Krylov, Anna
2008-10-09
Vertical excitation energies in uracil in the gas phase and in water solution are investigated by the equation-of-motion coupled-cluster and multi-reference configuration interaction methods. Basis set effects are found to be important for converged results. The analysis of electronic wave functions reveals that the lowest singlet states are predominantly of a singly excited character and are therefore well described by single-reference equation-of-motion methods augmented by a perturbative triples correction to account for dynamical correlation. Our best estimates for the vertical excitation energies for the lowest singlet n and are 5.0±0.1 eV and 5.3±0.1 eV, respectively. The solvent effects for these states are estimated to be +0.5 eV and ±0.1 eV, respectively. We attribute the difference between the computed vertical excitations and the maximum of the experimental absorption to strong vibronic interaction between the lowest A00 and A0 states leading to intensity borrowing by the forbidden transition.
NASA Astrophysics Data System (ADS)
Ahmed, Hilal; Khan, Shakeel; Khan, Wasi; Nongjai, Razia; Khan, Imran
2014-11-01
We have systematically investigated structural, electrical and magnetic properties of Fe doped La0.33Sr0.67MnO3 manganites synthesized through solid-state reaction-route. All the samples are found to have rhombohedral crystal structure. The crystallite sizes obtained by XRD data are much smaller than the average grain size obtained by scanning electron microscope (SEM). Temperature dependent resistivity data were fitted using Mott's variable-range hopping (VRH) and small polaron hopping (SPH) models for obtaining different parameters. The adiabatic SPH conduction mechanism is followed almost for both samples in the absence of magnetic field but a switching from adiabatic to non-adiabatic SPH conduction mechanism is found in the presence of magnetic field. Temperature dependent magnetization (M-T) measurements confirm the decrease in Curie-temperature (TC) with Fe doping. Both the samples exhibited ferromagnetic behavior at 10 K and 300 K with a small hysteresis loop and low coercivity.
Trapped Ion Quantum Computation by Adiabatic Passage
Feng Xuni; Wu Chunfeng; Lai, C. H.; Oh, C. H.
2008-11-07
We propose a new universal quantum computation scheme for trapped ions in thermal motion via the technique of adiabatic passage, which incorporates the advantages of both the adiabatic passage and the model of trapped ions in thermal motion. Our scheme is immune from the decoherence due to spontaneous emission from excited states as the system in our scheme evolves along a dark state. In our scheme the vibrational degrees of freedom are not required to be cooled to their ground states because they are only virtually excited. It is shown that the fidelity of the resultant gate operation is still high even when the magnitude of the effective Rabi frequency moderately deviates from the desired value.
NASA Astrophysics Data System (ADS)
Landahl, Andrew
2012-10-01
Quantum computers promise to exploit counterintuitive quantum physics principles like superposition, entanglement, and uncertainty to solve problems using fundamentally fewer steps than any conventional computer ever could. The mere possibility of such a device has sharpened our understanding of quantum coherent information, just as lasers did for our understanding of coherent light. The chief obstacle to developing quantum computer technology is decoherence--one of the fastest phenomena in all of physics. In principle, decoherence can be overcome by using clever entangled redundancies in a process called fault-tolerant quantum error correction. However, the quality and scale of technology required to realize this solution appears distant. An exciting alternative is a proposal called ``adiabatic'' quantum computing (AQC), in which adiabatic quantum physics keeps the computer in its lowest-energy configuration throughout its operation, rendering it immune to many decoherence sources. The Adiabatic Quantum Architectures In Ultracold Systems (AQUARIUS) Grand Challenge Project at Sandia seeks to demonstrate this robustness in the laboratory and point a path forward for future hardware development. We are building devices in AQUARIUS that realize the AQC architecture on up to three quantum bits (``qubits'') in two platforms: Cs atoms laser-cooled to below 5 microkelvin and Si quantum dots cryo-cooled to below 100 millikelvin. We are also expanding theoretical frontiers by developing methods for scalable universal AQC in these platforms. We have successfully demonstrated operational qubits in both platforms and have even run modest one-qubit calculations using our Cs device. In the course of reaching our primary proof-of-principle demonstrations, we have developed multiple spinoff technologies including nanofabricated diffractive optical elements that define optical-tweezer trap arrays and atomic-scale Si lithography commensurate with placing individual donor atoms with
Electronically shielded solid state charged particle detector
Balmer, D.K.; Haverty, T.W.; Nordin, C.W.; Tyree, W.H.
1996-08-20
An electronically shielded solid state charged particle detector system having enhanced radio frequency interference immunity includes a detector housing with a detector entrance opening for receiving the charged particles. A charged particle detector having an active surface is disposed within the housing. The active surface faces toward the detector entrance opening for providing electrical signals representative of the received charged particles when the received charged particles are applied to the active surface. A conductive layer is disposed upon the active surface. In a preferred embodiment, a nonconductive layer is disposed between the conductive layer and the active surface. The conductive layer is electrically coupled to the detector housing to provide a substantially continuous conductive electrical shield surrounding the active surface. The inner surface of the detector housing is supplemented with a radio frequency absorbing material such as ferrite. 1 fig.
Electronically shielded solid state charged particle detector
Balmer, D.K.; Haverty, T.W.; Nordin, C.W.; Tyree, W.H.
1995-12-31
An electronically shielded solid state charged particle detector system having enhanced radio frequency interference immunity includes a detector housing with a detector entrance opening for receiving the charged particles. A charged particle detector having an active surface is disposed within the housing. The active surface faces toward the detector entrance opening for providing electrical signals representative of the received charged particles when the received charged particles are applied to the active surface. A conductive layer is disposed upon the active surface. In a preferred embodiment, a nonconductive layer is disposed between the conductive layer and the active surface. The conductive layer is electrically coupled to the detector housing to provide a substantially continuous conductive electrical shield surrounding the active surface. The inner surface of the detector housing is supplemented with a radio frequency absorbing material such as ferrite.
Electronically shielded solid state charged particle detector
Balmer, David K.; Haverty, Thomas W.; Nordin, Carl W.; Tyree, William H.
1996-08-20
An electronically shielded solid state charged particle detector system having enhanced radio frequency interference immunity includes a detector housing with a detector entrance opening for receiving the charged particles. A charged particle detector having an active surface is disposed within the housing. The active surface faces toward the detector entrance opening for providing electrical signals representative of the received charged particles when the received charged particles are applied to the active surface. A conductive layer is disposed upon the active surface. In a preferred embodiment, a nonconductive layer is disposed between the conductive layer and the active surface. The conductive layer is electrically coupled to the detector housing to provide a substantially continuous conductive electrical shield surrounding the active surface. The inner surface of the detector housing is supplemented with a radio frequency absorbing material such as ferrite.
Geometry of the Adiabatic Theorem
ERIC Educational Resources Information Center
Lobo, Augusto Cesar; Ribeiro, Rafael Antunes; Ribeiro, Clyffe de Assis; Dieguez, Pedro Ruas
2012-01-01
We present a simple and pedagogical derivation of the quantum adiabatic theorem for two-level systems (a single qubit) based on geometrical structures of quantum mechanics developed by Anandan and Aharonov, among others. We have chosen to use only the minimum geometric structure needed for the understanding of the adiabatic theorem for this case.…
Robust quantum logic in neutral atoms via adiabatic Rydberg dressing
Keating, Tyler; Cook, Robert L.; Hankin, Aaron M.; Jau, Yuan -Yu; Biedermann, Grant W.; Deutsch, Ivan H.
2015-01-28
We study a scheme for implementing a controlled-Z (CZ) gate between two neutral-atom qubits based on the Rydberg blockade mechanism in a manner that is robust to errors caused by atomic motion. By employing adiabatic dressing of the ground electronic state, we can protect the gate from decoherence due to random phase errors that typically arise because of atomic thermal motion. In addition, the adiabatic protocol allows for a Doppler-free configuration that involves counterpropagating lasers in a σ_{+}/σ_{-} orthogonal polarization geometry that further reduces motional errors due to Doppler shifts. The residual motional error is dominated by dipole-dipole forces acting on doubly-excited Rydberg atoms when the blockade is imperfect. As a result, for reasonable parameters, with qubits encoded into the clock states of ^{133}Cs, we predict that our protocol could produce a CZ gate in < 10 μs with error probability on the order of 10^{-3}.
Robust quantum logic in neutral atoms via adiabatic Rydberg dressing
Keating, Tyler; Cook, Robert L.; Hankin, Aaron M.; Jau, Yuan -Yu; Biedermann, Grant W.; Deutsch, Ivan H.
2015-01-28
We study a scheme for implementing a controlled-Z (CZ) gate between two neutral-atom qubits based on the Rydberg blockade mechanism in a manner that is robust to errors caused by atomic motion. By employing adiabatic dressing of the ground electronic state, we can protect the gate from decoherence due to random phase errors that typically arise because of atomic thermal motion. In addition, the adiabatic protocol allows for a Doppler-free configuration that involves counterpropagating lasers in a σ+/σ- orthogonal polarization geometry that further reduces motional errors due to Doppler shifts. The residual motional error is dominated by dipole-dipole forces actingmore » on doubly-excited Rydberg atoms when the blockade is imperfect. As a result, for reasonable parameters, with qubits encoded into the clock states of 133Cs, we predict that our protocol could produce a CZ gate in < 10 μs with error probability on the order of 10-3.« less
NASA Astrophysics Data System (ADS)
Chan, Y. C.; Harding, D. R.; Stwalley, W. C.; Vidal, C. R.
1986-09-01
Laser-induced fluorescence (LIF) spectra of the A-X system of the LiH isotopes, excited by the UV lines of an argon and a krypton ion laser, were observed and analyzed. Three long LIF series of different LiH isotopes were taken with a 3.4 m high resolution spectrograph. The results were combined with previous experimental data to study the breakdown of the Born-Oppenheimer approximation in the X 1Σ+ electronic ground state of the isotopic LiH molecules. Using a quantum mechanical variational method, potential energy curves of the four LiH isotopes were extended almost up to the dissociation limits.
Low-lying electronic states of carotenoids.
DeCoster, B; Christensen, R L; Gebhard, R; Lugtenburg, J; Farhoosh, R; Frank, H A
1992-08-28
Four all-trans carotenoids, spheroidene, 3,4-dihydrospheroidene, 3,4,5,6-tetrahydrospheroidene, and 3,4,7,8-tetrahydrospheroidene, have been purified using HPLC techniques and analyzed using absorption, fluorescence and fluorescence excitation spectroscopy of room temperature solutions. This series of molecules, for which the extent of pi-electron conjugation decreases from 10 to seven carbon-carbon double bonds, exhibits a systematic crossover from S2----S0 (1(1)Bu----1(1)Ag) to S1----S0 (2(1)Ag----1(1)Ag) emission with decreasing chain length. Extrapolation of the S1----S0 transition energies indicates that the 2(1)Ag states of longer carotenoids have considerably lower energies than previously thought. The energies of the S1 states of spheroidenes and other long carotenoids are correlated with the S1 energies of their chlorophyll partners in antenna complexes of photosynthetic systems. Implications for energy transfer in photosynthetic antenna are discussed. PMID:1510992
Dynamics of Charged Particles in an Adiabatic Thermal Beam Equilibrium
NASA Astrophysics Data System (ADS)
Chen, Chiping; Wei, Haofei
2010-11-01
Charged-particle motion is studied in the self-electric and self-magnetic fields of a well-matched, intense charged-particle beam and an applied periodic solenoidal magnetic focusing field. The beam is assumed to be in a state of adiabatic thermal equilibrium. The phase space is analyzed and compared with that of the well-known Kapchinskij-Vladimirskij (KV)-type beam equilibrium. It is found that the widths of nonlinear resonances in the adiabatic thermal beam equilibrium are narrower than those in the KV-type beam equilibrium. Numerical evidence is presented, indicating almost complete elimination of chaotic particle motion in the adiabatic thermal beam equilibrium.
Adiabatic heating in impulsive solar flares
NASA Technical Reports Server (NTRS)
Maetzler, C.; Bai, T.; Crannell, C. J.; Frost, K. J.
1978-01-01
A study is made of adiabatic heating in two impulsive solar flares on the basis of dynamic X-ray spectra in the 28-254 keV range, H-alpha, microwave, and meter-wave radio observations. It is found that the X-ray spectra of the events are like those of thermal bremsstrahlung from single-temperature plasmas in the 10-60 keV range if photospheric albedo is taken into account. The temperature-emission correlation indicates adiabatic compression followed by adiabatic expansion and that the electron distribution remains isotropic. H-alpha data suggest compressive energy transfer. The projected areas and volumes of the flares are estimated assuming that X-ray and microwave emissions are produced in a single thermal plasma. Electron densities of about 10 to the 9th/cu cm are found for homogeneous, spherically symmetric sources. It is noted that the strong self-absorption of hot-plasma gyrosynchrotron radiation reveals low magnetic field strengths.
Creation of ultracold Sr(2) molecules in the electronic ground state.
Stellmer, Simon; Pasquiou, Benjamin; Grimm, Rudolf; Schreck, Florian
2012-09-14
We report on the creation of ultracold (84)Sr(2) molecules in the electronic ground state. The molecules are formed from atom pairs on sites of an optical lattice using stimulated Raman adiabatic passage (STIRAP). We achieve a transfer efficiency of 30% and obtain 4×10(4) molecules with full control over the external and internal quantum state. STIRAP is performed near the narrow (1)S(0)-(3)P(1) intercombination transition, using a vibrational level of the 1(0(u)(+)) potential as an intermediate state. In preparation of our molecule association scheme, we have determined the binding energies of the last vibrational levels of the 1(0(u)(+)), 1(1(u)) excited-state and the X (1)Σ(g)(+) ground-state potentials. Our work overcomes the previous limitation of STIRAP schemes to systems with magnetic Feshbach resonances, thereby establishing a route that is applicable to many systems beyond alkali-metal dimers. PMID:23005642
Acceleration of adiabatic quantum dynamics in electromagnetic fields
Masuda, Shumpei; Nakamura, Katsuhiro
2011-10-15
We show a method to accelerate quantum adiabatic dynamics of wave functions under electromagnetic field (EMF) by developing the preceding theory [Masuda and Nakamura, Proc. R. Soc. London Ser. A 466, 1135 (2010)]. Treating the orbital dynamics of a charged particle in EMF, we derive the driving field which accelerates quantum adiabatic dynamics in order to obtain the final adiabatic states in any desired short time. The scheme is consolidated by describing a way to overcome possible singularities in both the additional phase and driving potential due to nodes proper to wave functions under EMF. As explicit examples, we exhibit the fast forward of adiabatic squeezing and transport of excited Landau states with nonzero angular momentum, obtaining the result consistent with the transitionless quantum driving applied to the orbital dynamics in EMF.
Non-adiabatic perturbations in Ricci dark energy model
Karwan, Khamphee; Thitapura, Thiti E-mail: nanodsci2523@hotmail.com
2012-01-01
We show that the non-adiabatic perturbations between Ricci dark energy and matter can grow both on superhorizon and subhorizon scales, and these non-adiabatic perturbations on subhorizon scales can lead to instability in this dark energy model. The rapidly growing non-adiabatic modes on subhorizon scales always occur when the equation of state parameter of dark energy starts to drop towards -1 near the end of matter era, except that the parameter α of Ricci dark energy equals to 1/2. In the case where α = 1/2, the rapidly growing non-adiabatic modes disappear when the perturbations in dark energy and matter are adiabatic initially. However, an adiabaticity between dark energy and matter perturbations at early time implies a non-adiabaticity between matter and radiation, this can influence the ordinary Sachs-Wolfe (OSW) effect. Since the amount of Ricci dark energy is not small during matter domination, the integrated Sachs-Wolfe (ISW) effect is greatly modified by density perturbations of dark energy, leading to a wrong shape of CMB power spectrum. The instability in Ricci dark energy is difficult to be alleviated if the effects of coupling between baryon and photon on dark energy perturbations are included.
AB INITIO SIMULATIONS FOR MATERIAL PROPERTIES ALONG THE JUPITER ADIABAT
French, Martin; Becker, Andreas; Lorenzen, Winfried; Nettelmann, Nadine; Bethkenhagen, Mandy; Redmer, Ronald; Wicht, Johannes
2012-09-15
We determine basic thermodynamic and transport properties of hydrogen-helium-water mixtures for the extreme conditions along Jupiter's adiabat via ab initio simulations, which are compiled in an accurate and consistent data set. In particular, we calculate the electrical and thermal conductivity, the shear and longitudinal viscosity, and diffusion coefficients of the nuclei. We present results for associated quantities like the magnetic and thermal diffusivity and the kinematic shear viscosity along an adiabat that is taken from a state-of-the-art interior structure model. Furthermore, the heat capacities, the thermal expansion coefficient, the isothermal compressibility, the Grueneisen parameter, and the speed of sound are calculated. We find that the onset of dissociation and ionization of hydrogen at about 0.9 Jupiter radii marks a region where the material properties change drastically. In the deep interior, where the electrons are degenerate, many of the material properties remain relatively constant. Our ab initio data will serve as a robust foundation for applications that require accurate knowledge of the material properties in Jupiter's interior, e.g., models for the dynamo generation.
Coverage dependent non-adiabaticity of CO on a copper surface
Omiya, Takuma; Arnolds, Heike
2014-12-07
We have studied the coverage-dependent energy transfer dynamics between hot electrons and CO on Cu(110) with femtosecond visible pump, sum frequency probe spectroscopy. We find that transients of the C–O stretch frequency display a red shift, which increases from 3 cm{sup −1} at 0.1 ML to 9 cm{sup −1} at 0.77 ML. Analysis of the transients reveals that the non-adiabatic coupling between the adsorbate vibrational motion and the electrons becomes stronger with increasing coverage. This trend requires the frustrated rotational mode to be the cause of the non-adiabatic behavior, even for relatively weak laser excitation of the adsorbate. We attribute the coverage dependence to both an increase in the adsorbate electronic density of states and an increasingly anharmonic potential energy surface caused by repulsive interactions between neighboring CO adsorbates. This work thus reveals adsorbate-adsorbate interactions as a new way to control adsorbate non-adiabaticity.
Sen, Ananya; Matthews, Edward M.; Hou, Gao-Lei; Wang, Xue B.; Dessent, Caroline
2015-11-14
We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ~1.7 eV, values that are lower than the RCB of the uncomplexed PtCl6 2- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl6 2-∙thymine and PtCl6 2-∙adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)4 2-∙nucleobase complexes [Sen et al, J. Phys. Chem. B, 119, 11626, 2015]. The observation of delayed electron emission bands in the PtCl6 2-∙nucleobase spectra obtained in this work, as for the previously studied Pt(CN)4 2-∙nucleobase complexes, is attributed to onephoton excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase decays over a timescale long enough to allow autodetachment.
An incompressible state of a photo-excited electron gas
Chepelianskii, Alexei D.; Watanabe, Masamitsu; Nasyedkin, Kostyantyn; Kono, Kimitoshi; Konstantinov, Denis
2015-01-01
Two-dimensional electrons in a magnetic field can form new states of matter characterized by topological properties and strong electronic correlations as displayed in the integer and fractional quantum Hall states. In these states, the electron liquid displays several spectacular characteristics, which manifest themselves in transport experiments with the quantization of the Hall resistance and a vanishing longitudinal conductivity or in thermodynamic equilibrium when the electron fluid becomes incompressible. Several experiments have reported that dissipationless transport can be achieved even at weak, non-quantizing magnetic fields when the electrons absorb photons at specific energies related to their cyclotron frequency. Here we perform compressibility measurements on electrons on liquid helium demonstrating the formation of an incompressible electronic state under these resonant excitation conditions. This new state provides a striking example of irradiation-induced self-organization in a quantum system. PMID:26007282
Shortcuts to adiabaticity from linear response theory.
Acconcia, Thiago V; Bonança, Marcus V S; Deffner, Sebastian
2015-10-01
A shortcut to adiabaticity is a finite-time process that produces the same final state as would result from infinitely slow driving. We show that such shortcuts can be found for weak perturbations from linear response theory. With the help of phenomenological response functions, a simple expression for the excess work is found-quantifying the nonequilibrium excitations. For two specific examples, i.e., the quantum parametric oscillator and the spin 1/2 in a time-dependent magnetic field, we show that finite-time zeros of the excess work indicate the existence of shortcuts. Finally, we propose a degenerate family of protocols, which facilitates shortcuts to adiabaticity for specific and very short driving times. PMID:26565209
Arbitrary qudit gates by adiabatic passage
NASA Astrophysics Data System (ADS)
Rousseaux, B.; Guérin, S.; Vitanov, N. V.
2013-03-01
We derive an adiabatic technique that implements the most general SU(d) transformation in a quantum system of d degenerate states, featuring a qudit. This technique is based on the factorization of the SU(d) transformation into d generalized quantum Householder reflections, each of which is implemented by a two-shot stimulated Raman adiabatic passage with appropriate static phases. The energy of the lasers needed to synthesize a single Householder reflection is shown to be remarkably constant as a function of d. This technique is directly applicable to a linear trapped ion system with d+1 ions. We implement the quantum Fourier transform numerically in a qudit with d=4 (defined as a quartit) as an example.
Adiabatic Quantum Optimization for Associative Memory Recall
NASA Astrophysics Data System (ADS)
Seddiqi, Hadayat; Humble, Travis
2014-12-01
Hopfield networks are a variant of associative memory that recall patterns stored in the couplings of an Ising model. Stored memories are conventionally accessed as fixed points in the network dynamics that correspond to energetic minima of the spin state. We show that memories stored in a Hopfield network may also be recalled by energy minimization using adiabatic quantum optimization (AQO). Numerical simulations of the underlying quantum dynamics allow us to quantify AQO recall accuracy with respect to the number of stored memories and noise in the input key. We investigate AQO performance with respect to how memories are stored in the Ising model according to different learning rules. Our results demonstrate that AQO recall accuracy varies strongly with learning rule, a behavior that is attributed to differences in energy landscapes. Consequently, learning rules offer a family of methods for programming adiabatic quantum optimization that we expect to be useful for characterizing AQO performance.
Quantum adiabatic evolution with energy degeneracy levels
NASA Astrophysics Data System (ADS)
Zhang, Qi
2016-01-01
A classical-kind phase-space formalism is developed to address the tiny intrinsic dynamical deviation from what is predicted by Wilczek-Zee theorem during quantum adiabatic evolution on degeneracy levels. In this formalism, the Hilbert space and the aggregate of degenerate eigenstates become the classical-kind phase space and a high-dimensional subspace in the phase space, respectively. Compared with the previous analogous study by a different method, the current result is qualitatively different in that the first-order deviation derived here is always perpendicular to the degeneracy subspace. A tripod-scheme Hamiltonian with two degenerate dark states is employed to illustrate the adiabatic deviation with degeneracy levels.
Shortcuts to adiabaticity from linear response theory
NASA Astrophysics Data System (ADS)
Acconcia, Thiago V.; Bonança, Marcus V. S.; Deffner, Sebastian
2015-10-01
A shortcut to adiabaticity is a finite-time process that produces the same final state as would result from infinitely slow driving. We show that such shortcuts can be found for weak perturbations from linear response theory. With the help of phenomenological response functions, a simple expression for the excess work is found—quantifying the nonequilibrium excitations. For two specific examples, i.e., the quantum parametric oscillator and the spin 1/2 in a time-dependent magnetic field, we show that finite-time zeros of the excess work indicate the existence of shortcuts. Finally, we propose a degenerate family of protocols, which facilitates shortcuts to adiabaticity for specific and very short driving times.
Adiabatic quantum optimization for associative memory recall
Seddiqi, Hadayat; Humble, Travis S.
2014-12-22
Hopfield networks are a variant of associative memory that recall patterns stored in the couplings of an Ising model. Stored memories are conventionally accessed as fixed points in the network dynamics that correspond to energetic minima of the spin state. We show that memories stored in a Hopfield network may also be recalled by energy minimization using adiabatic quantum optimization (AQO). Numerical simulations of the underlying quantum dynamics allow us to quantify AQO recall accuracy with respect to the number of stored memories and noise in the input key. We investigate AQO performance with respect to how memories are storedmore » in the Ising model according to different learning rules. Our results demonstrate that AQO recall accuracy varies strongly with learning rule, a behavior that is attributed to differences in energy landscapes. Consequently, learning rules offer a family of methods for programming adiabatic quantum optimization that we expect to be useful for characterizing AQO performance.« less
Adiabatic quantum optimization for associative memory recall
Seddiqi, Hadayat; Humble, Travis S.
2014-12-22
Hopfield networks are a variant of associative memory that recall patterns stored in the couplings of an Ising model. Stored memories are conventionally accessed as fixed points in the network dynamics that correspond to energetic minima of the spin state. We show that memories stored in a Hopfield network may also be recalled by energy minimization using adiabatic quantum optimization (AQO). Numerical simulations of the underlying quantum dynamics allow us to quantify AQO recall accuracy with respect to the number of stored memories and noise in the input key. We investigate AQO performance with respect to how memories are stored in the Ising model according to different learning rules. Our results demonstrate that AQO recall accuracy varies strongly with learning rule, a behavior that is attributed to differences in energy landscapes. Consequently, learning rules offer a family of methods for programming adiabatic quantum optimization that we expect to be useful for characterizing AQO performance.
Shortcuts to adiabaticity from linear response theory
Acconcia, Thiago V.; Bonança, Marcus V. S.; Deffner, Sebastian
2015-10-23
A shortcut to adiabaticity is a finite-time process that produces the same final state as would result from infinitely slow driving. We show that such shortcuts can be found for weak perturbations from linear response theory. Moreover, with the help of phenomenological response functions, a simple expression for the excess work is found—quantifying the nonequilibrium excitations. For two specific examples, i.e., the quantum parametric oscillator and the spin 1/2 in a time-dependent magnetic field, we show that finite-time zeros of the excess work indicate the existence of shortcuts. We finally propose a degenerate family of protocols, which facilitates shortcuts to adiabaticity for specific and very short driving times.
Shortcuts to adiabaticity from linear response theory
Acconcia, Thiago V.; Bonança, Marcus V. S.; Deffner, Sebastian
2015-10-23
A shortcut to adiabaticity is a finite-time process that produces the same final state as would result from infinitely slow driving. We show that such shortcuts can be found for weak perturbations from linear response theory. Moreover, with the help of phenomenological response functions, a simple expression for the excess work is found—quantifying the nonequilibrium excitations. For two specific examples, i.e., the quantum parametric oscillator and the spin 1/2 in a time-dependent magnetic field, we show that finite-time zeros of the excess work indicate the existence of shortcuts. We finally propose a degenerate family of protocols, which facilitates shortcuts tomore » adiabaticity for specific and very short driving times.« less
Adiabatic Quantization of Andreev Quantum Billiard Levels
NASA Astrophysics Data System (ADS)
Silvestrov, P. G.; Goorden, M. C.; Beenakker, C. W.
2003-03-01
We identify the time T between Andreev reflections as a classical adiabatic invariant in a ballistic chaotic cavity (Lyapunov exponent λ), coupled to a superconductor by an N-mode constriction. Quantization of the adiabatically invariant torus in phase space gives a discrete set of periods Tn, which in turn generate a ladder of excited states ɛnm=(m+1/2)πℏ/Tn. The largest quantized period is the Ehrenfest time T0=λ-1ln(N. Projection of the invariant torus onto the coordinate plane shows that the wave functions inside the cavity are squeezed to a transverse dimension W/(N), much below the width W of the constriction.
Pulse sequences in photoassociation via adiabatic passage
NASA Astrophysics Data System (ADS)
Li, Xuan; Dupre, William; Parker, Gregory A.
2012-07-01
We perform a detailed study of pulse sequences in a photoassociation via adiabatic passage (PAP) process to transfer population from an ensemble of ultracold atomic clouds to a vibrationally cold molecular state. We show that an appreciable final population of ultracold NaCs molecules can be achieved with optimized pulses in either the ‘counter-intuitive’ (tP > tS) or ‘intuitive’ (tP < tS) PAP pulse sequences, with tP and tS denoting the temporal centers of the pump and Stokes pulses, respectively. By investigating the dependence of the reactive yield on pulse sequences, in a wide range of tP-tS, we show that there is not a fundamental preference to either pulse sequence in a PAP process. We explain this no-sequence-preference phenomenon by analyzing a multi-bound model so that an analogy can be drawn to the conventional stimulated Raman adiabatic passage.
Guest, G.E.; Dandl, R.A.; Miller, R.L.
1989-01-17
The Plasma Electron Microwave Source (PEMS) concept is a relativistic-electron plasma confined in a magnetic-mirror device. The stored energy is transformed into microwaves through amplification of whistler waves that can be launched externally for amplifier operation or generated spontaneously for oscillator operation. The anisotropy of the hot-electron temperature governs the maximum plasma energy density that can be stored, the amplification rates, and the saturated power level of the unstable whistler waves. This report summarizes the results of theoretical studies of (1) the critical aspects of hot-electron plasmas generated by ECH techniques, such as the Upper Off-Resonant Heating pioneered by Dandl in the ELMO series of experiments; and, (2) the spatial amplification rates of unstable whistler waves in these plasmas. It is shown that a substantial fraction of the energy stored in a hot-electron plasma can be transformed into repetitive pulses of microwave power by employing the PEMS approach, with typical values of gain, about 40db and bandwidth.
45 CFR 265.6 - Must States file reports electronically?
Code of Federal Regulations, 2010 CFR
2010-10-01
... (ASSISTANCE PROGRAMS), ADMINISTRATION FOR CHILDREN AND FAMILIES, DEPARTMENT OF HEALTH AND HUMAN SERVICES DATA COLLECTION AND REPORTING REQUIREMENTS § 265.6 Must States file reports electronically? Each State must...
Taming the low-lying electronic states of FeH.
DeYonker, Nathan J; Allen, Wesley D
2012-12-21
The low-lying electronic states (X (4)Δ, A (4)Π, a (6)Δ, b (6)Π) of the iron monohydride radical, which are especially troublesome for electronic structure theory, have been successfully described using a focal point analysis (FPA) approach that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through hextuple (CCSDTQPH) excitations. Adiabatic excitation energies (T(0)) and spectroscopic constants (r(e), r(0), B(e), B(0), D(e), ω(e), v(0), α(e), ω(e)x(e)) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pwCV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, spin-orbit coupling, and the diagonal Born-Oppenheimer correction. The purely ab initio FPA approach yields the following T(0) results (in eV) for the lowest spin-orbit components of each electronic state: 0 (X (4)Δ) < 0.132 (A (4)Π) < 0.190 (a (6)Δ) < 0.444 (b (6)Π). The computed anharmonic fundamental vibrational frequencies (v(0)) for the (4,6)Δ electronic states are within 3 cm(-1) of experiment and provide reliable predictions for the (4,6)Π states. With the cc-pVDZ basis set, even CCSDTQPH energies give an incorrect ground state of FeH, highlighting the importance of combining high-order electron correlation treatments with robust basis sets when studying transition-metal radicals. The FPA computations provide D(0) = 1.86 eV (42.9 kcal mol(-1)) for the 0 K dissociation energy of FeH and Δ(f)H(298) (∘) [FeH((g))] = 107.7 kcal mol(-1) for the enthalpy of formation at room temperature. Despite sizable multireference character in the quartet states, high-order single-reference coupled cluster computations improve the spectroscopic parameters over previous multireference theoretical studies; for example, the X (4)Δ → A (4)Π and a (6)Δ → b (6)Π transition energies are reproduced to 0
Adiabatic passage in the presence of noise
NASA Astrophysics Data System (ADS)
Noel, T.; Dietrich, M. R.; Kurz, N.; Shu, G.; Wright, J.; Blinov, B. B.
2012-02-01
We report on an experimental investigation of rapid adiabatic passage (RAP) in a trapped barium ion system. RAP is implemented on the transition from the 6S1/2 ground state to the metastable 5D5/2 level by applying a laser at 1.76 μm. We focus on the interplay of laser frequency noise and laser power in shaping the effectiveness of RAP, which is commonly assumed to be a robust tool for high-efficiency population transfer. However, we note that reaching high state transfer fidelity requires a combination of small laser linewidth and large Rabi frequency.
Local entanglement generation in the adiabatic regime
Cliche, M.; Veitia, Andrzej
2010-09-15
We study entanglement generation in a pair of qubits interacting with an initially correlated system. Using time-independent perturbation theory and the adiabatic theorem, we show conditions under which the qubits become entangled as the joint system evolves into the ground state of the interacting theory. We then apply these results to the case of qubits interacting with a scalar quantum field. We study three different variations of this setup; a quantum field subject to Dirichlet boundary conditions, a quantum field interacting with a classical potential, and a quantum field that starts in a thermal state.
Random matrix model of adiabatic quantum computing
Mitchell, David R.; Adami, Christoph; Lue, Waynn; Williams, Colin P.
2005-05-15
We present an analysis of the quantum adiabatic algorithm for solving hard instances of 3-SAT (an NP-complete problem) in terms of random matrix theory (RMT). We determine the global regularity of the spectral fluctuations of the instantaneous Hamiltonians encountered during the interpolation between the starting Hamiltonians and the ones whose ground states encode the solutions to the computational problems of interest. At each interpolation point, we quantify the degree of regularity of the average spectral distribution via its Brody parameter, a measure that distinguishes regular (i.e., Poissonian) from chaotic (i.e., Wigner-type) distributions of normalized nearest-neighbor spacings. We find that for hard problem instances - i.e., those having a critical ratio of clauses to variables - the spectral fluctuations typically become irregular across a contiguous region of the interpolation parameter, while the spectrum is regular for easy instances. Within the hard region, RMT may be applied to obtain a mathematical model of the probability of avoided level crossings and concomitant failure rate of the adiabatic algorithm due to nonadiabatic Landau-Zener-type transitions. Our model predicts that if the interpolation is performed at a uniform rate, the average failure rate of the quantum adiabatic algorithm, when averaged over hard problem instances, scales exponentially with increasing problem size.
Aspects of adiabatic population transfer and control
NASA Astrophysics Data System (ADS)
Demirplak, Mustafa
This thesis explores two different questions. The first question we answer is how to restore a given population transfer scenario given that it works efficiently in the adiabatic limit but fails because of lack of intensity and/or short duration. We derive a very simple algorithm to do this and apply it to both toy and realistic models. Two results emerge from this study. While the mathematical existence of the programme is certain it might not always be physically desirable. The restoration of adiabaticity is phase sensitive. The second question that is answered in this thesis is not how to invent new control paradigms, but rather what would happen to them in the presence of stochastic perturbers. We first use a phenomenological model to study the effect of stochastic dephasing on population transfer by stimulated Raman adiabatic passage. The results of this Monte Carlo calculation are qualitatively explained with a perturbation theoretical result in the dressed state basis. The reliability of our phenomenological model is questioned through a more rigorous hybrid quantal-classical simulation of controlled population transfer in HCl in Ar.
Adiabatic charging of nickel-hydrogen batteries
NASA Technical Reports Server (NTRS)
Lurie, Chuck; Foroozan, S.; Brewer, Jeff; Jackson, Lorna
1995-01-01
Battery management during prelaunch activities has always required special attention and careful planning. The transition from nickel-cadium to nickel-hydrogen batteries, with their high self discharge rate and lower charge efficiency, as well as longer prelaunch scenarios, has made this aspect of spacecraft battery management even more challenging. The AXAF-I Program requires high battery state of charge at launch. The use of active cooling, to ensure efficient charging, was considered and proved to be difficult and expensive. Alternative approaches were evaluated. Optimized charging, in the absence of cooling, appeared promising and was investigated. Initial testing was conducted to demonstrate the feasibility of the 'Adiabatic Charging' approach. Feasibility was demonstrated and additional testing performed to provide a quantitative, parametric data base. The assumption that the battery is in an adiabatic environment during prelaunch charging is a conservative approximation because the battery will transfer some heat to its surroundings by convective air cooling. The amount is small compared to the heat dissipated during battery overcharge. Because the battery has a large thermal mass, substantial overcharge can occur before the cells get too hot to charge efficiently. The testing presented here simulates a true adiabatic environment. Accordingly the data base may be slightly conservative. The adiabatic charge methodology used in this investigation begins with stabilizing the cell at a given starting temperature. The cell is then fully insulated on all sides. Battery temperature is carefully monitored and the charge terminated when the cell temperature reaches 85 F. Charging has been evaluated with starting temperatures from 55 to 75 F.
Experimental breaking of an adiabatic invariant
NASA Astrophysics Data System (ADS)
Notte, J.; Fajans, J.; Chu, R.; Wurtele, J. S.
1993-06-01
When a cylindrical pure electron plasma is displaced from the center of the trap, it performs a bulk circular orbital motion known as the l=1 diocotron mode. The slow application of a perturbing potential to a patch on the trap wall distorts the orbit into a noncircular closed path. Experiments and a simple theoretical model indicate that the area by the loop is an adiabatic invariant. Detailed studies are made of the breaking of the invariant when perturbations are rapidly applied. When the perturbation is applied with discontinuous time derivatives, the invariant breaking greatly exceeds the predictions of the standard theory for smooth perturbations.
Electron states in semiconductor quantum dots
Dhayal, Suman S.; Ramaniah, Lavanya M.; Ruda, Harry E.; Nair, Selvakumar V.
2014-11-28
In this work, the electronic structures of quantum dots (QDs) of nine direct band gap semiconductor materials belonging to the group II-VI and III-V families are investigated, within the empirical tight-binding framework, in the effective bond orbital model. This methodology is shown to accurately describe these systems, yielding, at the same time, qualitative insights into their electronic properties. Various features of the bulk band structure such as band-gaps, band curvature, and band widths around symmetry points affect the quantum confinement of electrons and holes. These effects are identified and quantified. A comparison with experimental data yields good agreement with the calculations. These theoretical results would help quantify the optical response of QDs of these materials and provide useful input for applications.
Trends in solid state electronics, part 2
NASA Technical Reports Server (NTRS)
Gassaway, J. D.
1972-01-01
Developments in the fields of semiconductors and magnetics are surveyed. Materials, devices, theory, and fabrication technology are discussed. Important events up until the present time are reported, and events are interpreted through historical perspective. A brief analysis of forces which have driven the development of today's electronic technology and some projections of present trends are given. More detailed discussions are presented for four areas of contemporary interest: amorphous semiconductors, bubble domain devices, charge-coupled devices, and electron and ion beam techniques. Beam addressed magnetic memories are reviewed to a lesser extent.
NASA Astrophysics Data System (ADS)
Khait, Yuriy G.; Azenkeng, Alexander; Wang, Hefeng; Dudley, Timothy J.; Hoffmann, Mark R.
2005-03-01
A multireference configuration interaction (CI) method which includes single and double excitations based description of adiabatic Floquet states for the electronic structure of a molecule in an intense laser field is introduced. Using a variant of a recently introduced configuration state function (CSF) based Table-CI methodology, it is shown that the multiple states of several irreducible representations required for a good description of low-lying Floquet states can be obtained using modifications of computational molecular electronic structure techniques. In particular, formulas for all components of the transition dipole moment matrix elements within the CSF-based Table-CI method are derived and presented. Moreover, the flexibility of the recently introduced macroconfiguration description of model and external configuration spaces is shown to lead to multiple potential energy surfaces of sufficiently uniform quality to allow construction of useful Floquet states. The formalism and computer programs developed are demonstrated on Li2+ in a 0.9×1012W/cm2 field. In analogy with Na2+, the 1,2Σg+2, 1,2Σu+2, 1Πg2, and 1Πu2 states are of relevance, although the pattern of couplings is shown to be more complex. A hitherto unnoticed metastable state, which correlates asymptotically with 2Σu+2, is described.
Electron and electron-hole quasiparticle states in a driven quantum contact
NASA Astrophysics Data System (ADS)
Vanević, Mihajlo; Gabelli, Julien; Belzig, Wolfgang; Reulet, Bertrand
2016-01-01
We study the many-body electronic state created by a time-dependent drive of a mesoscopic contact. The many-body state is expressed manifestly in terms of single-electron and electron-hole quasiparticle excitations with the amplitudes and probabilities of creation which depend on the details of the applied voltage. We experimentally probe the time dependence of the constituent electronic states by using an analog of the optical Hong-Ou-Mandel correlation experiment where electrons emitted from the terminals with a relative time delay collide at the contact. The electron wave packet overlap is directly related to the current noise power in the contact. We have confirmed the time dependence of the electronic states predicted theoretically by measurements of the current noise power in a tunnel junction under harmonic excitation.
Adiabatic connection at negative coupling strengths
Seidl, Michael; Gori-Giorgi, Paola
2010-01-15
The adiabatic connection of density functional theory (DFT) for electronic systems is generalized here to negative values of the coupling strength alpha (with attractive electrons). In the extreme limit alpha->-infinity a simple physical solution is presented and its implications for DFT (as well as its limitations) are discussed. For two-electron systems (a case in which the present solution can be calculated exactly), we find that an interpolation between the limit alpha->-infinity and the opposite limit of infinitely strong repulsion (alpha->+infinity) yields a rather accurate estimate of the second-order correlation energy E{sub c}{sup GL2}[rho] for several different densities rho, without using virtual orbitals. The same procedure is also applied to the Be isoelectronic series, analyzing the effects of near degeneracy.
Non-adiabatic molecular dynamics with complex quantum trajectories. II. The adiabatic representation
NASA Astrophysics Data System (ADS)
Zamstein, Noa; Tannor, David J.
2012-12-01
We present a complex quantum trajectory method for treating non-adiabatic dynamics. Each trajectory evolves classically on a single electronic surface but with complex position and momentum. The equations of motion are derived directly from the time-dependent Schrödinger equation, and the population exchange arises naturally from amplitude-transfer terms. In this paper the equations of motion are derived in the adiabatic representation to complement our work in the diabatic representation [N. Zamstein and D. J. Tannor, J. Chem. Phys. 137, 22A517 (2012)], 10.1063/1.4739845. We apply our method to two benchmark models introduced by John Tully [J. Chem. Phys. 93, 1061 (1990)], 10.1063/1.459170, and get very good agreement with converged quantum-mechanical calculations. Specifically, we show that decoherence (spatial separation of wavepackets on different surfaces) is already contained in the equations of motion and does not require ad hoc augmentation.
Non-adiabatic molecular dynamics with complex quantum trajectories. II. The adiabatic representation
Zamstein, Noa; Tannor, David J.
2012-12-14
We present a complex quantum trajectory method for treating non-adiabatic dynamics. Each trajectory evolves classically on a single electronic surface but with complex position and momentum. The equations of motion are derived directly from the time-dependent Schroedinger equation, and the population exchange arises naturally from amplitude-transfer terms. In this paper the equations of motion are derived in the adiabatic representation to complement our work in the diabatic representation [N. Zamstein and D. J. Tannor, J. Chem. Phys. 137, 22A517 (2012)]. We apply our method to two benchmark models introduced by John Tully [J. Chem. Phys. 93, 1061 (1990)], and get very good agreement with converged quantum-mechanical calculations. Specifically, we show that decoherence (spatial separation of wavepackets on different surfaces) is already contained in the equations of motion and does not require ad hoc augmentation.
Electronic states and stability of selenium clusters
NASA Astrophysics Data System (ADS)
Li, Z. Q.; Yu, J. Z.; Ohno, K.; Gu, B. L.; Czajka, R.; Kasuya, A.; Nishina, Y.; Kawazoe, Y.
1995-07-01
Electronic structures and stability of Sen (n=3,4,5,6,7,8) clusters have been studied by using the discrete variational method in the framework of the local-density approximation. Binding energy, ionization potential, affinity energy, and other electronic properties using the structure models of Hohl et al. [Chem. Phys. Lett. 139, 540 (1987)] are presented and compared with the available experiments. In addition, a rectangular lattice arrangement of selenium clusters has been fabricated on highly oriented pyrolytic graphite, and examined by the scanning tunnel microscope image which was found to consist of a 0.72×0.85 nm2 lattice spacing with individual molecules of 0.53+/-0.05 nm in diameter. Theoretical calculations reproduce well the experimental observations.
Adiabatic evolution of plasma equilibrium
Grad, H.; Hu, P. N.; Stevens, D. C.
1975-01-01
A new theory of plasma equilibrium is introduced in which adiabatic constraints are specified. This leads to a mathematically nonstandard structure, as compared to the usual equilibrium theory, in which prescription of pressure and current profiles leads to an elliptic partial differential equation. Topologically complex configurations require further generalization of the concept of adiabaticity to allow irreversible mixing of plasma and magnetic flux among islands. Matching conditions across a boundary layer at the separatrix are obtained from appropriate conservation laws. Applications are made to configurations with planned islands (as in Doublet) and accidental islands (as in Tokamaks). Two-dimensional, axially symmetric, helically symmetric, and closed line equilibria are included. PMID:16578729
Taple-top imaging of the non-adiabatically driven isomerization in the acetylene cation
NASA Astrophysics Data System (ADS)
Beaulieu, Samuel; Ibrahim, Heide; Wales, Benji; Schmidt, Bruno E.; Thiré, Nicolas; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguere, Mathieu; Kieffer, Jean-Claude; Sanderson, Joe; Schuurman, Michael S.; Légaré, François
2014-05-01
One of the primary goals of modern ultrafast science is to follow nuclear and electronic evolution of molecules as they undergo a photo-chemical reaction. Most of the interesting dynamics phenomena in molecules occur when an electronically excited state is populated. When the energy difference between electronic ground and excited states is large, Free Electron Laser (FEL) and HHG-based VUV sources were, up to date, the only light sources able to efficiently initiate those non-adiabatic dynamics. We have developed a simple table-top approach to initiate those rich dynamics via multiphoton absorption. As a proof of principle, we studied the ultrafast isomerization of the acetylene cation. We have chosen this model system for isomerization since the internal conversion mechanism which leads to proton migration is still under debate since decades. Using 266 nm multiphoton absorption as a pump and 800 nm induced Coulomb Explosion as a probe, we have shoot the first high-resolution molecular movie of the non-adiabatically driven proton migration in the acetylene cation. The experimental results are in excellent agreement with high level ab initio trajectory simulations.
An investigation into low-lying electronic states of HCS{sub 2} via threshold photoelectron imaging
Qin, Zhengbo; Cong, Ran; Liu, Zhiling; Xie, Hua; Tang, Zichao E-mail: fanhj@dicp.ac.cn; Fan, Hongjun E-mail: fanhj@dicp.ac.cn
2014-06-07
Low-energy photoelectron imaging spectra of HCS{sub 2}{sup −} are reported for the first time. Vibrationally resolved photodetachment transitions from the ground state of HCS{sub 2}{sup −} to the ground state and low-lying excited states of HCS{sub 2} are observed. Combined with the ab intio calculations and Franck-Condon simulations, well-resolved vibrational spectra demonstrate definitive evidence for the resolution of the ground-state and excited states of HCS{sub 2} radical in the gaseous phase. The ground state and two low-lying excited states of HCS{sub 2} radical are assigned as {sup 2}B{sub 2}, {sup 2}A{sub 2}, and {sup 2}A{sub 1} states, respectively. The adiabatic electron affinity is determined to be 2.910 ± 0.007 eV. And the term energies of the excited states, T{sub 0} = 0.451 ± 0.009 eV and 0.553 ± 0.009 eV, are directly measured from the experimental data, respectively. Angular filtering photoelectron spectra are carried out to assist in the spectral band assignment.
Decoherence in a scalable adiabatic quantum computer
Ashhab, S.; Johansson, J. R.; Nori, Franco
2006-11-15
We consider the effects of decoherence on Landau-Zener crossings encountered in a large-scale adiabatic-quantum-computing setup. We analyze the dependence of the success probability--i.e., the probability for the system to end up in its new ground state--on the noise amplitude and correlation time. We determine the optimal sweep rate that is required to maximize the success probability. We then discuss the scaling of decoherence effects with increasing system size. We find that those effects can be important for large systems, even if they are small for each of the small building blocks.
Pressure Oscillations in Adiabatic Compression
ERIC Educational Resources Information Center
Stout, Roland
2011-01-01
After finding Moloney and McGarvey's modified adiabatic compression apparatus, I decided to insert this experiment into my physical chemistry laboratory at the last minute, replacing a problematic experiment. With insufficient time to build the apparatus, we placed a bottle between two thick textbooks and compressed it with a third textbook forced…
Adiabatic dynamics of magnetic vortices
NASA Astrophysics Data System (ADS)
Papanicolaou, N.
1994-03-01
We formulate a reasonably detailed adiabatic conjecture concerning the dynamics of skew deflection of magnetic vortices in a field gradient, which is expected to be valid at sufficiently large values of the winding number. The conjecture is consistent with the golden rule used to describe the dynamics of realistic magnetic bubbles and is verified here numerically within the 2-D isotropic Heisenberg model.
Butler, L.J.
1993-02-28
The adiabatic Born-Oppenheimer potential energy surface approximation is not valid for reaction of a wide variety of energetic materials and organic fuels; coupling between electronic states of reacting species plays a key role in determining the selectivity of the chemical reactions induced. This research program initially studies this coupling in (1) selective C-Br bond fission in 1,3- bromoiodopropane, (2) C-S:S-H bond fission branching in CH{sub 3}SH, and (3) competition between bond fission channels and H{sub 2} elimination in CH{sub 3}NH{sub 2}.
BLF-SSH polarons coupled to acoustic phonons in the adiabatic limit
NASA Astrophysics Data System (ADS)
Chandler, Carl J.; Marsiglio, F.
2014-12-01
We survey polaron formation in the Barisić-Labbé-Friedel and Su-Schrieffer-Heeger (BLF-SSH) model using acoustic phonons in the adiabatic limit. Multiple different numerical optimization routines and strong-coupling analytical calculations are used to find a robust ground-state energy for a wide range of coupling strengths. The electronic configuration and accompanying ionic distortions of the polaron were determined, as well as a nonzero critical coupling strength for polaron formation in two and three dimensions.
Non-adiabatic effects on the optical response of driven systems
NASA Astrophysics Data System (ADS)
Fregoso, Benjamin M.; Kolodrubetz, Michael; Moore, Joel
Periodically driven systems have received renewed interest due to their capacity to engineer non-trivial effective Hamiltonians. A characteristic of such systems is how they respond to weak periodicity-breaking drive, as for example when a laser is pulsed instead of continuous wave. We develop semi-classical equations of motion of a wave packet in the presence of electric and magnetic fields which are turned on non-adiabatically. We then show the emergence of significant corrections to electronic collective excitations and optical responses of topological insulator surface states, Weyl metals and semiconductor mono-chalcogenides.
Complex Study of Electronic States and Spectra of 3-Nitroformazans
NASA Astrophysics Data System (ADS)
Valiev, R. R.; Drozdova, A. K.; Petunin, P. V.; Postnikov, P. S.; Trusova, M. E.; Cherepanov, V. N.
2016-06-01
A theoretical and experimental study of electronic states and the absorption spectra of 3-nitroformazan molecules was conducted. The results of the study show that the first electron transition is σ→π-transition, and the second one is π→π-transition. The energies of the transitions calculated using methods RI-CC2 and TDDFT correlate well with the experimental measurements. The dependence of the first electron transition wavenumber on the degree of electron donating and accepting of substitutituents was studied using empirical constants. High correlation between the constants of Hammett, Braun, and wavenumbers (TDDFT) of the first electron transition shows that the description of electronic states of the studied 3-nitroformazans is correct.
NASA Astrophysics Data System (ADS)
Oh, Yun-Tak; Higashi, Yoichi; Chan, Ching-Kit; Han, Jung Hoon
2016-08-01
The Lang-Firsov Hamiltonian, a well-known solvable model of interacting fermion-boson system with sideband features in the fermion spectral weight, is generalized to have the time-dependent fermion-boson coupling constant. We show how to derive the two-time Green's function for the time-dependent problem in the adiabatic limit, defined as the slow temporal variation of the coupling over the characteristic oscillator period. The idea we use in deriving the Green's function is akin to the use of instantaneous basis states in solving the adiabatic evolution problem in quantum mechanics. With such "adiabatic Green's function" at hand we analyze the transient behavior of the spectral weight as the coupling is gradually tuned to zero. Time-dependent generalization of a related model, the spin-boson Hamiltonian, is analyzed in the same way. In both cases the sidebands arising from the fermion-boson coupling can be seen to gradually lose their spectral weights over time. Connections of our solution to the two-dimensional Dirac electrons coupled to quantized photons are discussed.
Semiclassical Monte Carlo: A first principles approach to non-adiabatic molecular dynamics
White, Alexander J.; Gorshkov, Vyacheslav N.; Wang, Ruixi; Tretiak, Sergei; Mozyrsky, Dmitry
2014-11-14
Modeling the dynamics of photophysical and (photo)chemical reactions in extended molecular systems is a new frontier for quantum chemistry. Many dynamical phenomena, such as intersystem crossing, non-radiative relaxation, and charge and energy transfer, require a non-adiabatic description which incorporate transitions between electronic states. Additionally, these dynamics are often highly sensitive to quantum coherences and interference effects. Several methods exist to simulate non-adiabatic dynamics; however, they are typically either too expensive to be applied to large molecular systems (10's-100's of atoms), or they are based on ad hoc schemes which may include severe approximations due to inconsistencies in classical and quantum mechanics. We present, in detail, an algorithm based on Monte Carlo sampling of the semiclassical time-dependent wavefunction that involves running simple surface hopping dynamics, followed by a post-processing step which adds little cost. The method requires only a few quantities from quantum chemistry calculations, can systematically be improved, and provides excellent agreement with exact quantum mechanical results. Here we show excellent agreement with exact solutions for scattering results of standard test problems. Additionally, we find that convergence of the wavefunction is controlled by complex valued phase factors, the size of the non-adiabatic coupling region, and the choice of sampling function. These results help in determining the range of applicability of the method, and provide a starting point for further improvement.
Semiclassical Monte Carlo: A first principles approach to non-adiabatic molecular dynamics
NASA Astrophysics Data System (ADS)
White, Alexander J.; Gorshkov, Vyacheslav N.; Wang, Ruixi; Tretiak, Sergei; Mozyrsky, Dmitry
2014-11-01
Modeling the dynamics of photophysical and (photo)chemical reactions in extended molecular systems is a new frontier for quantum chemistry. Many dynamical phenomena, such as intersystem crossing, non-radiative relaxation, and charge and energy transfer, require a non-adiabatic description which incorporate transitions between electronic states. Additionally, these dynamics are often highly sensitive to quantum coherences and interference effects. Several methods exist to simulate non-adiabatic dynamics; however, they are typically either too expensive to be applied to large molecular systems (10's-100's of atoms), or they are based on ad hoc schemes which may include severe approximations due to inconsistencies in classical and quantum mechanics. We present, in detail, an algorithm based on Monte Carlo sampling of the semiclassical time-dependent wavefunction that involves running simple surface hopping dynamics, followed by a post-processing step which adds little cost. The method requires only a few quantities from quantum chemistry calculations, can systematically be improved, and provides excellent agreement with exact quantum mechanical results. Here we show excellent agreement with exact solutions for scattering results of standard test problems. Additionally, we find that convergence of the wavefunction is controlled by complex valued phase factors, the size of the non-adiabatic coupling region, and the choice of sampling function. These results help in determining the range of applicability of the method, and provide a starting point for further improvement.
Tsirkin, S. S. Eremeev, S. V.; Chulkov, E. V.
2012-10-15
The contribution of inelastic electron-electron scattering to the decay rate of excitations in the surface states and first two image potential states at the Y-bar point on the surface is calculated in the GW approximation, and the quasi-momentum dependence of the corresponding contribution for the surface states is analyzed. The mechanisms of electron scattering in these states are studied, and the temperature dependence of the excitation lifetime is analyzed with allowance for the contribution of the electron-phonon interaction calculated earlier.
Electronic aperture control devised for solid state imaging system
NASA Technical Reports Server (NTRS)
Anders, R. A.; Callahan, D. E.; Mc Cann, D. H.
1968-01-01
Electronic means of performing the equivalent of automatic aperture control has been devised for the new class of television cameras that incorporates a solid state imaging device in the form of phototransistor mosaic sensors.
Effect of dephasing on stimulated Raman adiabatic passage
Ivanov, P.A.; Vitanov, N.V.; Bergmann, K.
2004-12-01
This work explores the effect of phase relaxation on the population transfer efficiency in stimulated Raman adiabatic passage (STIRAP). The study is based on the Liouville equation, which is solved analytically in the adiabatic limit. The transfer efficiency of STIRAP is found to decrease exponentially with the dephasing rate; this effect is stronger for shorter pulse delays and weaker for larger delays, since the transition time is found to be inversely proportional to the pulse delay. Moreover, it is found that the transfer efficiency of STIRAP in the presence of dephasing does not depend on the peak Rabi frequencies at all, as long as they are sufficiently large to enforce adiabatic evolution; hence increasing the field intensity cannot reduce the dephasing losses. It is shown also that for any dephasing rate, the final populations of the initial state and the intermediate state are equal. For strong dephasing all three populations tend to (1/3)
Shortcuts to adiabaticity in a time-dependent box
Campo, A. del; Boshier, M. G.
2012-01-01
A method is proposed to drive an ultrafast non-adiabatic dynamics of an ultracold gas trapped in a time-dependent box potential. The resulting state is free from spurious excitations associated with the breakdown of adiabaticity, and preserves the quantum correlations of the initial state up to a scaling factor. The process relies on the existence of an adiabatic invariant and the inversion of the dynamical self-similar scaling law dictated by it. Its physical implementation generally requires the use of an auxiliary expulsive potential. The method is extended to a broad family of interacting many-body systems. As illustrative examples we consider the ultrafast expansion of a Tonks-Girardeau gas and of Bose-Einstein condensates in different dimensions, where the method exhibits an excellent robustness against different regimes of interactions and the features of an experimentally realizable box potential. PMID:22970340
Adiabatic quantum pump in a zigzag graphene nanoribbon junction
NASA Astrophysics Data System (ADS)
Zhang, Lin
2015-11-01
The adiabatic electron transport is theoretically studied in a zigzag graphene nanoribbon (ZGNR) junction with two time-dependent pumping electric fields. By modeling a ZGNR p-n junction and applying the Keldysh Green’s function method, we find that a pumped charge current is flowing in the device at a zero external bias, which mainly comes from the photon-assisted tunneling process and the valley selection rule in an even-chain ZGNR junction. The pumped charge current and its ON and OFF states can be efficiently modulated by changing the system parameters such as the pumping frequency, the pumping phase difference, and the Fermi level. A ferromagnetic ZGNR device is also studied to generate a pure spin current and a fully polarized spin current due to the combined spin pump effect and the valley valve effect. Our finding might pave the way to manipulate the degree of freedom of electrons in a graphene-based electronic device. Project supported by the National Natural Science Foundation of China (Grant No. 110704033), the Natural Science Foundation of Jiangsu Province, China (Grant No. BK2010416), and the Natural Science Foundation for Colleges and Universities in Jiangsu Province, China (Grant No. 13KJB140005).
Detection of excited-state electron bubbles in superfluid helium.
Konstantinov, Denis; Maris, Humphrey J
2003-01-17
We report on experiments in which the pressure oscillation associated with a sound wave is used to explode electron bubbles in liquid helium. Using this technique, we are able to detect the presence of electron bubbles in excited states. PMID:12570553
REFLECTIONS ON THE TWO-STATE ELECTRON TRANSFER MODEL.
Brunschwig, B.S.
2000-01-12
There is general agreement that the two most important factors determining electron transfer rates in solution are the degree of electronic interaction between the donor and acceptor sites, and the changes in the nuclear configurations of the donor, acceptor, and surrounding medium that occur upon the gain or loss of an electron Ll-51. The electronic interaction of the sites will be very weak, and the electron transfer slow, when the sites are far apart or their interaction is symmetry or spin forbidden. Since electron motion is much faster than nuclear motion, energy conservation requires that, prior to the actual electron transfer, the nuclear configurations of the reactants and the surrounding medium adjust from their equilibrium values to a configuration (generally) intermediate between that of the reactants and products. In the case of electron transfer between , two metal complexes in a polar solvent, the nuclear configuration changes involve adjustments in the metal-ligand and intraligand bond lengths and angles, and changes in the orientations of the surrounding solvent molecules. In common with ordinary chemical reactions, an electron transfer reaction can then be described in terms of the motion of the system on an energy surface from the reactant equilibrium configuration (initial state) to the product equilibrium configuration (final state) via the activated complex (transition state) configuration.
The Ground and Two Lowest-lying Singlet Excited Electronic States of Copper Hydroxide (CuOH)
Wang, Suyun; Paul, Ankan; DeYonker, Nathan John; Yamaguchi, Yukio; Schaefer, Henry F
2005-07-12
The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Various ab initio methods, including self-consistent field (SCF), configuration interaction, coupled cluster (CC), and complete-active-space SCF (CASSCF), have been employed to study the electronic structure of copper hydroxide (CuOH). Geometries, total energies, dipole moments, harmonic vibrational frequencies, and zero-point vibrational energies are reported for the linear^{ 1}Σ^{+} and 1Π stationary points, and for the bent ground-state X˜ ^{1}A', and excited-states 2 ^{1}A" and 1^{ 1}A". Six different basis sets have been used in the study, Wachters/DZP being the smallest and QZVPP being the largest. The ground- and excited-state bending modes present imaginary frequencies for the linear stationary points, indicating that bent structures are more favorable. The effects of relativity for CuOH are important and have been considered using the Douglas–Kroll approach with cc-pVTZ/cc-pVTZ_DK and cc-pVQZ/cc-pVQZ_DK basis sets. The bent ground and two lowest-lying singlet excited states of the CuOH molecule are indeed energetically more stable than the corresponding linear structures. The optimized geometrical parameters for the X˜ ^{1}A' and 1 ^{1}A" states agree fairly well with available experimental values. However, the 2 ^{1}A' structure and rotational constants are in poor agreement with experiment, and we suggest that the latter are in error. The predicted adiabatic excitation energies are also inconsistent with the experimental values of 45.5 kcal mol^{-1} for the 2 ^{1}A' state and 52.6 kcal mol^{-1} for the 1^{ 1}A" state. The theoretical CC and CASSCF methods show lower
Ab initio adiabatic and diabatic potential-energy curves of the LiH molecule
NASA Astrophysics Data System (ADS)
Boutalib, A.; Gadéa, F. X.
1992-07-01
For nearly all states below the ionic limit [i.e., Li(2s, 2p, 3s, 3p, 3d, 4s, and 4p)+H] we perform the first adiabatic and diabatic studies. This treatment involves a nonempirical pseudopotential for Li and a full configuration-interaction treatment of the valence-electron system. Core-valence correlation is taken into account according to a core-polarization-potential method. We present an analysis of the diabatic curves and introduce appropriate small corrections accounting for basis-set limitations. For the low-lying states, our vibrational level spacings and spectroscopic constants are in excellent agreement with the available experimental data and with the best all-electron results. Experimental suggestions are given for the higher states.
Adiabatic approximation in time-dependent reduced-density-matrix functional theory
Requist, Ryan; Pankratov, Oleg
2010-04-15
With the aim of describing real-time electron dynamics, we introduce an adiabatic approximation for the equation of motion of the one-body reduced density matrix (one-matrix). The eigenvalues of the one-matrix, which represent the occupation numbers of single-particle orbitals, are obtained from the constrained minimization of the instantaneous ground-state energy functional rather than from their dynamical equations. The performance of the approximation vis-a-vis nonadiabatic effects is assessed in real-time simulations of a two-site Hubbard model. Due to Landau-Zener-type transitions, the system evolves into a nonstationary state with persistent oscillations in the observables. The amplitude of the oscillations displays a strongly nonmonotonic dependence on the strength of the electron-electron interaction and the rate of variation of the external potential. We interpret an associated resonance behavior in the phase of the oscillations in terms of 'scattering' with spectator energy levels. To clarify the motivation for the minimization condition, we derive a sequence of energy functionals E{sub v}{sup (n)}, for which the corresponding sequence of minimizing one-matrices is asymptotic to the exact one-matrix in the adiabatic limit.
Surface-electronic-state effects in electron emission from the Be(0001) surface
Archubi, C. D.; Gravielle, M. S.; Silkin, V. M.
2011-07-15
We study the electron emission produced by swift protons impinging grazingly on a Be(0001) surface. The process is described within a collisional formalism using the band-structure-based (BSB) approximation to represent the electron-surface interaction. The BSB model provides an accurate description of the electronic band structure of the solid and the surface-induced potential. Within this approach we derive both bulk and surface electronic states, with these latter characterized by a strong localization at the crystal surface. We found that such surface electronic states play an important role in double-differential energy- and angle-resolved electron emission probabilities, producing noticeable structures in the electron emission spectra.
Quantum Adiabatic Algorithms and Large Spin Tunnelling
NASA Technical Reports Server (NTRS)
Boulatov, A.; Smelyanskiy, V. N.
2003-01-01
We provide a theoretical study of the quantum adiabatic evolution algorithm with different evolution paths proposed in this paper. The algorithm is applied to a random binary optimization problem (a version of the 3-Satisfiability problem) where the n-bit cost function is symmetric with respect to the permutation of individual bits. The evolution paths are produced, using the generic control Hamiltonians H (r) that preserve the bit symmetry of the underlying optimization problem. In the case where the ground state of H(0) coincides with the totally-symmetric state of an n-qubit system the algorithm dynamics is completely described in terms of the motion of a spin-n/2. We show that different control Hamiltonians can be parameterized by a set of independent parameters that are expansion coefficients of H (r) in a certain universal set of operators. Only one of these operators can be responsible for avoiding the tunnelling in the spin-n/2 system during the quantum adiabatic algorithm. We show that it is possible to select a coefficient for this operator that guarantees a polynomial complexity of the algorithm for all problem instances. We show that a successful evolution path of the algorithm always corresponds to the trajectory of a classical spin-n/2 and provide a complete characterization of such paths.
Molecular electronics with single molecules in solid-state devices.
Moth-Poulsen, Kasper; Bjørnholm, Thomas
2009-09-01
The ultimate aim of molecular electronics is to understand and master single-molecule devices. Based on the latest results on electron transport in single molecules in solid-state devices, we focus here on new insights into the influence of metal electrodes on the energy spectrum of the molecule, and on how the electron transport properties of the molecule depend on the strength of the electronic coupling between it and the electrodes. A variety of phenomena are observed depending on whether this coupling is weak, intermediate or strong. PMID:19734925
Multi-pair states in electron-positron pair creation
NASA Astrophysics Data System (ADS)
Wöllert, Anton; Bauke, Heiko; Keitel, Christoph H.
2016-09-01
Ultra strong electromagnetic fields can lead to spontaneous creation of single or multiple electron-positron pairs. A quantum field theoretical treatment of the pair creation process combined with numerical methods provides a description of the fermionic quantum field state, from which all observables of the multiple electron-positron pairs can be inferred. This allows to study the complex multi-particle dynamics of electron-positron pair creation in-depth, including multi-pair statistics as well as momentum distributions and spin. To illustrate the potential benefit of this approach, it is applied to the intermediate regime of pair creation between nonperturbative Schwinger pair creation and perturbative multiphoton pair creation where the creation of multi-pair states becomes nonnegligible but cascades do not yet set in. Furthermore, it is demonstrated how spin and helicity of the created electrons and positrons are affected by the polarization of the counterpropagating laser fields, which induce the creation of electron-positron pairs.
NASA Astrophysics Data System (ADS)
Bogdanova, Yu. A.; Gubin, S. A.; Victorov, S. B.; Anikeev, A. A.
2016-06-01
An improved version of the equation of state model for two-component fluid mixtures whose molecules interact with the Exp-6 type potential has been proposed in previous works. The thermodynamic parameters of N2, O2, and CO2 shock-wave compression are calculated using the equation of state model for two-component fluid mixtures based on perturbation theory. Products of compression of these substances are two-component mixtures. Analogous calculations are also performed using an effective one-fluid model. A comparison of the results obtained with the available experimental data and results of Monte Carlo simulation allows us to conclude that the proposed theoretical equation of state model is superior to effective one-fluid model in accuracy and reliably describes the thermodynamic properties of two-component fluid mixtures in a wide pressure and temperature ranges.
Sen, Ananya; Matthews, Edward M.; Dessent, Caroline E. H. E-mail: xuebin.wang@pnnl.gov; Hou, Gao-Lei; Wang, Xue-Bin E-mail: xuebin.wang@pnnl.gov
2015-11-14
We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine, and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ∼1.7 eV, values that are lower than the RCB of the uncomplexed PtCl{sub 6}{sup 2−} dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl{sub 6}{sup 2−} ⋅ thymine and PtCl{sub 6}{sup 2−} ⋅ adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN){sub 4}{sup 2−} ⋅ nucleobase complexes [A. Sen et al., J. Phys. Chem. B 119, 11626 (2015)]. The observation of delayed electron emission bands in the PtCl{sub 6}{sup 2−} ⋅ nucleobase spectra obtained in this work, as for the previously studied Pt(CN){sub 4}{sup 2−} ⋅ nucleobase complexes, is attributed to one-photon excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase decays over a time scale long enough to
Stimulated Raman adiabatic passage in a three-level superconducting circuit
Kumar, K. S.; Vepsäläinen, A.; Danilin, S.; Paraoanu, G. S.
2016-01-01
The adiabatic manipulation of quantum states is a powerful technique that opened up new directions in quantum engineering—enabling tests of fundamental concepts such as geometrical phases and topological transitions, and holding the promise of alternative models of quantum computation. Here we benchmark the stimulated Raman adiabatic passage for circuit quantum electrodynamics by employing the first three levels of a transmon qubit. In this ladder configuration, we demonstrate a population transfer efficiency >80% between the ground state and the second excited state using two adiabatic Gaussian-shaped control microwave pulses. By doing quantum tomography at successive moments during the Raman pulses, we investigate the transfer of the population in time domain. Furthermore, we show that this protocol can be reversed by applying a third adiabatic pulse, we study a hybrid nondiabatic–adiabatic sequence, and we present experimental results for a quasi-degenerate intermediate level. PMID:26902454
Stimulated Raman adiabatic passage in a three-level superconducting circuit
NASA Astrophysics Data System (ADS)
Kumar, K. S.; Vepsäläinen, A.; Danilin, S.; Paraoanu, G. S.
2016-02-01
The adiabatic manipulation of quantum states is a powerful technique that opened up new directions in quantum engineering--enabling tests of fundamental concepts such as geometrical phases and topological transitions, and holding the promise of alternative models of quantum computation. Here we benchmark the stimulated Raman adiabatic passage for circuit quantum electrodynamics by employing the first three levels of a transmon qubit. In this ladder configuration, we demonstrate a population transfer efficiency >80% between the ground state and the second excited state using two adiabatic Gaussian-shaped control microwave pulses. By doing quantum tomography at successive moments during the Raman pulses, we investigate the transfer of the population in time domain. Furthermore, we show that this protocol can be reversed by applying a third adiabatic pulse, we study a hybrid nondiabatic-adiabatic sequence, and we present experimental results for a quasi-degenerate intermediate level.
Stimulated Raman adiabatic passage in a three-level superconducting circuit.
Kumar, K S; Vepsäläinen, A; Danilin, S; Paraoanu, G S
2016-01-01
The adiabatic manipulation of quantum states is a powerful technique that opened up new directions in quantum engineering--enabling tests of fundamental concepts such as geometrical phases and topological transitions, and holding the promise of alternative models of quantum computation. Here we benchmark the stimulated Raman adiabatic passage for circuit quantum electrodynamics by employing the first three levels of a transmon qubit. In this ladder configuration, we demonstrate a population transfer efficiency >80% between the ground state and the second excited state using two adiabatic Gaussian-shaped control microwave pulses. By doing quantum tomography at successive moments during the Raman pulses, we investigate the transfer of the population in time domain. Furthermore, we show that this protocol can be reversed by applying a third adiabatic pulse, we study a hybrid nondiabatic-adiabatic sequence, and we present experimental results for a quasi-degenerate intermediate level. PMID:26902454
Tunable topological states in electron-doped HTT-Pt
NASA Astrophysics Data System (ADS)
Zhang, Xiaoming; Wang, Zhenhai; Zhao, Mingwen; Liu, Feng
2016-04-01
Modulating topologically nontrivial states in trivial materials is of both scientific and technological interest. Using first-principles calculations, we propose a demonstration of electron-doping- (or gate-voltage-) induced multiple quantum states; namely, quantum spin Hall (QSH) and quantum anomalous Hall (QAH) states, in a single material of the organometallic framework (HTT-Pt) synthesized from triphenylene hexathiol molecules (HTT) and PtC l2 . At a low doping level, the trivial HTT-Pt converts to a QSH insulator protected by time-reversal symmetry (TRS). When the electronic doping concentration is further increased, TRS will be broken, making the HTT-Pt a QAH insulator. The band gaps of these topologically nontrivial states can be as large as 42.5 meV, suggesting robustness at high temperatures. The possibility of switching between the QSH and QAH states offers an intriguing platform for a different device paradigm by interfacing between QSH and QAH states.
NASA Astrophysics Data System (ADS)
Kato, Tsuyoshi; Ide, Yoshihiro; Yamanouchi, Kaoru
2015-12-01
We first calculate the ground-state molecular wave function of 1D model H2 molecule by solving the coupled equations of motion formulated in the extended multi-configuration time-dependent Hartree-Fock (MCTDHF) method by the imaginary time propagation. From the comparisons with the results obtained by the Born-Huang (BH) expansion method as well as with the exact wave function, we observe that the memory size required in the extended MCTDHF method is about two orders of magnitude smaller than in the BH expansion method to achieve the same accuracy for the total energy. Second, in order to provide a theoretical means to understand dynamical behavior of the wave function, we propose to define effective adiabatic potential functions and compare them with the conventional adiabatic electronic potentials, although the notion of the adiabatic potentials is not used in the extended MCTDHF approach. From the comparison, we conclude that by calculating the effective potentials we may be able to predict the energy differences among electronic states even for a time-dependent system, e.g., time-dependent excitation energies, which would be difficult to be estimated within the BH expansion approach.
Kato, Tsuyoshi; Ide, Yoshihiro; Yamanouchi, Kaoru
2015-12-31
We first calculate the ground-state molecular wave function of 1D model H{sub 2} molecule by solving the coupled equations of motion formulated in the extended multi-configuration time-dependent Hartree-Fock (MCTDHF) method by the imaginary time propagation. From the comparisons with the results obtained by the Born-Huang (BH) expansion method as well as with the exact wave function, we observe that the memory size required in the extended MCTDHF method is about two orders of magnitude smaller than in the BH expansion method to achieve the same accuracy for the total energy. Second, in order to provide a theoretical means to understand dynamical behavior of the wave function, we propose to define effective adiabatic potential functions and compare them with the conventional adiabatic electronic potentials, although the notion of the adiabatic potentials is not used in the extended MCTDHF approach. From the comparison, we conclude that by calculating the effective potentials we may be able to predict the energy differences among electronic states even for a time-dependent system, e.g., time-dependent excitation energies, which would be difficult to be estimated within the BH expansion approach.
NASA Astrophysics Data System (ADS)
Xie, Changjian; Zhu, Xiaolei; Ma, Jianyi; Yarkony, David R.; Xie, Daiqian; Guo, Hua
2015-03-01
Non-adiabatic processes play an important role in photochemistry, but the mechanism for conversion of electronic energy to chemical energy is still poorly understood. To explore the possibility of vibrational control of non-adiabatic dynamics in a prototypical photoreaction, namely, the A-band photodissociation of NH 3 ( X ˜ 1 A 1 ) , full-dimensional state-to-state quantum dynamics of symmetric or antisymmetric stretch excited NH 3 ( X ˜ 1 A 1 ) is investigated on recently developed coupled diabatic potential energy surfaces. The experimentally observed H atom kinetic energy distributions are reproduced. However, contrary to previous inferences, the NH 2 ( A ˜ 2 A 1 ) /NH 2 ( X ˜ 2 B 1 ) branching ratio is found to be small regardless of the initial preparation of NH 3 ( X ˜ 1 A 1 ) , while the internal state distribution of the preeminent fragment, NH 2 ( X ˜ 2 B 1 ) , is found to depend strongly on the initial vibrational excitation of NH 3 ( X ˜ 1 A 1 ) . The slow H atoms in photodissociation mediated by the antisymmetric stretch fundamental state are due to energy sequestered in the internally excited NH 2 ( X ˜ 2 B 1 ) fragment, rather than in NH 2 ( A ˜ 2 A 1 ) as previously proposed. The high internal excitation of the NH 2 ( X ˜ 2 B 1 ) fragment is attributed to the torques exerted on the molecule as it passes through the conical intersection seam to the ground electronic state of NH3. Thus in this system, contrary to previous assertions, the control of electronic state branching by selective excitation of ground state vibrational modes is concluded to be ineffective. The juxtaposition of precise quantum mechanical results with complementary results based on quasi-classical surface hopping trajectories provides significant insights into the non-adiabatic process.
Fast electronic resistance switching involving hidden charge density wave states
Vaskivskyi, I.; Mihailovic, I. A.; Brazovskii, S.; Gospodaric, J.; Mertelj, T.; Svetin, D.; Sutar, P.; Mihailovic, D.
2016-01-01
The functionality of computer memory elements is currently based on multi-stability, driven either by locally manipulating the density of electrons in transistors or by switching magnetic or ferroelectric order. Another possibility is switching between metallic and insulating phases by the motion of ions, but their speed is limited by slow nucleation and inhomogeneous percolative growth. Here we demonstrate fast resistance switching in a charge density wave system caused by pulsed current injection. As a charge pulse travels through the material, it converts a commensurately ordered polaronic Mott insulating state in 1T–TaS2 to a metastable electronic state with textured domain walls, accompanied with a conversion of polarons to band states, and concurrent rapid switching from an insulator to a metal. The large resistance change, high switching speed (30 ps) and ultralow energy per bit opens the way to new concepts in non-volatile memory devices manipulating all-electronic states. PMID:27181483
Fast electronic resistance switching involving hidden charge density wave states
NASA Astrophysics Data System (ADS)
Vaskivskyi, I.; Mihailovic, I. A.; Brazovskii, S.; Gospodaric, J.; Mertelj, T.; Svetin, D.; Sutar, P.; Mihailovic, D.
2016-05-01
The functionality of computer memory elements is currently based on multi-stability, driven either by locally manipulating the density of electrons in transistors or by switching magnetic or ferroelectric order. Another possibility is switching between metallic and insulating phases by the motion of ions, but their speed is limited by slow nucleation and inhomogeneous percolative growth. Here we demonstrate fast resistance switching in a charge density wave system caused by pulsed current injection. As a charge pulse travels through the material, it converts a commensurately ordered polaronic Mott insulating state in 1T-TaS2 to a metastable electronic state with textured domain walls, accompanied with a conversion of polarons to band states, and concurrent rapid switching from an insulator to a metal. The large resistance change, high switching speed (30 ps) and ultralow energy per bit opens the way to new concepts in non-volatile memory devices manipulating all-electronic states.
Fast electronic resistance switching involving hidden charge density wave states.
Vaskivskyi, I; Mihailovic, I A; Brazovskii, S; Gospodaric, J; Mertelj, T; Svetin, D; Sutar, P; Mihailovic, D
2016-01-01
The functionality of computer memory elements is currently based on multi-stability, driven either by locally manipulating the density of electrons in transistors or by switching magnetic or ferroelectric order. Another possibility is switching between metallic and insulating phases by the motion of ions, but their speed is limited by slow nucleation and inhomogeneous percolative growth. Here we demonstrate fast resistance switching in a charge density wave system caused by pulsed current injection. As a charge pulse travels through the material, it converts a commensurately ordered polaronic Mott insulating state in 1T-TaS2 to a metastable electronic state with textured domain walls, accompanied with a conversion of polarons to band states, and concurrent rapid switching from an insulator to a metal. The large resistance change, high switching speed (30 ps) and ultralow energy per bit opens the way to new concepts in non-volatile memory devices manipulating all-electronic states. PMID:27181483
Robust adiabatic sum frequency conversion.
Suchowski, Haim; Prabhudesai, Vaibhav; Oron, Dan; Arie, Ady; Silberberg, Yaron
2009-07-20
We discuss theoretically and demonstrate experimentally the robustness of the adiabatic sum frequency conversion method. This technique, borrowed from an analogous scheme of robust population transfer in atomic physics and nuclear magnetic resonance, enables the achievement of nearly full frequency conversion in a sum frequency generation process for a bandwidth up to two orders of magnitude wider than in conventional conversion schemes. We show that this scheme is robust to variations in the parameters of both the nonlinear crystal and of the incoming light. These include the crystal temperature, the frequency of the incoming field, the pump intensity, the crystal length and the angle of incidence. Also, we show that this extremely broad bandwidth can be tuned to higher or lower central wavelengths by changing either the pump frequency or the crystal temperature. The detailed study of the properties of this converter is done using the Landau-Zener theory dealing with the adiabatic transitions in two level systems. PMID:19654679
Adiabatic condition and the quantum hitting time of Markov chains
Krovi, Hari; Ozols, Maris; Roland, Jeremie
2010-08-15
We present an adiabatic quantum algorithm for the abstract problem of searching marked vertices in a graph, or spatial search. Given a random walk (or Markov chain) P on a graph with a set of unknown marked vertices, one can define a related absorbing walk P{sup '} where outgoing transitions from marked vertices are replaced by self-loops. We build a Hamiltonian H(s) from the interpolated Markov chain P(s)=(1-s)P+sP{sup '} and use it in an adiabatic quantum algorithm to drive an initial superposition over all vertices to a superposition over marked vertices. The adiabatic condition implies that, for any reversible Markov chain and any set of marked vertices, the running time of the adiabatic algorithm is given by the square root of the classical hitting time. This algorithm therefore demonstrates a novel connection between the adiabatic condition and the classical notion of hitting time of a random walk. It also significantly extends the scope of previous quantum algorithms for this problem, which could only obtain a full quadratic speedup for state-transitive reversible Markov chains with a unique marked vertex.
Electronic Ground and Excited State Spectral Diffusion of a Photocatalyst
NASA Astrophysics Data System (ADS)
Kiefer, Laura M.; King, John T.; Kubarych, Kevin J.
2014-06-01
Re(bpy)(CO)_3Cl is a well studied CO_2 reduction catalyst, known for its ability as both a photosensitizer and a catalyst with a high quantum yield and product selectivity. The catalysis reaction is initiated by a 400 nm excitation, followed by an intersystem crossing (ISC) and re-equilibration in the lowest triplet state. We utilize the quasi-equilibrium nature of this long-lived triplet metal-to-ligand charge-transfer (3MLCT) state to completely characterize the solvent dynamics using the technique of transient two-dimensional infrared (t-2DIR) spectroscopy to extract observables such as the frequency-frequency correlation function (FFCF), an equilibrium function. The electronic ground state solvent dynamics are characterized using equilibrium two-dimensional infrared spectroscopy (2D IR). Our technique allows us to independently observe the solvent dynamics of different electronic states and compare them. In this study, three carbonyl stretching modes were utilized to probe both the intramolecular and solvent environments in each electronic state. In the electronic ground state, the totally symmetric mode exhibits pure homogeneous broadening and a lack of spectral dynamics, while the two other modes have similar FFCF decay times of ˜ 1.5 ps. In the 3MLCT, however, all three modes experience similar spectral dynamics and have a FFCF decay time of ˜ 4.5 ps, three times slower than in the electronic ground state. Our technique allows us to directly observe the differences in spectral dynamics of the ground and excited electronic states and allows us to attribute the differences to specific origins such as solvent-solute coupling and molecular flexibility.
Adiabatic Rosen-Zener interferometry with ultracold atoms
Fu Libin; Ye Defa; Lee Chaohong; Zhang Weiping; Liu Jie
2009-07-15
We propose a time-domain 'interferometer' based on double-well ultracold atoms through a so-called adiabatic Rosen-Zener process, that is, the barrier between two wells is ramped down slowly, held for a while, and then ramped back. After the adiabatic Rosen-Zener process, we count the particle population in each well. We find that the final occupation probability shows nice interference fringes. The fringe pattern is sensitive to the initial state as well as the intrinsic parameters of the system such as interatomic interaction or energy bias between two wells. The underlying mechanism is revealed and possible applications are discussed.
Quantum dynamics by the constrained adiabatic trajectory method
Leclerc, A.; Jolicard, G.; Guerin, S.; Killingbeck, J. P.
2011-03-15
We develop the constrained adiabatic trajectory method (CATM), which allows one to solve the time-dependent Schroedinger equation constraining the dynamics to a single Floquet eigenstate, as if it were adiabatic. This constrained Floquet state (CFS) is determined from the Hamiltonian modified by an artificial time-dependent absorbing potential whose forms are derived according to the initial conditions. The main advantage of this technique for practical implementation is that the CFS is easy to determine even for large systems since its corresponding eigenvalue is well isolated from the others through its imaginary part. The properties and limitations of the CATM are explored through simple examples.
Two-electron states and state exchange time control in parabolic quantum dot
NASA Astrophysics Data System (ADS)
Baghdasaryan, D. A.; Kazaryan, E. M.; Sarkisyan, H. A.
2014-04-01
Using the Heisenberg uncertainty relationship and the stationary perturbation theory we consider two-electron states in a spherically symmetric parabolic quantum dot (parabolic helium atom). The dependence of ground-state energy on the QD size is studied. The energy of two-electron system monotonically decreases with QD radius increase. The problem of the state exchange time control in QD is discussed, taking into account the spins of the electrons in the Russell-Saunders approximation. With the increase of the QD radius the state exchange time increases.
Singularity of the time-energy uncertainty in adiabatic perturbation and cycloids on a Bloch sphere.
Oh, Sangchul; Hu, Xuedong; Nori, Franco; Kais, Sabre
2016-01-01
Adiabatic perturbation is shown to be singular from the exact solution of a spin-1/2 particle in a uniformly rotating magnetic field. Due to a non-adiabatic effect, its quantum trajectory on a Bloch sphere is a cycloid traced by a circle rolling along an adiabatic path. As the magnetic field rotates more and more slowly, the time-energy uncertainty, proportional to the length of the quantum trajectory, calculated by the exact solution is entirely different from the one obtained by the adiabatic path traced by the instantaneous eigenstate. However, the non-adiabatic Aharonov-Anandan geometric phase, measured by the area enclosed by the exact path, approaches smoothly the adiabatic Berry phase, proportional to the area enclosed by the adiabatic path. The singular limit of the time-energy uncertainty and the regular limit of the geometric phase are associated with the arc length and arc area of the cycloid on a Bloch sphere, respectively. Prolate and curtate cycloids are also traced by different initial states outside and inside of the rolling circle, respectively. The axis trajectory of the rolling circle, parallel to the adiabatic path, is shown to be an example of transitionless driving. The non-adiabatic resonance is visualized by the number of cycloid arcs. PMID:26916031
Singularity of the time-energy uncertainty in adiabatic perturbation and cycloids on a Bloch sphere
Oh, Sangchul; Hu, Xuedong; Nori, Franco; Kais, Sabre
2016-01-01
Adiabatic perturbation is shown to be singular from the exact solution of a spin-1/2 particle in a uniformly rotating magnetic field. Due to a non-adiabatic effect, its quantum trajectory on a Bloch sphere is a cycloid traced by a circle rolling along an adiabatic path. As the magnetic field rotates more and more slowly, the time-energy uncertainty, proportional to the length of the quantum trajectory, calculated by the exact solution is entirely different from the one obtained by the adiabatic path traced by the instantaneous eigenstate. However, the non-adiabatic Aharonov- Anandan geometric phase, measured by the area enclosed by the exact path, approaches smoothly the adiabatic Berry phase, proportional to the area enclosed by the adiabatic path. The singular limit of the time-energy uncertainty and the regular limit of the geometric phase are associated with the arc length and arc area of the cycloid on a Bloch sphere, respectively. Prolate and curtate cycloids are also traced by different initial states outside and inside of the rolling circle, respectively. The axis trajectory of the rolling circle, parallel to the adiabatic path, is shown to be an example of transitionless driving. The non-adiabatic resonance is visualized by the number of cycloid arcs. PMID:26916031
NASA Astrophysics Data System (ADS)
Farasat, M.; Shojaei, S. H. R.; Morini, F.; Golzan, M. M.; Deleuze, M. S.
2016-04-01
The electronic structure, electron binding energy spectrum and (e, 2e) momentum distributions of aniline have been theoretically predicted at an electron impact energy of 1.500 keV on the basis of Born-Oppenheimer molecular dynamical simulations, in order to account for thermally induced nuclear motions in the initial electronic ground state. Most computed momentum profiles are rather insensitive to thermally induced alterations of the molecular structure, with the exception of the profiles corresponding to two ionization bands at electron binding energies comprised between ˜10.0 and ˜12.0 eV (band C) and between ˜16.5 and ˜20.0 eV (band G). These profiles are found to be strongly influenced by nuclear dynamics in the electronic ground state, especially in the low momentum region. The obtained results show that thermal averaging smears out most generally the spectral fingerprints that are induced by nitrogen inversion.
Alternative ground states enable pathway switching in biological electron transfer
Abriata, Luciano A.; Álvarez-Paggi, Damián; Ledesma, Gabriela N.; Blackburn, Ninian J.; Vila, Alejandro J.; Murgida, Daniel H.
2012-01-01
Electron transfer is the simplest chemical reaction and constitutes the basis of a large variety of biological processes, such as photosynthesis and cellular respiration. Nature has evolved specific proteins and cofactors for these functions. The mechanisms optimizing biological electron transfer have been matter of intense debate, such as the role of the protein milieu between donor and acceptor sites. Here we propose a mechanism regulating long-range electron transfer in proteins. Specifically, we report a spectroscopic, electrochemical, and theoretical study on WT and single-mutant CuA redox centers from Thermus thermophilus, which shows that thermal fluctuations may populate two alternative ground-state electronic wave functions optimized for electron entry and exit, respectively, through two different and nearly perpendicular pathways. These findings suggest a unique role for alternative or “invisible” electronic ground states in directional electron transfer. Moreover, it is shown that this energy gap and, therefore, the equilibrium between ground states can be fine-tuned by minor perturbations, suggesting alternative ways through which protein–protein interactions and membrane potential may optimize and regulate electron–proton energy transduction. PMID:23054836
Integrating proton coupled electron transfer (PCET) and excited states
Gagliardi, Christopher J.; Westlake, Brittany C.; Kent, Caleb A.; Paul, Jared J.; Papanikolas, John M.; Meyer, Thomas J.
2010-11-01
In many of the chemical steps in photosynthesis and artificial photosynthesis, proton coupled electron transfer (PCET) plays an essential role. An important issue is how excited state reactivity can be integrated with PCET to carry out solar fuel reactions such as water splitting into hydrogen and oxygen or water reduction of CO_{2} to methanol or hydrocarbons. The principles behind PCET and concerted electron–proton transfer (EPT) pathways are reasonably well understood. In Photosystem II antenna light absorption is followed by sensitization of chlorophyll P_{680} and electron transfer quenching to give P_{680}^{+}. The oxidized chlorophyll activates the oxygen evolving complex (OEC), a CaMn4 cluster, through an intervening tyrosine–histidine pair, Y_{Z}. EPT plays a major role in a series of four activation steps that ultimately result in loss of 4e^{-}/4H^{+} from the OEC with oxygen evolution. The key elements in photosynthesis and artificial photosynthesis – light absorption, excited state energy and electron transfer, electron transfer activation of multiple-electron, multiple-proton catalysis – can also be assembled in dye sensitized photoelectrochemical synthesis cells (DS-PEC). In this approach, molecular or nanoscale assemblies are incorporated at separate electrodes for coupled, light driven oxidation and reduction. Separate excited state electron transfer followed by proton transfer can be combined in single semi-concerted steps (photo-EPT) by photolysis of organic charge transfer excited states with H-bonded bases or in metal-to-ligand charge transfer (MLCT) excited states in pre-associated assemblies with H-bonded electron transfer donors or acceptors. In these assemblies, photochemically induced electron and proton transfer occur in a single, semi-concerted event to give high-energy, redox active intermediates.
SIMULATION OF CONTINUOUS-CONTACT SEPARATION PROCESSES: MULTICOMPONENT, ADIABATIC ABSORPTION
A new algorithm has been developed for the steady-state simulation of multicomponent, adiabatic absorption in packed columns. The system of differential model equations that describe the physical absorption process is reduced to algebraic equations by using a finite difference me...
Computing electronic structures: A new multiconfiguration approach for excited states
Cances, Eric . E-mail: cances@cermics.enpc.fr; Galicher, Herve . E-mail: galicher@cermics.enpc.fr; Lewin, Mathieu . E-mail: lewin@cermic.enpc.fr
2006-02-10
We present a new method for the computation of electronic excited states of molecular systems. This method is based upon a recent theoretical definition of multiconfiguration excited states [due to one of us, see M. Lewin, Solutions of the multiconfiguration equations in quantum chemistry, Arch. Rat. Mech. Anal. 171 (2004) 83-114]. Our algorithm, dedicated to the computation of the first excited state, always converges to a stationary state of the multiconfiguration model, which can be interpreted as an approximate excited state of the molecule. The definition of this approximate excited state is variational. An interesting feature is that it satisfies a non-linear Hylleraas-Undheim-MacDonald type principle: the energy of the approximate excited state is an upper bound to the true excited state energy of the N-body Hamiltonian. To compute the first excited state, one has to deform paths on a manifold, like this is usually done in the search for transition states between reactants and products on potential energy surfaces. We propose here a general method for the deformation of paths which could also be useful in other settings. We also compare our method to other approaches used in Quantum Chemistry and give some explanation of the unsatisfactory behaviours which are sometimes observed when using the latter. Numerical results for the special case of two-electron systems are provided: we compute the first singlet excited state potential energy surface of the H {sub 2} molecule.
Estévez-Fregoso, Mar; Hernández-Trujillo, Jesús
2016-04-28
The four lowest singlet electronic states of benzene, the acenes from naphthalene to pentacene, phenanthrene and pyrene were studied by means of theoretical methods. Their vertical excitation energies from the ground electronic states were computed at the CASPT2 approximation. As an attempt to explain the trends observed in the excitation energies, several descriptors based on the electron density were used and the similarity of these molecules with their ground state counterparts was analyzed. It was found that the changes of the topological properties at the C-C bond critical points do not explain the decreasing trends for the excitation energies with the increase of the number of rings, in part because the small changes that take place in the electron density occur above and below the molecular plane. A similarity index based on electron delocalization between quantum topological atoms was defined to compare a molecule in two different electronic states. It was found that, mainly for the acenes, this index goes in line with the excitation energies to the first excited state. Implications of the changes in electron delocalization on the aromatic character of these molecules are also discussed. In general, local aromaticity decreases upon excitation. PMID:26795361
Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S
2015-10-14
Using a simple model Hamiltonian, the three correction terms for Born-Oppenheimer (BO) breakdown, the adiabatic diagonal correction (DC), the first-derivative momentum non-adiabatic correction (FD), and the second-derivative kinetic-energy non-adiabatic correction (SD), are shown to all contribute to thermodynamic and spectroscopic properties as well as to thermal non-diabatic chemical reaction rates. While DC often accounts for >80% of thermodynamic and spectroscopic property changes, the commonly used practice of including only the FD correction in kinetics calculations is rarely found to be adequate. For electron-transfer reactions not in the inverted region, the common physical picture that diabatic processes occur because of surface hopping at the transition state is proven inadequate as the DC acts first to block access, increasing the transition state energy by (ℏω)(2)λ/16J(2) (where λ is the reorganization energy, J the electronic coupling and ω the vibration frequency). However, the rate constant in the weakly-coupled Golden-Rule limit is identified as being only inversely proportional to this change rather than exponentially damped, owing to the effects of tunneling and surface hopping. Such weakly-coupled long-range electron-transfer processes should therefore not be described as "non-adiabatic" processes as they are easily described by Born-Huang ground-state adiabatic surfaces made by adding the DC to the BO surfaces; instead, they should be called just "non-Born-Oppenheimer" processes. The model system studied consists of two diabatic harmonic potential-energy surfaces coupled linearly through a single vibration, the "two-site Holstein model". Analytical expressions are derived for the BO breakdown terms, and the model is solved over a large parameter space focusing on both the lowest-energy spectroscopic transitions and the quantum dynamics of coherent-state wavepackets. BO breakdown is investigated pertinent to: ammonia inversion, aromaticity
Arbitrary Amplitude DIA and DA Solitary Waves in Adiabatic Dusty Plasmas
Mamun, A. A.; Jahan, N.; Shukla, P. K.
2008-10-15
The dust-ion-acoustic (DIA) as well as the dust-acoustic (DA) solitary waves (SWs) in an adiabatic dusty plasma are investigated by the pseudo-potential approach which is valid for arbitrary amplitude SWs. The role of the adiabaticity of electrons and ions in modifying the basic features (polarity, speed, amplitude and width) of arbitrary amplitude DIA and DA SWs are explicitly examined. It is found that the effects of the adiabaticity of electrons and ions significantly modify the basic features (polarity, speed, amplitude and width) of the DIA and DA SWs. The implications of our results in space and laboratory dusty plasmas are briefly discussed.
Nonadiabatic Transitions in Adiabatic Rapid Passage
NASA Astrophysics Data System (ADS)
Lu, T.; Miao, X.; Metcalf, H.
2006-05-01
Optical forces much larger than the ordinary radiative force can be achieved on a two-level atom by multiple repetitions of adiabatic rapid passage sweeps with counterpropagating light beams. Chirped light pulses drive the atom-laser system up a ladder of dressed state energy sheets on sequential trajectories, thereby decreasing the atomic kinetic energy. Nonadiabatic transitions between the energy sheets must be avoided for this process to be effective. We have calculated the nonadiabatic transition probability for various chirped light pulses numerically. These results were compared to the first Demkov-Kunike model and the well-known Landau-Zener model. In addition, an analytical form of the nonadiabatic transition probability has been found for linearly chirped pulses and an approximate form for generic symmetric finite-time pulses has been found for the entire parameter space using the technique of unitary integration. From this, the asymptotic transition probability in the adiabatic limit was derived. T. Lu, X. Miao, and H. Metcalf, Phys., Rev. A 71 061405(R) (2005). Yu. Demkov and M. Kunike, Vestn. Leningr. Univ. Fis. Khim., 16, 39 (1969); K.-A. Suominen and B. Garraway, Phys. Rev. A45, 374 (1992)
Effect of the Heat Pipe Adiabatic Region.
Brahim, Taoufik; Jemni, Abdelmajid
2014-04-01
The main motivation of conducting this work is to present a rigorous analysis and investigation of the potential effect of the heat pipe adiabatic region on the flow and heat transfer performance of a heat pipe under varying evaporator and condenser conditions. A two-dimensional steady-state model for a cylindrical heat pipe coupling, for both regions, is presented, where the flow of the fluid in the porous structure is described by Darcy-Brinkman-Forchheimer model which accounts for the boundary and inertial effects. The model is solved numerically by using the finite volumes method, and a fortran code was developed to solve the system of equations obtained. The results show that a phase change can occur in the adiabatic region due to temperature gradient created in the porous structure as the heat input increases and the heat pipe boundary conditions change. A recirculation zone may be created at the condenser end section. The effect of the heat transfer rate on the vapor radial velocities and the performance of the heat pipe are discussed. PMID:24895467
Trapping Image State Electrons on Graphene Layers and Islands
NASA Astrophysics Data System (ADS)
Dadap, Jerry; Niesner, Daniel; Fauster, Thomas; Zaki, Nader; Knox, Kevin; Yeh, Po-Chi; Bhandari, Rohan; Osgood, Richard M.; Petrovic, Marin; Kralj, Marko
2012-02-01
The understanding of graphene-metal interfaces is of utmost importance in graphene transport phenomena. To probe this interface we use time- and angle-resolved two-photon photoemission to map the bound, unoccupied electronic structure of the weakly coupled graphene/Ir(111) system. The energy, dispersion, and lifetime of the lowest three image-potential states are measured. In addition, the weak interaction between Ir and the smooth, epitaxial graphene permits observation of resonant transitions from an unquenched Shockley-type surface state of the Ir substrate to graphene/Ir image-potential states. The image-potential-state lifetimes are comparable to those of mid-gap clean metal surfaces. Evidence of localization of the excited image-state electrons on single-atom-layer graphene islands is provided by coverage-dependent measurements.
Yamamoto, Kentaro Takatsuka, Kazuo
2014-03-28
We develop the path-branching representation for nonadiabatic electron wavepacket dynamics [T. Yonehara and K. Takatsuka, J. Chem. Phys. 132, 244102 (2010)] so as to treat dynamics in an energy range comparable to the barrier height of adiabatic potential energy curves. With this representation two characteristic chemical reaction dynamics are studied, in which an incident nuclear wavepacket encounters a potential barrier, on top of which lies another nonadiabatically coupled adiabatic potential curve: (1) Dynamics of initial paths coming into the nonadiabatic interaction region with energy lower than the barrier height. They branch into two pieces (and repeat branching subsequently), the upper counterparts of which can penetrate into a classically inaccessible high energy region and eventually branch back to the product region on the ground state curve. This is so to say surmounting the potential barrier via nonadiabatically coupled excited state, and phenomenologically looks like the so-called deep tunneling. (2) Dynamics of classical paths whose initial energies are a little higher than the barrier but may be lower than the bottom of the excited state. They can undergo branching and some of those components are trapped on top of the potential barrier, being followed by the population decay down to the lower state flowing both to product and reactant sites. Such expectations arising from the path-branching representation are numerically confirmed with full quantum mechanical wavepacket dynamics. This phenomenon may be experimentally observed as time-delayed pulses of wavepacket trains.
Yamamoto, Kentaro; Takatsuka, Kazuo
2014-03-28
We develop the path-branching representation for nonadiabatic electron wavepacket dynamics [T. Yonehara and K. Takatsuka, J. Chem. Phys. 132, 244102 (2010)] so as to treat dynamics in an energy range comparable to the barrier height of adiabatic potential energy curves. With this representation two characteristic chemical reaction dynamics are studied, in which an incident nuclear wavepacket encounters a potential barrier, on top of which lies another nonadiabatically coupled adiabatic potential curve: (1) Dynamics of initial paths coming into the nonadiabatic interaction region with energy lower than the barrier height. They branch into two pieces (and repeat branching subsequently), the upper counterparts of which can penetrate into a classically inaccessible high energy region and eventually branch back to the product region on the ground state curve. This is so to say surmounting the potential barrier via nonadiabatically coupled excited state, and phenomenologically looks like the so-called deep tunneling. (2) Dynamics of classical paths whose initial energies are a little higher than the barrier but may be lower than the bottom of the excited state. They can undergo branching and some of those components are trapped on top of the potential barrier, being followed by the population decay down to the lower state flowing both to product and reactant sites. Such expectations arising from the path-branching representation are numerically confirmed with full quantum mechanical wavepacket dynamics. This phenomenon may be experimentally observed as time-delayed pulses of wavepacket trains. PMID:24697428
Photoionization of furan from the ground and excited electronic states
NASA Astrophysics Data System (ADS)
Ponzi, Aurora; Sapunar, Marin; Angeli, Celestino; Cimiraglia, Renzo; Došlić, Nada; Decleva, Piero
2016-02-01
Here we present a comparative computational study of the photoionization of furan from the ground and the two lowest-lying excited electronic states. The study aims to assess the quality of the computational methods currently employed for treating bound and continuum states in photoionization. For the ionization from the ground electronic state, we show that the Dyson orbital approach combined with an accurate solution of the continuum one particle wave functions in a multicenter B-spline basis, at the density functional theory (DFT) level, provides cross sections and asymmetry parameters in excellent agreement with experimental data. On the contrary, when the Dyson orbitals approach is combined with the Coulomb and orthogonalized Coulomb treatments of the continuum, the results are qualitatively different. In excited electronic states, three electronic structure methods, TDDFT, ADC(2), and CASSCF, have been used for the computation of the Dyson orbitals, while the continuum was treated at the B-spline/DFT level. We show that photoionization observables are sensitive probes of the nature of the excited states as well as of the quality of excited state wave functions. This paves the way for applications in more complex situations such as time resolved photoionization spectroscopy.
On the correct electronic ground state of Tc( g )
Rard, J.A. ); Rand, M.H. ); Thornback, J.R. ); Wanner, H. )
1991-05-01
The electronic ground state of Tc({ital g}) is {sup 6}{ital S}{sub 5/2}, which arises from a 4{ital d}{sup 5}5{ital s}{sup 2} valence electron configuration. However, there are several treatises and review articles in which the ground state is incorrectly given as {ital S}{sub 9/2} with a valence electron configuration of 4{ital d}{sup 6}5{ital s}{sup 1}. The origin of this incorrect assignment was traced to the misinterpretation of a paper on the hyperfine splitting of the optical spectrum of technetium, and to confusion between nuclear and electronic spins.
NASA Astrophysics Data System (ADS)
Acharya, Shree Ram; Baral, Nisha; Turkowski, Volodymyr; Rahman, Talat S.
2015-03-01
We apply Dynamical Mean-Field Theory (DMFT) to calculate the non-adiabatic (frequency-dependent) exchange-correlation kernel for the three-dimensional Hubbard model. We analyze the dependence of the kernel on the electron doping, local Coulomb repulsion and frequency by using three different impurity solvers: Hubbard-I, Iterative Perturbation Theory (IPT) and Continuous-Time Quantum Monte Carlo (CT-QMC). From the calculated data, we obtain approximate analytical expressions for the kernel. We apply the exact numerical and analytical kernels to study the non-equilibrium response of the system for applied ultrafast laser pulse. We demonstrate that the non-adiabaticity of the kernel plays an important role in the system response; in particular, leading to new excited-states involved in the system dynamics. Work supported in part by DOE Grant No. DOE-DE-FG02-07ER46354.
Non-adiabatic and adiabatic transitions at level crossing with decay: two- and three-level systems
NASA Astrophysics Data System (ADS)
Kenmoe, M. B.; Mkam Tchouobiap, S. E.; Kenfack Sadem, C.; Tchapda, A. B.; Fai, L. C.
2015-03-01
We investigate the Landau-Zener (LZ) like dynamics of decaying two- and three-level systems with decay rates {{Γ }1} and {{Γ }2} for levels with minimum and maximum spin projection. Non-adiabatic and adiabatic transition probabilities are calculated from diabatic and adiabatic bases for two- and three-level systems. We extend the familiar two-level model of atoms with decay from the excited state out of the system into the hierarchy of three-level models which can be solved analytically or computationally in a non-perturbative manner. Exact analytical solutions are obtained within the framework of an extended form of the proposed procedure which enables to take into account all possible initial moments rather than large negative time {{t}0}=-∞ as in standard LZ problems. We elucidate the applications of our results from a unified theoretical basis that numerically analyzes the dynamics of a system as probed by experiments.
Confined electronic states and their modulations in graphene nanorings
NASA Astrophysics Data System (ADS)
Zhu, Jia-Lin; Wang, Xingyuan; Yang, Ning
2012-09-01
Confined electronic states in quantum rings formed by spatially modulated finite Dirac gap (FDGQR) in graphene are systematically studied by series-expansion method, and are compared with those in infinite-mass-boundary and one-dimensional quantum rings. The shape-size effect of FDGQR is illustrated to be distinct from that in graphene quantum dots. The Aharonov-Bohm effect in FDGQR is clearly shown by the energy spectrum and the optical-transition probabilities. The FDGQR coupled with the electrostatic-potential induced nanoring is found useful for modulating the Dirac electronic states and the optical-transition probabilities. These results may help us to understand and to control the quantum behaviors of confined electronic states in graphene.
Fragmentation pathwaysfor selected electronic states of theacetylene dication
Osipov, Timur; Rescigno, Thomas N.; Weber, Thorsten; Miyabe,Shungo; Jahnke, T.; Alnaser, A.; Hertlein, Markus P.; Jagutzki, O.; Schmidt, L.Ph.H.; Schoffler, M.; Foucar, L.; Schossler, S.; Havermeier,T.; Odenweller,M.; Voss, S.; Feinberg, Ben; Landers, Alan; Prior, MichaelH.; Dorner, Reinhart; Cocke, C.L.; Belkacem, Ali
2007-12-18
Coincident measurement of the Auger electron and fragmention momenta emitted after carbon core-level photoionization of acetylenehas yielded new understanding of how the dication fragments. Ab initiocalculations and experimental data, including body-frame Auger angulardistributions, are used to identify the parent electronic states andtogether yield a comprehensive map of the dissociation pathways whichinclude surface crossings and barriers to direct dissociation. The Augerangular distributions show evidence of core-holelocalization.
Sliding seal materials for adiabatic engines
NASA Technical Reports Server (NTRS)
Lankford, J.
1985-01-01
The sliding friction coefficients and wear rates of promising carbide, oxide, and nitride materials were measured under temperature, environmental, velocity, loading conditions that are representative of the adiabatic engine environment. In order to provide guidance needed to improve materials for this application, the program stressed fundamental understanding of the mechanisms involved in friction and wear. Microhardness tests were performed on the candidate materials at elevated temperatures, and in atmospheres relevant to the piston seal application, and optical and electron microscopy were used to elucidate the micromechanisms of wear following wear testing. X-ray spectroscopy was used to evaluate interface/environment interactions which seemed to be important in the friction and wear process. Electrical effects in the friction and wear processes were explored in order to evaluate the potential usefulness of such effects in modifying the friction and wear rates in service. However, this factor was found to be of negligible significance in controlling friction and wear.
TOPICAL REVIEW Electronic states of graphene nanoribbons and analytical solutions
NASA Astrophysics Data System (ADS)
Wakabayashi, Katsunori; Sasaki, Ken-ichi; Nakanishi, Takeshi; Enoki, Toshiaki
2010-10-01
Graphene is a one-atom-thick layer of graphite, where low-energy electronic states are described by the massless Dirac fermion. The orientation of the graphene edge determines the energy spectrum of π-electrons. For example, zigzag edges possess localized edge states with energies close to the Fermi level. In this review, we investigate nanoscale effects on the physical properties of graphene nanoribbons and clarify the role of edge boundaries. We also provide analytical solutions for electronic dispersion and the corresponding wavefunction in graphene nanoribbons with their detailed derivation using wave mechanics based on the tight-binding model. The energy band structures of armchair nanoribbons can be obtained by making the transverse wavenumber discrete, in accordance with the edge boundary condition, as in the case of carbon nanotubes. However, zigzag nanoribbons are not analogous to carbon nanotubes, because in zigzag nanoribbons the transverse wavenumber depends not only on the ribbon width but also on the longitudinal wavenumber. The quantization rule of electronic conductance as well as the magnetic instability of edge states due to the electron-electron interaction are briefly discussed.
NASA Astrophysics Data System (ADS)
Li, Yong-Qing; Song, Yu-Zhi; Joaquim de Campos Varandas, António
2015-01-01
An accurate single-sheeted double many-body expansion potential energy surface is reported for the title system. It is obtained by using the aug-cc-pVTZ and aug-cc-pVQZ basis sets with extrapolation of the electron correlation energy to the complete basis set limit, plus extrapolation to the complete basis set limit of the complete-active-space self-consistent field energy. The collinear and bending barrier heights of the new global potential energy surface is 2.301 and 1.768 kcal mol-1, in very good agreement with the values of 2.222 and 1.770 kcal mol-1 from the current best potential energy surface. In particular, the new potential energy surface describes well the important van der Waals interactions which is very useful for investigating the dynamics of the title system. Thus, the new potential energy surface can both be recommended for dynamics studies of the F + H2 reaction and as building block for constructing the potential energy surfaces of larger fluorine/hydrogen containing systems. Based on the new potential energy surface, a preliminary theoretical study of the reaction F(2P) + H2 (X1 Σg+) → FH(X1Σ+) + H(2S) has been carried out with the methods of quasi-classical trajectory and quantum mechanical. The results have shown that the new PES is suitable for any kind of dynamics studies. Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjd/e2014-50445-3
Two-electron photoionization of ground-state lithium
Kheifets, A. S.; Fursa, D. V.; Bray, I.
2009-12-15
We apply the convergent close-coupling (CCC) formalism to single-photon two-electron ionization of the lithium atom in its ground state. We treat this reaction as single-electron photon absorption followed by inelastic scattering of the photoelectron on a heliumlike Li{sup +} ion. The latter scattering process can be described accurately within the CCC formalism. We obtain integrated cross sections of single photoionization leading to the ground and various excited states of the Li{sup +} ion as well as double photoionization extending continuously from the threshold to the asymptotic limit of infinite photon energy. Comparison with available experimental and theoretical data validates the CCC model.
Neves, R F C; Jones, D B; Lopes, M C A; Blanco, F; García, G; Ratnavelu, K; Brunger, M J
2015-05-21
We report on measurements of integral cross sections (ICSs) for electron impact excitation of a series of composite vibrational modes and electronic-states in phenol, where the energy range of those experiments was 15-250 eV. There are currently no other results against which we can directly compare those measured data. We also report results from our independent atom model with screened additivity rule correction computations, namely, for the inelastic ICS (all discrete electronic states and neutral dissociation) and the total ionisation ICS. In addition, for the relevant dipole-allowed excited electronic states, we also report f-scaled Born-level and energy-corrected and f-scaled Born-level (BEf-scaled) ICS. Where possible, our measured and calculated ICSs are compared against one another with the general level of accord between them being satisfactory to within the measurement uncertainties. PMID:26001459
Neves, R. F. C.; Jones, D. B.; Lopes, M. C. A.; Blanco, F.; García, G.; Ratnavelu, K.; Brunger, M. J.
2015-05-21
We report on measurements of integral cross sections (ICSs) for electron impact excitation of a series of composite vibrational modes and electronic-states in phenol, where the energy range of those experiments was 15–250 eV. There are currently no other results against which we can directly compare those measured data. We also report results from our independent atom model with screened additivity rule correction computations, namely, for the inelastic ICS (all discrete electronic states and neutral dissociation) and the total ionisation ICS. In addition, for the relevant dipole-allowed excited electronic states, we also report f-scaled Born-level and energy-corrected and f-scaled Born-level (BEf-scaled) ICS. Where possible, our measured and calculated ICSs are compared against one another with the general level of accord between them being satisfactory to within the measurement uncertainties.
Electron-impact excitation of the low-lying electronic states of formaldehyde
NASA Technical Reports Server (NTRS)
Chutjian, A.
1974-01-01
Electron-impact excitation has been observed at incident electron energies of 10.1 and 20.1 eV to the first five excited electronic states of formaldehyde lying at and below the 1B2 state at 7.10 eV. These excitations include two new transitions in the energy-loss range 5.6-6.2 eV and 6.7-7.0 eV which have been detected for the first time, either through electron-impact excitation or photon absorption. The differential cross sections of these new excitations are given at scattering angles between 15 and 135 deg. These cross-section ratios peak at large scattering angles - a characteristic of triplet - singlet excitations. The design and performance of the electron-impact spectrometer used in the above observations is outlined and discussed.
NASA Astrophysics Data System (ADS)
Wójcik, P.; Zegrodnik, M.; Rzeszotarski, B.; Adamowski, J.
2016-09-01
The tunneling conductance through the half-metal/conical magnet/superconductor (HM/CM/SC) junctions is investigated with the use of the Bogoliubov-de Gennes equations in the framework of Blonder-Tinkham-Klapwijk formalism. Due to the spin band separation in the HM, the conductance in the subgap region is mainly determined by the anomalous Andreev reflection, the probability of which strongly depends on the spin transmission in the CM layer. We show that the spins of electrons injected from the HM can be transmitted through the CM to the SC either adiabatically or non-adiabatically depending on the period of the spatial modulation of the exchange field. We find that the conductance in the subgap region oscillates as a function of the CM layer thickness wherein the oscillations transform from the irregular pattern in the non-adiabatic regime to the regular one in the adiabatic regime. For both adiabatic and non-adiabatic transport regimes the conductance is studied over a broad range of parameters determining the spiral magnetization in the CM. We find that in the non-adiabatic regime, the decrease of the exchange field amplitude in the CM leads to the emergence of the conductance peak for the particular CM thickness in agreement with recent experiments.
Nature of ground and electronic excited states of higher acenes.
Yang, Yang; Davidson, Ernest R; Yang, Weitao
2016-08-30
Higher acenes have drawn much attention as promising organic semiconductors with versatile electronic properties. However, the nature of their ground state and electronic excited states is still not fully clear. Their unusual chemical reactivity and instability are the main obstacles for experimental studies, and the potentially prominent diradical character, which might require a multireference description in such large systems, hinders theoretical investigations. Here, we provide a detailed answer with the particle-particle random-phase approximation calculation. The (1)Ag ground states of acenes up to decacene are on the closed-shell side of the diradical continuum, whereas the ground state of undecacene and dodecacene tilts more to the open-shell side with a growing polyradical character. The ground state of all acenes has covalent nature with respect to both short and long axes. The lowest triplet state (3)B2u is always above the singlet ground state even though the energy gap could be vanishingly small in the polyacene limit. The bright singlet excited state (1)B2u is a zwitterionic state to the short axis. The excited (1)Ag state gradually switches from a double-excitation state to another zwitterionic state to the short axis, but always keeps its covalent nature to the long axis. An energy crossing between the (1)B2u and excited (1)Ag states happens between hexacene and heptacene. Further energetic consideration suggests that higher acenes are likely to undergo singlet fission with a low photovoltaic efficiency; however, the efficiency might be improved if a singlet fission into multiple triplets could be achieved. PMID:27528690
Experimental Studies of Interacting Electronic States in NaCs
NASA Astrophysics Data System (ADS)
Faust, Carl E.
This dissertation describes methods and results of spectroscopic studies of the NaCs molecule. NaCs is of particular interest in many labs where experimental studies of ultra-cold molecules are being conducted. Data obtained in the present work will also be useful as benchmarks for various theoretical calculations. Our goals in studying this molecule were to map out high lying electronic states and to understand how these states interact with one another. Sodium and cesium metal were heated in a heat-pipe oven to form a vapor of NaCs molecules. These molecules were excited using narrow band, continuous wave (cw), tunable lasers. We employed the optical-optical double resonance (OODR) technique to obtain Doppler-free spectra of transitions to rotational and vibrational levels of high lying electronic states. One state of particular interest was the 12(0+) electronic state. Rovibrational level energies corresponding to this state were measured and used to generate a potential energy curve using computer programs to implement both the Rydberg-Klein-Rees (RKR) method and the inverted perturbation approach (IPA). By observing fluorescence from the 12(0+) state resolved as a function of wavelength, we determined that this state interacts with the nearby 11(0+) electronic state, which was previously mapped out by Ashman et al. A two-stage coupling model was devised to describe the resolved fluorescence originating from these two interacting states. The electronic states interact via spin-orbit coupling, while the individual rovibrational levels interact via a second mechanism, likely nonadiabatic coupling. This two-stage coupling between the levels of these states causes quantum interference between fluorescence pathways associated with different components of the wavefunctions describing these levels. This interference results in more complicated resolved fluorescence spectra. The model was used to fit parameters describing these interactions so that the resolved
Adiabatic Wankel type rotary engine
NASA Technical Reports Server (NTRS)
Kamo, R.; Badgley, P.; Doup, D.
1988-01-01
This SBIR Phase program accomplished the objective of advancing the technology of the Wankel type rotary engine for aircraft applications through the use of adiabatic engine technology. Based on the results of this program, technology is in place to provide a rotor and side and intermediate housings with thermal barrier coatings. A detailed cycle analysis of the NASA 1007R Direct Injection Stratified Charge (DISC) rotary engine was performed which concluded that applying thermal barrier coatings to the rotor should be successful and that it was unlikely that the rotor housing could be successfully run with thermal barrier coatings as the thermal stresses were extensive.
Controlling autoionization in strontium two-electron-excited states
NASA Astrophysics Data System (ADS)
Fields, Robert; Zhang, Xinyue; Dunning, F. Barry; Yoshida, Shuhei; Burgdörfer, Joachim
2016-05-01
One challenge in engineering long-lived two-electron-excited states, i.e., so-called planetary atoms, is autoionization. Autoionization, however, can be suppressed if the outermost electron is placed in a high- n, n ~ 300 - 600 , high- L state because such states have only a very small overlap with the inner electron, even when this is also excited to a state of relatively high n and hence of relatively long lifetime. Here the L-dependence of the autoionization rate for high- n strontium Rydberg atoms is examined during excitation of the core ion 5 s 2S1 / 2 - 5 p 2P3 / 2 transition. Measurements in which the angular momentum of the Rydberg electron is controlled using a pulsed electric field show that the autoionization rate decreases rapidly with increasing L and becomes very small for values larger than ~ 20 . The data are analyzed with the aid of calculations undertaken using complex scaling. Research supported by the NSF and Robert A. Welch Foundation.
Imaging the dynamics of free-electron Landau states
Schattschneider, P.; Schachinger, Th.; Stöger-Pollach, M.; Löffler, S.; Steiger-Thirsfeld, A.; Bliokh, K. Y.; Nori, Franco
2014-01-01
Landau levels and states of electrons in a magnetic field are fundamental quantum entities underlying the quantum Hall and related effects in condensed matter physics. However, the real-space properties and observation of Landau wave functions remain elusive. Here we report the real-space observation of Landau states and the internal rotational dynamics of free electrons. States with different quantum numbers are produced using nanometre-sized electron vortex beams, with a radius chosen to match the waist of the Landau states, in a quasi-uniform magnetic field. Scanning the beams along the propagation direction, we reconstruct the rotational dynamics of the Landau wave functions with angular frequency ~100 GHz. We observe that Landau modes with different azimuthal quantum numbers belong to three classes, which are characterized by rotations with zero, Larmor and cyclotron frequencies, respectively. This is in sharp contrast to the uniform cyclotron rotation of classical electrons, and in perfect agreement with recent theoretical predictions. PMID:25105563
OhioLINK Electronic Journal Use at Ohio State University
ERIC Educational Resources Information Center
Connell, Tschera Harkness; Rogers, Sally A.; Diedrichs, Carol Pitts
2005-01-01
A five-question survey randomly presented to users at Ohio State University (OSU) as they viewed articles in OhioLINK's Electronic Journal Center (EJC) in fall 2002 probed the user's status, academic unit, reason for viewing, path to the article, and frequency of EJC use. Usage by faculty and graduate students, by frequent users, and by those in…
Tuning ground states and excitations in complex electronic materials
Bishop, A.R.
1996-09-01
Modern electronic materials are characterized by a great variety of broken-symmetry ground states and excitations. Their control requires understanding and tuning underlying driving forces of spin-charge-lattice coupling, critical to macroscopic properties and applications. We report representative model calculations which demonstrate some of the richness of the phenomena and the challenges for successful microscopic modeling.
DETERMINING THE ORIGINS OF ELECTRONIC STATES IN SEMICONDUCTOR NANOSTRUCTURES
Goldman, Rachel
2014-12-16
With support from this program, we have generated key results in quantum dot (QD) formation, strain/electronic coupling, measurement and modeling of confined states, and examination of the influence of QDs on thermoelectric and photovoltaic properties of nanocomposite structures. This final report contains a description of our key findings followed by a list of personnel supported and publications generated.
Student Satisfaction with Electronic Library Resources at Wayne State University
ERIC Educational Resources Information Center
Holley, Robert P.; Powell, Ronald R.
2004-01-01
This paper reports the results of a survey of student satisfaction with electronic library resources other than the online catalog at Wayne State University. Undertaken in Fall Term 2000 as a class project for a marketing course, a student team designed, administered, and analyzed a survey of a random sample of students. Almost 40% of the…
Imaging the dynamics of free-electron Landau states.
Schattschneider, P; Schachinger, Th; Stöger-Pollach, M; Löffler, S; Steiger-Thirsfeld, A; Bliokh, K Y; Nori, Franco
2014-01-01
Landau levels and states of electrons in a magnetic field are fundamental quantum entities underlying the quantum Hall and related effects in condensed matter physics. However, the real-space properties and observation of Landau wave functions remain elusive. Here we report the real-space observation of Landau states and the internal rotational dynamics of free electrons. States with different quantum numbers are produced using nanometre-sized electron vortex beams, with a radius chosen to match the waist of the Landau states, in a quasi-uniform magnetic field. Scanning the beams along the propagation direction, we reconstruct the rotational dynamics of the Landau wave functions with angular frequency ~100 GHz. We observe that Landau modes with different azimuthal quantum numbers belong to three classes, which are characterized by rotations with zero, Larmor and cyclotron frequencies, respectively. This is in sharp contrast to the uniform cyclotron rotation of classical electrons, and in perfect agreement with recent theoretical predictions. PMID:25105563
Electron-state tuning of multilayer graphene by defects
NASA Astrophysics Data System (ADS)
Kishimoto, Ken; Okada, Susumu
2016-06-01
Electronic band structures of graphene thin films, in which the topmost layer possesses atomic and topological defects, are studied using the density functional theory. Our calculations showed that all graphene thin films studied here have a finite energy gap in their π electron states, although the thin films possess defect-free hexagonal networks, because of the spatially undulated local potential on pristine graphene layers induced by the defects. The energy gap in π states slightly decreases with increasing number of layers, while the gap sensitively depends on the interlayer stacking arrangement. Our analyses clarify that the interlayer interaction plays a crucial role for mediating the effect of the defects on the π electrons of pristine layers.
Vibrational coherences in charge-transfer dyes: A non-adiabatic picture
Sissa, Cristina; Delchiaro, Francesca; Di Maiolo, Francesco
2014-10-28
Essential-state models efficiently describe linear and nonlinear spectral properties of different families of charge-transfer chromophores. Here, the essential-state machinery is applied to the calculation of the early-stage dynamics after ultrafast (coherent) excitation of polar and quadrupolar chromophores. The fully non-adiabatic treatment of coupled electronic and vibrational motion allows for a reliable description of the dynamics of these intriguing systems. In particular, the proposed approach is reliable even when the adiabatic and harmonic approximations do not apply, such as for quadrupolar dyes that show a multistable, broken-symmetry excited state. Our approach quite naturally leads to a clear picture for a dynamical Jahn-Teller effect in these systems. The recovery of symmetry due to dynamical effects is however disrupted in polar solvents where a static symmetry lowering is observed. More generally, thermal disorder in polar solvents is responsible for dephasing phenomena, damping the coherent oscillations with particularly important effects in the case of polar dyes.
Vibrational coherences in charge-transfer dyes: A non-adiabatic picture
NASA Astrophysics Data System (ADS)
Sissa, Cristina; Delchiaro, Francesca; Di Maiolo, Francesco; Terenziani, Francesca; Painelli, Anna
2014-10-01
Essential-state models efficiently describe linear and nonlinear spectral properties of different families of charge-transfer chromophores. Here, the essential-state machinery is applied to the calculation of the early-stage dynamics after ultrafast (coherent) excitation of polar and quadrupolar chromophores. The fully non-adiabatic treatment of coupled electronic and vibrational motion allows for a reliable description of the dynamics of these intriguing systems. In particular, the proposed approach is reliable even when the adiabatic and harmonic approximations do not apply, such as for quadrupolar dyes that show a multistable, broken-symmetry excited state. Our approach quite naturally leads to a clear picture for a dynamical Jahn-Teller effect in these systems. The recovery of symmetry due to dynamical effects is however disrupted in polar solvents where a static symmetry lowering is observed. More generally, thermal disorder in polar solvents is responsible for dephasing phenomena, damping the coherent oscillations with particularly important effects in the case of polar dyes.
Digitized adiabatic quantum computing with a superconducting circuit.
Barends, R; Shabani, A; Lamata, L; Kelly, J; Mezzacapo, A; Las Heras, U; Babbush, R; Fowler, A G; Campbell, B; Chen, Yu; Chen, Z; Chiaro, B; Dunsworth, A; Jeffrey, E; Lucero, E; Megrant, A; Mutus, J Y; Neeley, M; Neill, C; O'Malley, P J J; Quintana, C; Roushan, P; Sank, D; Vainsencher, A; Wenner, J; White, T C; Solano, E; Neven, H; Martinis, John M
2016-06-01
Quantum mechanics can help to solve complex problems in physics and chemistry, provided they can be programmed in a physical device. In adiabatic quantum computing, a system is slowly evolved from the ground state of a simple initial Hamiltonian to a final Hamiltonian that encodes a computational problem. The appeal of this approach lies in the combination of simplicity and generality; in principle, any problem can be encoded. In practice, applications are restricted by limited connectivity, available interactions and noise. A complementary approach is digital quantum computing, which enables the construction of arbitrary interactions and is compatible with error correction, but uses quantum circuit algorithms that are problem-specific. Here we combine the advantages of both approaches by implementing digitized adiabatic quantum computing in a superconducting system. We tomographically probe the system during the digitized evolution and explore the scaling of errors with system size. We then let the full system find the solution to random instances of the one-dimensional Ising problem as well as problem Hamiltonians that involve more complex interactions. This digital quantum simulation of the adiabatic algorithm consists of up to nine qubits and up to 1,000 quantum logic gates. The demonstration of digitized adiabatic quantum computing in the solid state opens a path to synthesizing long-range correlations and solving complex computational problems. When combined with fault-tolerance, our approach becomes a general-purpose algorithm that is scalable. PMID:27279216
Digitized adiabatic quantum computing with a superconducting circuit
NASA Astrophysics Data System (ADS)
Barends, R.; Shabani, A.; Lamata, L.; Kelly, J.; Mezzacapo, A.; Heras, U. Las; Babbush, R.; Fowler, A. G.; Campbell, B.; Chen, Yu; Chen, Z.; Chiaro, B.; Dunsworth, A.; Jeffrey, E.; Lucero, E.; Megrant, A.; Mutus, J. Y.; Neeley, M.; Neill, C.; O’Malley, P. J. J.; Quintana, C.; Roushan, P.; Sank, D.; Vainsencher, A.; Wenner, J.; White, T. C.; Solano, E.; Neven, H.; Martinis, John M.
2016-06-01
Quantum mechanics can help to solve complex problems in physics and chemistry, provided they can be programmed in a physical device. In adiabatic quantum computing, a system is slowly evolved from the ground state of a simple initial Hamiltonian to a final Hamiltonian that encodes a computational problem. The appeal of this approach lies in the combination of simplicity and generality; in principle, any problem can be encoded. In practice, applications are restricted by limited connectivity, available interactions and noise. A complementary approach is digital quantum computing, which enables the construction of arbitrary interactions and is compatible with error correction, but uses quantum circuit algorithms that are problem-specific. Here we combine the advantages of both approaches by implementing digitized adiabatic quantum computing in a superconducting system. We tomographically probe the system during the digitized evolution and explore the scaling of errors with system size. We then let the full system find the solution to random instances of the one-dimensional Ising problem as well as problem Hamiltonians that involve more complex interactions. This digital quantum simulation of the adiabatic algorithm consists of up to nine qubits and up to 1,000 quantum logic gates. The demonstration of digitized adiabatic quantum computing in the solid state opens a path to synthesizing long-range correlations and solving complex computational problems. When combined with fault-tolerance, our approach becomes a general-purpose algorithm that is scalable.
Adiabatic theory for anisotropic cold molecule collisions
Pawlak, Mariusz; Shagam, Yuval; Narevicius, Edvardas; Moiseyev, Nimrod
2015-08-21
We developed an adiabatic theory for cold anisotropic collisions between slow atoms and cold molecules. It enables us to investigate the importance of the couplings between the projection states of the rotational motion of the atom about the molecular axis of the diatom. We tested our theory using the recent results from the Penning ionization reaction experiment {sup 4}He(1s2s {sup 3}S) + HD(1s{sup 2}) → {sup 4}He(1s{sup 2}) + HD{sup +}(1s) + e{sup −} [Lavert-Ofir et al., Nat. Chem. 6, 332 (2014)] and demonstrated that the couplings have strong effect on positions of shape resonances. The theory we derived provides cross sections which are in a very good agreement with the experimental findings.
Reversible logic gate using adiabatic superconducting devices
Takeuchi, N.; Yamanashi, Y.; Yoshikawa, N.
2014-01-01
Reversible computing has been studied since Rolf Landauer advanced the argument that has come to be known as Landauer's principle. This principle states that there is no minimum energy dissipation for logic operations in reversible computing, because it is not accompanied by reductions in information entropy. However, until now, no practical reversible logic gates have been demonstrated. One of the problems is that reversible logic gates must be built by using extremely energy-efficient logic devices. Another difficulty is that reversible logic gates must be both logically and physically reversible. Here we propose the first practical reversible logic gate using adiabatic superconducting devices and experimentally demonstrate the logical and physical reversibility of the gate. Additionally, we estimate the energy dissipation of the gate, and discuss the minimum energy dissipation required for reversible logic operations. It is expected that the results of this study will enable reversible computing to move from the theoretical stage into practical usage. PMID:25220698
Symmetry-protected adiabatic quantum transistors
NASA Astrophysics Data System (ADS)
Williamson, Dominic J.; Bartlett, Stephen D.
2015-05-01
Adiabatic quantum transistors (AQT) allow quantum logic gates to be performed by applying a large field to a quantum many-body system prepared in its ground state, without the need for local control. The basic operation of such a device can be viewed as driving a spin chain from a symmetry-protected (SP) phase to a trivial phase. This perspective offers an avenue to generalize the AQT and to design several improvements. The performance of quantum logic gates is shown to depend only on universal symmetry properties of a SP phase rather than any fine tuning of the Hamiltonian, and it is possible to implement a universal set of logic gates in this way by combining several different types of SP matter. Such SP AQTs are argued to be robust to a range of relevant noise processes.
Number Partitioning via Quantum Adiabatic Computation
NASA Technical Reports Server (NTRS)
Smelyanskiy, Vadim N.; Toussaint, Udo; Clancy, Daniel (Technical Monitor)
2002-01-01
We study both analytically and numerically the complexity of the adiabatic quantum evolution algorithm applied to random instances of combinatorial optimization problems. We use as an example the NP-complete set partition problem and obtain an asymptotic expression for the minimal gap separating the ground and exited states of a system during the execution of the algorithm. We show that for computationally hard problem instances the size of the minimal gap scales exponentially with the problem size. This result is in qualitative agreement with the direct numerical simulation of the algorithm for small instances of the set partition problem. We describe the statistical properties of the optimization problem that are responsible for the exponential behavior of the algorithm.
Adiabatic theory for anisotropic cold molecule collisions.
Pawlak, Mariusz; Shagam, Yuval; Narevicius, Edvardas; Moiseyev, Nimrod
2015-08-21
We developed an adiabatic theory for cold anisotropic collisions between slow atoms and cold molecules. It enables us to investigate the importance of the couplings between the projection states of the rotational motion of the atom about the molecular axis of the diatom. We tested our theory using the recent results from the Penning ionization reaction experiment (4)He(1s2s (3)S) + HD(1s(2)) → (4)He(1s(2)) + HD(+)(1s) + e(-) [Lavert-Ofir et al., Nat. Chem. 6, 332 (2014)] and demonstrated that the couplings have strong effect on positions of shape resonances. The theory we derived provides cross sections which are in a very good agreement with the experimental findings. PMID:26298122
Charge and electronic states of cuprite: Experiment and theory
NASA Astrophysics Data System (ADS)
Kim, Miyoung
The bonding characteristics of cuprite have been studied by the using convergent beam electron diffraction (CBED) method. The low-order structure factors are closely related to the valence electron density, and the CBED is one of the most accurate methods of measuring the low order structure factors. The multipole model is used for converting the structure factors into charge density. The multipole expansion takes into account non-spherical valence electron density due to atomic bonding based on the crystal symmetry. The charge transfer from copper to oxygen is determined from the multipole fitting parameters. The hybridization state between 4s-3d orbitals of copper is also estimated. Electronic states of CU2O are investigated by studying the fine structure of the electron-energy loss spectrum (EELS). The cross section of the near edge structure is proportional to the density of state times an atomic transition site-projected matrix element which generally varies slowly in the region of interest. Both the fine structure of Cu- L2'3 and O-K of Cu2O are significantly different from those of CuO, which shows the sensitivity of EELS fine structure to the crystal bonding. Full-potential Linearized Augmented Plane Wave (FLAPW) calculations have been used to compare experimental results with theory. The structure factors and bonding charge density are compared with the results obtained by the CBED method, and the density of states is compared with the EELS. The FLAPW method has also been used in the local density approximations CLDA) to calculate values of the mean inner Coulomb potential V 0 for Si, Ge and MgO. These values are compared with recent measurements by electron holography. The supercell calculations are performed for crystal slabs, so that the effects of different crystal orientations and surface structures on V0 can be evaluated.
Foucault's Pendulum, Analog for an Electron Spin State
NASA Astrophysics Data System (ADS)
Linck, Rebecca
2012-11-01
The classical Lagrangian that describes the coupled oscillations of Foucault's pendulum presents an interesting analog to an electron's spin state in an external magnetic field. With a simple modification, this classical Lagrangian yields equations of motion that directly map onto the Schrodinger-Pauli Equation. This analog goes well beyond the geometric phase, reproducing a broad range of behavior from Zeeman-like frequency splitting to precession of the spin state. By demonstrating that unmeasured spin states can be fully described in classical terms, this research opens the door to using the tools of classical physics to examine an inherently quantum phenomenon.
Two Electron States in a Quantum Ring on a Sphere
NASA Astrophysics Data System (ADS)
Kazaryan, Eduard M.; Shahnazaryan, Vanik A.; Sarkisyan, Hayk A.
2014-02-01
Two electron states in a quantum ring on a spherical surface are discussed. The problem is discussed within the frameworks of Russell-Saunders coupling scheme, that is, the spin-orbit coupling is neglected. Treating Coulomb interaction as a perturbation, the energy correction for different states is calculated. The dependence of the Coulomb interaction energy on external polar boundary angle of quantum ring is obtained. In analogue with the helium atom the concept of states exchange time is introduced, and its dependence on geometrical parameters of the ring is shown.
The Electronic Properties of Superatom States of Hollow Molecules
Feng, Min; Zhao, Jin; Huang, Tian; Zhu, Xiaoyang; Petek, Hrvoje
2011-05-17
Electronic and optical properties of molecules and molecular solids are traditionally considered from the perspective of the frontier orbitals and their intermolecular interactions. How molecules condense into crystalline solids, however, is mainly attributed to the long-range polarization interaction. In this Account, we show that long-range polarization also introduces a distinctive set of diffuse molecular electronic states, which in quantum structures or solids can combine into nearly-free-electron (NFE) bands. These NFE properties, which are usually associated with good metals, are vividly evident in sp2 hybridized carbon materials, specifically graphene and its derivatives. The polarization interaction is primarily manifested in the screening of an external charge at a solid/vacuum interface. It is responsible for the universal image potential and the associated unoccupied image potential (IP) states, which are observed even at the He liquid/vacuum interface. The molecular electronic properties that we describe are derived from the IP states of graphene, which float above and below the molecular plane and undergo free motion parallel to it. Rolling or wrapping a graphene sheet into a nanotube or a fullerene transforms the IP states into diffuse atom-like orbitals that are bound primarily to hollow molecular cores, rather than the component atoms. Therefore, we named them the superatom molecular orbitals (SAMOs). Like the excitonic states of semiconductor nanostructures or the plasmonic resonances of metallic nanoparticles, SAMOs of fullerene molecules, separated by their van der Waals distance, can combine to form diatomic molecule-like orbitals of C60 dimers. For larger aggregates, they form NFE bands of superatomic quantum structures and solids. The overlap of the diffuse SAMO wavefunctions in van der Waals solids provides a different paradigm for band formation than the valence or conduction bands formed by interaction of the more tightly bound
Calculation of electron scattering from the ground state of ytterbium
Bostock, Christopher J.; Fursa, Dmitry V.; Bray, Igor
2011-05-15
We report on the application of the convergent close-coupling method, in both relativistic and nonrelativistic formulations, to electron scattering from ytterbium. Angle-differential and integrated cross sections are presented for elastic scattering and excitation of the states (6s6p){sup 3}P{sub 0,1,2}, (6s6p){sup 1}P{sub 1}{sup o}, (6s7p){sup 1}P{sub 1}{sup o}, and (6s5d){sup 1}D{sub 2}{sup e} for a range of incident electron energies. We also present calculations of the total cross section, and angle-differential Stokes parameters for excitation of the (6s6p){sup 3}P{sub 1}{sup o} state from the ground state. A comparison is made with the relativistic distorted-wave method and experiments.
Foucault's pendulum, a classical analog for the electron spin state
NASA Astrophysics Data System (ADS)
Linck, Rebecca A.
Spin has long been regarded as a fundamentally quantum phenomena that is incapable of being described classically. To bridge the gap and show that aspects of spin's quantum nature can be described classically, this work uses a classical Lagrangian based on the coupled oscillations of Foucault's pendulum as an analog for the electron spin state in an external magnetic field. With this analog it is possible to demonstrate that Foucault's pendulum not only serves as a basis for explaining geometric phase, but is also a basis for reproducing a broad range of behavior from Zeeman-like frequency splitting to precession of the spin state. By demonstrating that unmeasured electron spin states can be fully described in classical terms, this research opens the door to using the tools of classical physics to examine an inherently quantum phenomenon.
Conical Intersections Between Vibrationally Adiabatic Surfaces in Methanol
NASA Astrophysics Data System (ADS)
Dawadi, Mahesh B.; Perry, David S.
2014-06-01
The discovery of a set of seven conical intersections (CI's) between vibrationally adiabatic surfaces in methanol is reported. The intersecting surfaces represent the energies of the two asymmetric CH stretch vibrations, νb{2} and νb{9}, regarded as adiabatic functions of the torsional angle, γ, and COH bend angle, ρ. One conical intersection, required by symmetry, is located at the C3v geometry where the COH group is linear (ρ = 0°); the other six are in eclipsed conformations with ρ = 62° and 94°. The three CI's at ρ = 62° are close to the equilibrium geometry (ρ = 71.4°), within the zero-point amplitude of the COH bending vibration. CI's between electronic surfaces have long been recognized as crucial conduits for ultrafast relaxation, and recently Hamm, and Stock have shown that vibrational CI's may also provide a mechanism for ultrafast vibrational relaxation. The ab initio data reported here are well described by an extended Zwanziger and Grant model for E ⊗ e Jahn-Teller systems in which Renner-Teller coupling is also active. However, in the present case, the distortion ρ from C3v symmetry is much larger than is typical in the Jahn-Teller coupling of electronic surfaces and accordingly higher-order terms in ρ are required. The present results are also consistent with the two-state model of Xu et al. The cusp-like features, which they found along the internal-rotation path, are explained in the context of the present work in terms of proximity to the CI's. The presence of multiple CI's near the torsional minimum energy path impacts the role of geometric phase in this three-fold internal-rotor system. When the dimensionality of the low-frequency space is extended to include the CO bond length as well as γ and ρ, the individual CI's become seams of CI's. It is shown that the CI's at ρ = 62° and 94° lie along the same seam of CI's in this higher dimensional space. P. Hamm and G. Stock, Phys. Rev. Lett., 109, 173201, (2012) P. Hamm, and G
Spectroscopic Constants of the Known Electronic States of Lead Monofluoride
McRaven, C.P.; Sivakumar, P.; Shafer-Ray, N.E.; Hall, G.E.; Sears, T.J.
2010-08-01
Based on measurements made by mass-resolved 1 + 1{prime} + 1{double_prime} resonance-enhanced multiphoton ionization spectroscopy, we have determined new molecular constants describing the rotational and fine structure levels of the B, D, E, and F states of the most abundant isotopic variant {sup 208}Pb{sup 19}F, and we summarize the spectroscopic constants for all the know electronic states of the radical. Many spectroscopic constants for the isotopologues {sup 206}Pb{sup 19}F and {sup 207}Pb{sup 19}F have also been determined. The symmetry of the D-state is found to be {sup 2}{pi}{sub 1/2}, and the F-state is found to be an {Omega} = 3/2 state.
Adiabatic nonlinear waves with trapped particles. II. Wave dispersion
Dodin, I. Y.; Fisch, N. J.
2012-01-15
A general nonlinear dispersion relation is derived in a nondifferential form for an adiabatic sinusoidal Langmuir wave in collisionless plasma, allowing for an arbitrary distribution of trapped electrons. The linear dielectric function is generalized, and the nonlinear kinetic frequency shift {omega}{sub NL} is found analytically as a function of the wave amplitude a. Smooth distributions yield {omega}{sub NL}{proportional_to}{radical}(a), as usual. However, beam-like distributions of trapped electrons result in different power laws, or even a logarithmic nonlinearity, which are derived as asymptotic limits of the same dispersion relation. Such beams are formed whenever the phase velocity changes, because the trapped distribution is in autoresonance and thus evolves differently from the passing distribution. Hence, even adiabatic {omega}{sub NL}(a) is generally nonlocal.
Energy-Efficient and Secure S-Box circuit using Symmetric Pass Gate Adiabatic Logic
Kumar, Dinesh; Mohammad, Azhar; Singh, Vijay; Perumalla, Kalyan S
2016-01-01
Differential Power Analysis (DPA) attack is considered to be a main threat while designing cryptographic processors. In cryptographic algorithms like DES and AES, S-Box is used to indeterminate the relationship between the keys and the cipher texts. However, S-box is prone to DPA attack due to its high power consumption. In this paper, we are implementing an energy-efficient 8-bit S-Box circuit using our proposed Symmetric Pass Gate Adiabatic Logic (SPGAL). SPGAL is energy-efficient as compared to the existing DPAresistant adiabatic and non-adiabatic logic families. SPGAL is energy-efficient due to reduction of non-adiabatic loss during the evaluate phase of the outputs. Further, the S-Box circuit implemented using SPGAL is resistant to DPA attacks. The results are verified through SPICE simulations in 180nm technology. SPICE simulations show that the SPGAL based S-Box circuit saves upto 92% and 67% of energy as compared to the conventional CMOS and Secured Quasi-Adiabatic Logic (SQAL) based S-Box circuit. From the simulation results, it is evident that the SPGAL based circuits are energy-efficient as compared to the existing DPAresistant adiabatic and non-adiabatic logic families. In nutshell, SPGAL based gates can be used to build secure hardware for lowpower portable electronic devices and Internet-of-Things (IoT) based electronic devices.
Study of low-lying electronic states of ozone by multireference Møller-Plesset perturbation method
NASA Astrophysics Data System (ADS)
Tsuneda, T.; Nakano, H.; Hirao, K.
1995-10-01
The geometry and relative energy of the seven low-lying electronic states of ozone and the ground state of ozonide anion have been determined in C2v symmetry by the complete active space self-consistent field (CASSCF) and the multireference Møller-Plesset perturbation (MRMP) methods. The results are compared with the photodetachment spectra of O-3 observed recently by Arnold et al. The theoretical electron affinity of ozone is 1.965 eV, which is 0.14 eV below the experimental result of 2.103 eV. The calculated adiabatic excitation energies (assignment of Arnold et al. in parentheses) of ozone are 3A2 0.90 eV (1.18 eV), 3B2, 1.19 eV (1.30 eV), 3B1, 1.18 eV (1.45 eV), 1A2, 1.15 eV (˜1.6 eV), 1B1, 1.65 eV (2.05 eV), and 1B2, 3.77 eV (3.41 eV), respectively. Overall the present theory supports the assignment of Arnold et al. However, the simple considerations of geometry and energy are insufficient to determine a specific assignment of the 3B2 and 3B1 states. The dissociation energy of the ground state of ozone is computed to be 0.834 eV at the present level of theory. The present theory also predicts that none of the excited states lies below the ground state dissociation limit of O3.
A non-adiabatic dynamics study of octatetraene: the radiationless conversion from S2 to S1.
Qu, Zexing; Liu, Chungen
2013-12-28
Simulation of the excited state dynamics of all-trans-1,3,5,7-octatetraene has been performed to investigate the ultrafast radiationless S2 → S1 internal conversion process. Multireference configuration interaction with single excitation method has been employed to optimize the equilibrium structure of the excited states, as well as the S2/S1 conical intersection, and to investigate the non-adiabatic molecular dynamics of the S2/S1 state transition. At the conical intersection, the molecule is found to be distorted from the original planar trans structure to a nearly perpendicular conformation around C3-C4 bond, with the torsion angle being about 107°. Such structural change can result in mutual approaching of states S2 and S1 in energy, and drastically increase the nonadiabatic coupling between the two states by destroying the inter-state symmetry prohibition in the electronic wavefunctions. Surface-hopping molecular dynamics simulations are performed to describe the non-adiabatic process. Upon the Franck-Condon excitation to the S2 state, the molecule quickly twists its C3-C4 bond and approaches the conical intersection region, where it can undergo efficient internal conversion to S1. The decay time constant (τ) of S2 state is estimated to be around 251 fs by fitting the occupation number of average fraction of trajectories using an exponential damping function. This value is reasonably consistent with previous experimental measurements of around 300-400 fs. PMID:24387367
Adiabatic trapping in coupled kinetic Alfven-acoustic waves
Shah, H. A.; Ali, Z.; Masood, W.
2013-03-15
In the present work, we have discussed the effects of adiabatic trapping of electrons on obliquely propagating Alfven waves in a low {beta} plasma. Using the two potential theory and employing the Sagdeev potential approach, we have investigated the existence of arbitrary amplitude coupled kinetic Alfven-acoustic solitary waves in both the sub and super Alfvenic cases. The results obtained have been analyzed and presented graphically and can be applied to regions of space where the low {beta} assumption holds true.
Khelifi, Neji
2011-04-15
First and second derivative of the nonadiabatic coupling between the several {sup 1}{Sigma}{sup +} adiabatic states of the KH molecule considered from accurate diabatic and adiabatic data have been evaluated. Such derivatives of the electronic wave function are determined through a numerical differentiation of the rotational matrix connecting the diabatic and adiabatic representations. The first as well as the second derivative present many peaks related to ionic-neutral and neutral-neutral coupling between the {sup 1}{Sigma}{sup +} states. Such radial coupling has been exploited to calculate the first adiabatic correction, which corresponds to the diagonal term of the second derivative divided by the reduced mass, for the ground and some excited states of the KH molecule. The second adiabatic correction has been determined using the virial theorem. The first adiabatic correction was added to the adiabatic potential energy curves to redetermine the corrected spectroscopic constants and vibrational energy levels. The vibrational shift, which is the difference between the corrected and the adiabatic levels, has been calculated for X, A, C, and D {sup 1}{Sigma}{sup +} states of the KH molecule. A shift of some 10 cm{sup -1} is observed for some vibrational levels showing the breakdown of the Born-Oppenheimer approximation.
Surface States and Negative Electron Affinity in Polyethylene
Righi, M. C.; Scandolo, S.; Serra, S.; Iarlori, S.; Tosatti, E.; Santoro, G.
2001-08-13
First-principles calculations are used to investigate the electronic properties of the surfaces of polyethylene. The calculations support the experimental evidence of a negative electron affinity, with calculated values of -0.17 eV and -0.10 eV for surfaces with chains perpendicular and parallel to the surface normal, respectively. Both surfaces exhibit a surface state with binding energy -1.2{+-}0.5 eV with respect to the bulk polyethylene conduction band minimum. Implications of these findings on spectroscopy, as well as on the transport and aging properties of polyethylene for high-voltage applications, are discussed.
Levy, Mel E-mail: mlevy@tulane.edu; Anderson, James S. M.; Zadeh, Farnaz Heidar; Ayers, Paul W. E-mail: mlevy@tulane.edu
2014-05-14
Properties of exact density functionals provide useful constraints for the development of new approximate functionals. This paper focuses on convex sums of ground-level densities. It is observed that the electronic kinetic energy of a convex sum of degenerate ground-level densities is equal to the convex sum of the kinetic energies of the individual degenerate densities. (The same type of relationship holds also for the electron-electron repulsion energy.) This extends a known property of the Levy-Valone Ensemble Constrained-Search and the Lieb Legendre-Transform refomulations of the Hohenberg-Kohn functional to the individual components of the functional. Moreover, we observe that the kinetic and electron-repulsion results also apply to densities with fractional electron number (even if there are no degeneracies), and we close with an analogous point-wise property involving the external potential. Examples where different degenerate states have different kinetic energy and electron-nuclear attraction energy are given; consequently, individual components of the ground state electronic energy can change abruptly when the molecular geometry changes. These discontinuities are predicted to be ubiquitous at conical intersections, complicating the development of universally applicable density-functional approximations.
Non-adiabatic dynamics of molecules in optical cavities
NASA Astrophysics Data System (ADS)
Kowalewski, Markus; Bennett, Kochise; Mukamel, Shaul
2016-02-01
Strong coupling of molecules to the vacuum field of micro cavities can modify the potential energy surfaces thereby opening new photophysical and photochemical reaction pathways. While the influence of laser fields is usually described in terms of classical field, coupling to the vacuum state of a cavity has to be described in terms of dressed photon-matter states (polaritons) which require quantized fields. We present a derivation of the non-adiabatic couplings for single molecules in the strong coupling regime suitable for the calculation of the dressed state dynamics. The formalism allows to use quantities readily accessible from quantum chemistry codes like the adiabatic potential energy surfaces and dipole moments to carry out wave packet simulations in the dressed basis. The implications for photochemistry are demonstrated for a set of model systems representing typical situations found in molecules.
Adiabatic transfer of coherences in a cluster of coupled nuclear spins
Lee, Jae-Seung; Cardwell, Kate E.; Khitrin, A. K.
2005-12-15
It is experimentally demonstrated that quantum coherences can be efficiently transferred using adiabatic energy-level crossing. In a cluster of six dipolar-coupled proton spins of benzene, oriented by a liquid-crystalline matrix, a single-quantum coherence between one pair of states has been adiabatically transferred to another pair of states, and the superposition survived even after ten successive energy-level crossings.
Electron teleportation via Majorana bound states in a mesoscopic superconductor.
Fu, Liang
2010-02-01
Zero-energy Majorana bound states in superconductors have been proposed to be potential building blocks of a topological quantum computer, because quantum information can be encoded nonlocally in the fermion occupation of a pair of spatially separated Majorana bound states. However, despite intensive efforts, nonlocal signatures of Majorana bound states have not been found in charge transport. In this work, we predict a striking nonlocal phase-coherent electron transfer process by virtue of tunneling in and out of a pair of Majorana bound states. This teleportation phenomenon only exists in a mesoscopic superconductor because of an all-important but previously overlooked charging energy. We propose an experimental setup to detect this phenomenon in a superconductor-quantum-spin-Hall-insulator-magnetic-insulator hybrid system. PMID:20366777
Adiabatic Quantum Algorithm for Search Engine Ranking
NASA Astrophysics Data System (ADS)
Garnerone, Silvano; Zanardi, Paolo; Lidar, Daniel A.
2012-06-01
We propose an adiabatic quantum algorithm for generating a quantum pure state encoding of the PageRank vector, the most widely used tool in ranking the relative importance of internet pages. We present extensive numerical simulations which provide evidence that this algorithm can prepare the quantum PageRank state in a time which, on average, scales polylogarithmically in the number of web pages. We argue that the main topological feature of the underlying web graph allowing for such a scaling is the out-degree distribution. The top-ranked log(n) entries of the quantum PageRank state can then be estimated with a polynomial quantum speed-up. Moreover, the quantum PageRank state can be used in “q-sampling” protocols for testing properties of distributions, which require exponentially fewer measurements than all classical schemes designed for the same task. This can be used to decide whether to run a classical update of the PageRank.
Understanding x-ray driven impulsive electronic state redistribution using a three-state model
NASA Astrophysics Data System (ADS)
Ware, Matthew R.; Cryan, James; Bucksbaum, Philip H.
2016-05-01
The natural timescale for electron motion is extremely fast; electrons can move across molecular bonds in less than a femtosecond. To understand this fast motion and the role of electronic coherence, we are interested in creating a superposition of valence excited states through excitation with a broad bandwidth (>5eV) laser pulse. In the x-ray regime, the molecular ground state can couple to valence-excited states through an intermediate autoionizing resonance in a process known as stimulated x-ray Raman scattering (SXRS). X-rays excite electrons from the highly localized K-shells in a molecule, creating a superposition of valence-excited states initially localized around a target atom in the molecule. Coherences between states in the superposition will subsequently drive charge transfer as the wavepacket spreads out across the molecule. We use an effective 3-state model coupling the ground, auto-ionizing, and valence-excited states in diatomic systems to study the cross-section of SXRS as function of x-ray intensity, central frequency, bandwidth, and chirp. We also make observations on how the x-ray parameters affect the degree of initial localization to an atom of the wavepacket created in SXRS. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.
Low-lying electronic states of LiF molecule with inner electrons correlation
NASA Astrophysics Data System (ADS)
Wan, Ming-jie; Huang, Duo-hui; Yang, Jun-sheng; Cao, Qi-long; Jin, Cheng-guo; Wang, Fan-hou
2015-06-01
The potential energy curves and dipole moments of the low-lying electronic states of LiF molecule are performed by using highly accurate multi-reference configuration interaction with Awcv5z basis sets. 1s, the inner shell of Li is considered as the closed orbit, which is used to characterise the spectroscopic properties of a manifold of singlet and triplet states. 16 electronic states correlate with two lowest dissociation channels Li(2S)+F(2P) and Li(2P)+F(2P) are investigated. Spectroscopic parameters of the ground state X1Σ+ have been evaluated and critically compared with the available experimental values and the other theoretical data. However, spectroscopic parameters of 13Π, 11Δ, 11Σ-, 11Π, 13Σ+, 23Σ+, 13Δ, 13Σ-, 23Π, 21Π, 33Π, 31Π and 33Σ+ states are studied for the first time. These 13 excited states have shallow potential wells, and the dispersion coefficients of these excited states are predicted. In additional, oscillator strengths of excited states at equilibrium distances are also predicted.
Localized Electron States Near a Metal-SemiconductorNanocontact
Demchenko, Denis O.; Wang, Lin-Wang
2007-04-25
The electronic structure of nanowires in contact withmetallic electrodes of experimentally relevant sizes is calculated byincorporating the electrostatic polarization potential into the atomisticsingle particle Schrodinger equation. We show that the presence of anelectrode produces localized electron/hole states near the electrode, aphenomenon only exhibited in nanostructures and overlooked in the past.This phenomenon will have profound implications on electron transport insuch nanosystems. We calculate several electrode/nanowire geometries,with varying contact depths and nanowire radii. We demonstrate the changein the band gap of up to 0.5 eV in 3 nm diameter CdSe nanowires andcalculate the magnitude of the applied electric field necessary toovercome the localization.
NASA Astrophysics Data System (ADS)
Tiwari, Vivek
2015-05-01
Understanding the fundamental physics of light-harvesting in both, natural and artificial systems is key for the development of efficient light-harvesting technologies. My thesis addresses the following topics, i.) the mechanism underlying the remarkably efficient electronic energy transfer in natural light harvesting antennas, ii.) a femtosecond time-resolved photonumeric technique to quantitatively characterize transient chemical species. This talk will concentrate on the first project, while briefly touching the key ideas of the second project. Light harvesting antennas use a set of closely spaced pigment molecules held in a controlled relative geometry by a protein. It is shown that in certain antenna proteins the excited state electronic energy gaps between the pigments are resonant with a quantum of pigment vibrational energy. With such a vibrational-electronic resonance, anti-correlated motions between the pigments lead to a strong coupling between the electronic and nuclear motions, that is, breakdown of the Born-Oppenheimer approximation, over a wide range of pigment vibrational motions. It is shown that the 2D spectroscopic signatures of the resulting unavoidable nested non-adiabatic energy funnel on the excited states of photosynthetic antennas are consistent with all the reported 2D signatures of long-lived coherent oscillations, including the ones that are not explained by prior models of excited state electronic energy transfer. Extensions that account for both resonant and near-resonant pigment vibrations suggest that photosynthetic energy transfer presents a novel design in which electronic energy transfer proceeds non-adiabatically through clusters of vibrations with frequencies distributed around electronic energy gaps. I will also briefly talk about our experiments demonstrating quantitative time-resolved measurement of absolute number of excited state molecules. Based on these measurements, an all-optical technique that simultaneously determines
Mapping the Electronic States of One Dimensional Peapod Structures
NASA Astrophysics Data System (ADS)
Hornbaker, D. J.
2003-03-01
A key issue of potential technological importance is how the electronic properties of single wall carbon nanotubes are altered by their interactions with other molecules. We address this question by examining the properties of carbon heterostructures formed by the encapsulation of C_60 molecules within the hollow interiors of single wall nanotubes.^1 We study the properties of these novel macromolecules (dubbed 'peapods') using a low temperature, ultra-high vacuum scanning tunneling microscope (STM). Our experiments reveal that while no discernable change in the atomic structure of the encapsulating nanotubes is evident, the presence of interior C_60 molecules can dramatically affect the electronic structure of the nanotube cage. Constant current STM images of peapods display pronounced spatial modulation of the electronic density at sample biases greater than 1V, with a periodicity consistent with the intermolecular spacing of close-packed C_60 molecules inside the nanotube. This effect has been observed on peapods displaying both semiconducting and metallic densities of states. Coincident with this modulation is the appearance of characteristic features in the electronic band structure measured via tunneling spectroscopy. Theoretical modeling^2,3 indicates these features arise from coupling between the valence states of the encapsulated fullerenes, leading to the formation of a hybrid electronic band. Our experiments demonstrate that encapsulation of molecules is a viable route for selectively altering the electronic properties of carbon nanotubes. ^1B.W. Smith and D.E. Luzzi, Chem. Phys. Lett. 321, 169 (2000). ^2D.J. Hornbaker et al. Science 295, 828 (2002). ^3C. Kane et al. Phys. Rev. B (submitted).
Minimal-excitation states for electron quantum optics using levitons
NASA Astrophysics Data System (ADS)
Dubois, J.; Jullien, T.; Portier, F.; Roche, P.; Cavanna, A.; Jin, Y.; Wegscheider, W.; Roulleau, P.; Glattli, D. C.
2013-10-01
The on-demand generation of pure quantum excitations is important for the operation of quantum systems, but it is particularly difficult for a system of fermions. This is because any perturbation affects all states below the Fermi energy, resulting in a complex superposition of particle and hole excitations. However, it was predicted nearly 20 years ago that a Lorentzian time-dependent potential with quantized flux generates a minimal excitation with only one particle and no hole. Here we report that such quasiparticles (hereafter termed levitons) can be generated on demand in a conductor by applying voltage pulses to a contact. Partitioning the excitations with an electronic beam splitter generates a current noise that we use to measure their number. Minimal-excitation states are observed for Lorentzian pulses, whereas for other pulse shapes there are significant contributions from holes. Further identification of levitons is provided in the energy domain with shot-noise spectroscopy, and in the time domain with electronic Hong-Ou-Mandel noise correlations. The latter, obtained by colliding synchronized levitons on a beam splitter, exemplifies the potential use of levitons for quantum information: using linear electron quantum optics in ballistic conductors, it is possible to imagine flying-qubit operation in which the Fermi statistics are exploited to entangle synchronized electrons emitted by distinct sources. Compared with electron sources based on quantum dots, the generation of levitons does not require delicate nanolithography, considerably simplifying the circuitry for scalability. Levitons are not limited to carrying a single charge, and so in a broader context n-particle levitons could find application in the study of full electron counting statistics. But they can also carry a fraction of charge if they are implemented in Luttinger liquids or in fractional quantum Hall edge channels; this allows the study of Abelian and non-Abelian quasiparticles in the
Quantum gates with controlled adiabatic evolutions
NASA Astrophysics Data System (ADS)
Hen, Itay
2015-02-01
We introduce a class of quantum adiabatic evolutions that we claim may be interpreted as the equivalents of the unitary gates of the quantum gate model. We argue that these gates form a universal set and may therefore be used as building blocks in the construction of arbitrary "adiabatic circuits," analogously to the manner in which gates are used in the circuit model. One implication of the above construction is that arbitrary classical boolean circuits as well as gate model circuits may be directly translated to adiabatic algorithms with no additional resources or complexities. We show that while these adiabatic algorithms fail to exhibit certain aspects of the inherent fault tolerance of traditional quantum adiabatic algorithms, they may have certain other experimental advantages acting as quantum gates.
Electronic and ground state properties of ThTe
NASA Astrophysics Data System (ADS)
Bhardwaj, Purvee; Singh, Sadhna
2016-05-01
The electronic properties of ThTe in cesium chloride (CsCl, B2) structure are investigated in the present paper. To study the ground state properties of thorium chalcogenide, the first principle calculations have been calculated. The bulk properties, including lattice constant, bulk modulus and its pressure derivative are obtained. The calculated equilibrium structural parameters are in good agreement with the available experimental and theoretical results.
NASA Astrophysics Data System (ADS)
George, D. X. F.; Kumar, Sanjay
2010-08-01
Ab initio global adiabatic as well as quasidiabatic potential energy surfaces for the ground and the first excited electronic states of the H + + CO system have been computed as a function of the Jacobi coordinates ( R, r, γ) using Dunning's cc-pVTZ basis set at the internally contracted multi-reference (single and double) configuration interaction level of accuracy. In addition, nonadiabatic coupling matrix elements arising from radial motion, mixing angle and coupling potential have been computed using the ab initio procedure [Simah et al. (1999) [66
Non-adiabatic molecular dynamic simulations of opening reaction of molecular junctions
NASA Astrophysics Data System (ADS)
Zobač, Vladmír; Lewis, James P.; Jelínek, Pavel
2016-07-01
We report non-adiabatic molecular dynamic simulations of the ring opening reaction of diarylethene (DAE) derivative molecules, both free standing and embedded between gold electrodes. Simulations are performed by the surface hopping method employing density functional theory. Typically, the free-standing molecules exhibit large quantum yields to open and close; however the process is quenched for the molecules embedded between electrodes. Our simulations reveal the importance of the DAE side chemical groups, which explain the efficiency of the quenching process. Namely, delocalization of the LUMO state contributes to electronic coupling between the molecule and electrodes, suppressing or enhancing the reaction process. The simulations indicate that a proper choice of the chemical side group, which provides the strong localization of the LUMO state, can substantially diminish the quenching mechanism. Additionally, we analyze a strong dependency of the quantum yield of the opening reaction coming from the mechanical strength of the molecules.
Non-adiabatic molecular dynamic simulations of opening reaction of molecular junctions.
Zobač, Vladmír; Lewis, James P; Jelínek, Pavel
2016-07-15
We report non-adiabatic molecular dynamic simulations of the ring opening reaction of diarylethene (DAE) derivative molecules, both free standing and embedded between gold electrodes. Simulations are performed by the surface hopping method employing density functional theory. Typically, the free-standing molecules exhibit large quantum yields to open and close; however the process is quenched for the molecules embedded between electrodes. Our simulations reveal the importance of the DAE side chemical groups, which explain the efficiency of the quenching process. Namely, delocalization of the LUMO state contributes to electronic coupling between the molecule and electrodes, suppressing or enhancing the reaction process. The simulations indicate that a proper choice of the chemical side group, which provides the strong localization of the LUMO state, can substantially diminish the quenching mechanism. Additionally, we analyze a strong dependency of the quantum yield of the opening reaction coming from the mechanical strength of the molecules. PMID:27255903
Liquid-state polaron theory of the hydrated electron revisited
NASA Astrophysics Data System (ADS)
Donley, James P.; Heine, David R.; Tormey, Caleb A.; Wu, David T.
2014-07-01
The quantum path integral/classical liquid-state theory of Chandler and co-workers, created to describe an excess electron in solvent, is re-examined for the hydrated electron. The portion that models electron-water density correlations is replaced by two equations: the range optimized random phase approximation (RO-RPA), and the Donley, Rajasekaran, and Liu (DRL) approximation to the "two-chain" equation, both shown previously to describe accurately the static structure and thermodynamics of strongly charged polyelectrolyte solutions. The static equilibrium properties of the hydrated electron are analyzed using five different electron-water pseudopotentials. The theory is then compared with data from mixed quantum/classical Monte Carlo and molecular dynamics simulations using these same pseudopotentials. It is found that the predictions of the RO-RPA and DRL-based polaron theories are similar and improve upon previous theory, with values for almost all properties analyzed in reasonable quantitative agreement with the available simulation data. Also, it is found using the Larsen, Glover, and Schwartz pseudopotential that the theories give values for the solvation free energy that are at least three times larger than that from experiment.
Liquid-state polaron theory of the hydrated electron revisited
Donley, James P.; Heine, David R.; Tormey, Caleb A.; Wu, David T.
2014-07-14
The quantum path integral/classical liquid-state theory of Chandler and co-workers, created to describe an excess electron in solvent, is re-examined for the hydrated electron. The portion that models electron-water density correlations is replaced by two equations: the range optimized random phase approximation (RO-RPA), and the Donley, Rajasekaran, and Liu (DRL) approximation to the “two-chain” equation, both shown previously to describe accurately the static structure and thermodynamics of strongly charged polyelectrolyte solutions. The static equilibrium properties of the hydrated electron are analyzed using five different electron-water pseudopotentials. The theory is then compared with data from mixed quantum/classical Monte Carlo and molecular dynamics simulations using these same pseudopotentials. It is found that the predictions of the RO-RPA and DRL-based polaron theories are similar and improve upon previous theory, with values for almost all properties analyzed in reasonable quantitative agreement with the available simulation data. Also, it is found using the Larsen, Glover, and Schwartz pseudopotential that the theories give values for the solvation free energy that are at least three times larger than that from experiment.
NASA Astrophysics Data System (ADS)
Shakib, Farnaz A.; Hanna, Gabriel
2016-01-01
In a previous study [F. A. Shakib and G. Hanna, J. Chem. Phys. 141, 044122 (2014)], we investigated a model proton-coupled electron transfer (PCET) reaction via the mixed quantum-classical Liouville (MQCL) approach and found that the trajectories spend the majority of their time on the mean of two coherently coupled adiabatic potential energy surfaces. This suggested a need for mean surface evolution to accurately simulate observables related to ultrafast PCET processes. In this study, we simulate the time-dependent populations of the three lowest adiabatic states in the ET-PT (i.e., electron transfer preceding proton transfer) version of the same PCET model via the MQCL approach and compare them to the exact quantum results and those obtained via the fewest switches surface hopping (FSSH) approach. We find that the MQCL population profiles are in good agreement with the exact quantum results and show a significant improvement over the FSSH results. All of the mean surfaces are shown to play a direct role in the dynamics of the state populations. Interestingly, our results indicate that the population transfer to the second-excited state can be mediated by dynamics on the mean of the ground and second-excited state surfaces, as part of a sequence of nonadiabatic transitions that bypasses the first-excited state surface altogether. This is made possible through nonadiabatic transitions between different mean surfaces, which is the manifestation of coherence transfer in MQCL dynamics. We also investigate the effect of the strength of the coupling between the proton/electron and the solvent coordinate on the state population dynamics. Drastic changes in the population dynamics are observed, which can be understood in terms of the changes in the potential energy surfaces and the nonadiabatic couplings. Finally, we investigate the state population dynamics in the PT-ET (i.e., proton transfer preceding electron transfer) and concerted versions of the model. The PT
Two electronic states and state exchange time control in spherical nanolayer
NASA Astrophysics Data System (ADS)
Aghekyan, N. G.; Kazaryan, E. M.; Kostanyan, A. A.; Sarkisyan, H. A.
2011-09-01
Two electronic states in impenetrable spherical quantum nanolayer are discussed. The Coulomb interaction between the electrons is considered as perturbation. The problem is discussed within the frameworks of Russell-Saunders coupling scheme, that is, the spin-orbit interaction is neglected. For this system the analogue of helium atom theory is represented. The dependence of the Coulomb interaction energy of the two electronic system is obtained both upon inner and outer radiuses of the studied nanolayer. The exchange interaction in the spherical nanolayer helium atom and its dependence upon the geometrical parameters of the nanolayer are investigated. It is shown that the exchange time of two electron states could be controlled via changing the geometrical parameters of the nanolayer.
NMR implementation of adiabatic SAT algorithm using strongly modulated pulses.
Mitra, Avik; Mahesh, T S; Kumar, Anil
2008-03-28
NMR implementation of adiabatic algorithms face severe problems in homonuclear spin systems since the qubit selective pulses are long and during this period, evolution under the Hamiltonian and decoherence cause errors. The decoherence destroys the answer as it causes the final state to evolve to mixed state and in homonuclear systems, evolution under the internal Hamiltonian causes phase errors preventing the initial state to converge to the solution state. The resolution of these issues is necessary before one can proceed to implement an adiabatic algorithm in a large system where homonuclear coupled spins will become a necessity. In the present work, we demonstrate that by using "strongly modulated pulses" (SMPs) for the creation of interpolating Hamiltonian, one can circumvent both the problems and successfully implement the adiabatic SAT algorithm in a homonuclear three qubit system. This work also demonstrates that the SMPs tremendously reduce the time taken for the implementation of the algorithm, can overcome problems associated with decoherence, and will be the modality in future implementation of quantum information processing by NMR. PMID:18376911
NMR implementation of adiabatic SAT algorithm using strongly modulated pulses
NASA Astrophysics Data System (ADS)
Mitra, Avik; Mahesh, T. S.; Kumar, Anil
2008-03-01
NMR implementation of adiabatic algorithms face severe problems in homonuclear spin systems since the qubit selective pulses are long and during this period, evolution under the Hamiltonian and decoherence cause errors. The decoherence destroys the answer as it causes the final state to evolve to mixed state and in homonuclear systems, evolution under the internal Hamiltonian causes phase errors preventing the initial state to converge to the solution state. The resolution of these issues is necessary before one can proceed to implement an adiabatic algorithm in a large system where homonuclear coupled spins will become a necessity. In the present work, we demonstrate that by using "strongly modulated pulses" (SMPs) for the creation of interpolating Hamiltonian, one can circumvent both the problems and successfully implement the adiabatic SAT algorithm in a homonuclear three qubit system. This work also demonstrates that the SMPs tremendously reduce the time taken for the implementation of the algorithm, can overcome problems associated with decoherence, and will be the modality in future implementation of quantum information processing by NMR.
Ionization of the hydrogen atom in strong magnetic fields. Beyond the adiabatic approximation.
NASA Astrophysics Data System (ADS)
Potekhin, A. Y.; Pavlov, G. G.; Ventura, J.
1997-01-01
High magnetic fields in neutron stars, B~10^11^-10^13^G, substantially modify the properties of atoms and their interaction with radiation. In particular, the photoionization cross section becomes anisotropic and polarization dependent, being strongly reduced when the radiation is polarized perpendicular to the field. In a number of previous works based on the adiabatic approximation the conclusion was drawn that this transverse cross section vanishes for frequencies ω smaller than the electron cyclotron frequency ω_c_=eB/(m_e_c). In other works (which employed a different form of the interaction operator) appreciable finite values were obtained, ~σ_0gamma^-1^ near the photoionization threshold, where σ_0_ is the cross section without magnetic field, and γ=B/(2.35x10^9^G). Since it is the transverse cross section which determines the properties of radiation emitted from neutron star atmospheres, an adequate interpretation of the neutron star thermal-like radiation requires a resolution of this controversy. In the present work we calculate the atomic wave functions for both discrete and continuum states by solving the coupled channel equations allowing the admixture between different Landau levels, which provides much higher accuracy than the adiabatic approximation. This enables us to resolve the above contradiction in favour of the finite transverse cross sections at ω<ω_c_. Moreover, for any form of the interaction operator the non-adiabatic corrections appear to be substantial for frequencies ω> 0.3ω_c_. The non-adiabatic treatment of the continuum includes coupling between closed and open channels, which leads to the autoionization of quasi-bound energy levels associated with the electron cyclotron (Landau) excitations and gives rise to Beutler-Fano resonances of the photoionization cross section. We calculate the autoionization widths of these quasi-bound levels and compare them with the radiative widths. The correlation of the open channels is
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Adiabatic Quantum Computation with Neutral Atoms
NASA Astrophysics Data System (ADS)
Biedermann, Grant
2013-03-01
We are implementing a new platform for adiabatic quantum computation (AQC)[2] based on trapped neutral atoms whose coupling is mediated by the dipole-dipole interactions of Rydberg states. Ground state cesium atoms are dressed by laser fields in a manner conditional on the Rydberg blockade mechanism,[3,4] thereby providing the requisite entangling interactions. As a benchmark we study a Quadratic Unconstrained Binary Optimization (QUBO) problem whose solution is found in the ground state spin configuration of an Ising-like model. In collaboration with Lambert Parazzoli, Sandia National Laboratories; Aaron Hankin, Center for Quantum Information and Control (CQuIC), University of New Mexico; James Chin-Wen Chou, Yuan-Yu Jau, Peter Schwindt, Cort Johnson, and George Burns, Sandia National Laboratories; Tyler Keating, Krittika Goyal, and Ivan Deutsch, Center for Quantum Information and Control (CQuIC), University of New Mexico; and Andrew Landahl, Sandia National Laboratories. This work was supported by the Laboratory Directed Research and Development program at Sandia National Laboratories
Squeezed states of electrons and transitions of the density of states
NASA Technical Reports Server (NTRS)
Lee, Seung Joo; Um, Chung IN
1993-01-01
Electron systems which have low dimensional properties have been constructed by squeezing the motion in zero, one, or two-directions. An isolated quantum dot is modeled by a potential box with delta-profiled, penetrable potential walls embedded in a large outer box with infinitely high potential walls which represent the world function with respect to vacuum. We show the smooth crossover of the density of states from the three-dimensional to the quasi-zero dimensional electron gas.
Low-Lying Electronic States of CuAu.
Alizadeh Sanati, Davood; Andrae, Dirk
2016-07-28
Coinage metal diatomic molecules are building blocks for nanostructured materials, electronic devices, and catalytically or photochemically active systems that are currently receiving lively interest in both fundamental and applied research. The theoretical study presented here elucidates the electronic structure in the ground and several low-lying excited states of the diatomic molecule CuAu that result from the combination of the atoms in their ground states nd(10)(n + 1)s(1 2)S and lowest excited d-hole states nd(9)(n + 1)s(2 2)D (n = 3 for Cu, n = 5 for Au). Full and smooth potential energy curves, obtained at the multireference configuration interaction (MRCI) level of theory, are presented for the complete set of the thus resulting 44 Λ-S terms and 86 Ω terms. Our approach is based on a scalar relativistic description using the Douglas-Kroll-Hess (DKH) Hamiltonian, with subsequent perturbative inclusion of spin-orbit (SO) coupling via the spin-orbit terms of the Breit-Pauli (BP) Hamiltonian. The Ω terms span an energy interval of about 7 eV at the ground state's equilibrium distance. Spectroscopic constants, calculated for all terms, are shown to accurately reproduce the observation for those nine terms that are experimentally known. PMID:27379475
Coherent tunneling by adiabatic process in a four-waveguide optical coupler
NASA Astrophysics Data System (ADS)
Shi, Jian; Ma, Rui-Qiong; Duan, Zuo-Liang; Liang, Meng; Zhang, Wen-wen; Dong, Jun
2016-07-01
We numerically simulate Schrödinger-like paraxial wave equation of a four-waveguide system. The coherent tunneling by adiabatic passage in a four-waveguide optical coupler is analyzed by borrowing the dressed state theory of coherent atom system. We discuss the optical coupling mechanism and coupling efficiency of light energy in both intuitive and counterintuitive tunneling schemes and analyze the threshold condition from adiabatic to non-adiabatic regimes in intuitive scheme. The results show that this coupler can be used as power splitter under certain conditions.
NASA Astrophysics Data System (ADS)
Jones, D. B.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Lima, M. A. P.; Blanco, F.; García, G.; Brunger, M. J.
2016-04-01
We report absolute experimental integral cross sections (ICSs) for electron impact excitation of bands of electronic-states in furfural, for incident electron energies in the range 20-250 eV. Wherever possible, those results are compared to corresponding excitation cross sections in the structurally similar species furan, as previously reported by da Costa et al. [Phys. Rev. A 85, 062706 (2012)] and Regeta and Allan [Phys. Rev. A 91, 012707 (2015)]. Generally, very good agreement is found. In addition, ICSs calculated with our independent atom model (IAM) with screening corrected additivity rule (SCAR) formalism, extended to account for interference (I) terms that arise due to the multi-centre nature of the scattering problem, are also reported. The sum of those ICSs gives the IAM-SCAR+I total cross section for electron-furfural scattering. Where possible, those calculated IAM-SCAR+I ICS results are compared against corresponding results from the present measurements with an acceptable level of accord being obtained. Similarly, but only for the band I and band II excited electronic states, we also present results from our Schwinger multichannel method with pseudopotentials calculations. Those results are found to be in good qualitative accord with the present experimental ICSs. Finally, with a view to assembling a complete cross section data base for furfural, some binary-encounter-Bethe-level total ionization cross sections for this collision system are presented.
Jones, D B; da Costa, R F; Varella, M T do N; Bettega, M H F; Lima, M A P; Blanco, F; García, G; Brunger, M J
2016-04-14
We report absolute experimental integral cross sections (ICSs) for electron impact excitation of bands of electronic-states in furfural, for incident electron energies in the range 20-250 eV. Wherever possible, those results are compared to corresponding excitation cross sections in the structurally similar species furan, as previously reported by da Costa et al. [Phys. Rev. A 85, 062706 (2012)] and Regeta and Allan [Phys. Rev. A 91, 012707 (2015)]. Generally, very good agreement is found. In addition, ICSs calculated with our independent atom model (IAM) with screening corrected additivity rule (SCAR) formalism, extended to account for interference (I) terms that arise due to the multi-centre nature of the scattering problem, are also reported. The sum of those ICSs gives the IAM-SCAR+I total cross section for electron-furfural scattering. Where possible, those calculated IAM-SCAR+I ICS results are compared against corresponding results from the present measurements with an acceptable level of accord being obtained. Similarly, but only for the band I and band II excited electronic states, we also present results from our Schwinger multichannel method with pseudopotentials calculations. Those results are found to be in good qualitative accord with the present experimental ICSs. Finally, with a view to assembling a complete cross section data base for furfural, some binary-encounter-Bethe-level total ionization cross sections for this collision system are presented. PMID:27083717
Adiabatic corrections to density functional theory energies and wave functions.
Mohallem, José R; Coura, Thiago de O; Diniz, Leonardo G; de Castro, Gustavo; Assafrão, Denise; Heine, Thomas
2008-09-25
The adiabatic finite-nuclear-mass-correction (FNMC) to the electronic energies and wave functions of atoms and molecules is formulated for density-functional theory and implemented in the deMon code. The approach is tested for a series of local and gradient corrected density functionals, using MP2 results and diagonal-Born-Oppenheimer corrections from the literature for comparison. In the evaluation of absolute energy corrections of nonorganic molecules the LDA PZ81 functional works surprisingly better than the others. For organic molecules the GGA BLYP functional has the best performance. FNMC with GGA functionals, mainly BLYP, show a good performance in the evaluation of relative corrections, except for nonorganic molecules containing H atoms. The PW86 functional stands out with the best evaluation of the barrier of linearity of H2O and the isotopic dipole moment of HDO. In general, DFT functionals display an accuracy superior than the common belief and because the corrections are based on a change of the electronic kinetic energy they are here ranked in a new appropriate way. The approach is applied to obtain the adiabatic correction for full atomization of alcanes C(n)H(2n+2), n = 4-10. The barrier of 1 mHartree is approached for adiabatic corrections, justifying its insertion into DFT. PMID:18537228
Electronic excited states and relaxation dynamics in polymer heterojunction systems
NASA Astrophysics Data System (ADS)
Ramon, John Glenn Santos
, we examine the effect of the nanoscale interfacial morphology and solvation on the electronic excited states of TFB/F8BT. Here, we employ time-dependent density functional theory (TD-DFT) to investigate the relevant excited states of two stacking configurations. We show that the calculated states agree with the excited states responsible for the experimentally observed emission peaks and that these states are blue shifted relative to those of the isolated chain. Furthermore, slight lateral shifts in the stacking orientation not only shift the excited state energies; more importantly, they alter the nature of these states altogether. Lastly, we see that solvation greatly stabilizes the charge-transfer states.
Breakdown of adiabaticity when loading ultracold atoms in optical lattices
NASA Astrophysics Data System (ADS)
Zakrzewski, Jakub; Delande, Dominique
2009-07-01
Realistic simulations of current ultracold atom experiments in optical lattices show that the ramping up of the optical lattice is significantly nonadiabatic, implying that experimentally prepared Mott insulators are not really in the ground state of the atomic system. The nonadiabaticity is even larger in the presence of a secondary quasiperiodic lattice simulating “disorder.” Alternative ramping schemes are suggested that improve the adiabaticity when the disorder is not too large.
Filatov, Michael
2014-09-28
Electron transfer in the ground and excited states of a model donor–acceptor (D–A) system is investigated using the single-reference and multi-reference density functional theory (DFT) methods. To analyze the results of the calculations, a simple two-site multi-reference model was derived that predicts a stepwise electron transfer in the S{sub 0} state and a wave-like dependence of the S{sub 1} electron transfer on the external stimulus. The standard single-reference Kohn-Sham (KS) DFT approach and the time-dependent DFT (TDDFT) method failed to describe the correct dependence of the S{sub 0} and S{sub 1} electron transfer on the external electric field applied along the donor–acceptor system. The multi-reference DFT approach, the spin-restricted ensemble-referenced KS (REKS) method, was able to successfully reproduce the correct behavior of the S{sub 0} and S{sub 1} electron transfer on the applied field. The REKS method was benchmarked against experimentally measured gas phase charge transfer excitations in a series of organic donor–acceptor complexes and displayed its ability to describe this type of electronic transitions with a very high accuracy, mean absolute error of 0.05 eV with the use of the standard range separated density functionals. On the basis of the calculations undertaken in this work, it is suggested that the non-adiabatic coupling between the S{sub 0} and S{sub 1} states may interfere with the electron transfer in a weakly coupled donor–acceptor system. It is also suggested that the electronic excitation of a D{sup +}–A{sup −} system may play a dual role by assisting the further electron transfer at certain magnitudes of the applied electric field and causing the backward transfer at lower electric field strengths.
Electronic structures of interfacial states formed at polymeric semiconductor heterojunctions
NASA Astrophysics Data System (ADS)
Huang, Ya-Shih; Westenhoff, Sebastian; Avilov, Igor; Sreearunothai, Paiboon; Hodgkiss, Justin M.; Deleener, Caroline; Friend, Richard H.; Beljonne, David
2008-06-01
Heterojunctions between organic semiconductors are central to the operation of light-emitting and photovoltaic diodes, providing respectively for electron-hole capture and separation. However, relatively little is known about the character of electronic excitations stable at the heterojunction. We have developed molecular models to study such interfacial excited electronic excitations that form at the heterojunction between model polymer donor and polymer acceptor systems: poly(9,9-dioctylfluorene-co-bis-N,N-(4-butylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine) (PFB) with poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT), and poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) with F8BT. We find that for stable ground-state geometries the excited state has a strong charge-transfer character. Furthermore, when partly covalent, modelled radiative lifetimes (~10-7s) and off-chain axis polarization (30∘) match observed `exciplex' emission. Additionally for the PFB:F8BT blend, geometries with fully ionic character are also found, thus accounting for the low electroluminescence efficiency of this system.
Highly parallel implementation of non-adiabatic Ehrenfest molecular dynamics
NASA Astrophysics Data System (ADS)
Kanai, Yosuke; Schleife, Andre; Draeger, Erik; Anisimov, Victor; Correa, Alfredo
2014-03-01
While the adiabatic Born-Oppenheimer approximation tremendously lowers computational effort, many questions in modern physics, chemistry, and materials science require an explicit description of coupled non-adiabatic electron-ion dynamics. Electronic stopping, i.e. the energy transfer of a fast projectile atom to the electronic system of the target material, is a notorious example. We recently implemented real-time time-dependent density functional theory based on the plane-wave pseudopotential formalism in the Qbox/qb@ll codes. We demonstrate that explicit integration using a fourth-order Runge-Kutta scheme is very suitable for modern highly parallelized supercomputers. Applying the new implementation to systems with hundreds of atoms and thousands of electrons, we achieved excellent performance and scalability on a large number of nodes both on the BlueGene based ``Sequoia'' system at LLNL as well as the Cray architecture of ``Blue Waters'' at NCSA. As an example, we discuss our work on computing the electronic stopping power of aluminum and gold for hydrogen projectiles, showing an excellent agreement with experiment. These first-principles calculations allow us to gain important insight into the the fundamental physics of electronic stopping.
Progress towards Generating Rydberg State, One Electron Ions
NASA Astrophysics Data System (ADS)
Dreiling, Joan; Fogwell Hoogerheide, Shannon; Naing, Aung; Tan, Joseph
2016-05-01
We report on progress towards producing hydrogen-like ions in Rydberg states from bare nuclei. Fully stripped neon atoms (Ne10+) are produced by the electron beam ion trap (EBIT) at NIST. These ions are extracted via a beamline from the EBIT into a second apparatus where they are captured at low energy in a unitary Penning trap. The second apparatus has a cross-beam configuration, with a perpendicular beam of laser excited Rb atoms intersecting the ion beam at the Penning trap. While stored in the trap, the ions can interact with the Rb and, through charge exchange interactions, the bare nuclei can capture one or more electrons from the Rb. The ions are then analyzed by dumping the trap to a time-of-flight detector, which allows determination of the ion charge state evolution. This work builds towards laser spectroscopy on hydrogen-like ions in circular Rydberg states to obtain a value for the Rydberg constant independent of nuclear size effects. Such a measurement could shed some light on the proton radius puzzle.
Heating and cooling in adiabatic mixing process
NASA Astrophysics Data System (ADS)
Zhou, Jing; Cai, Zi; Zou, Xu-Bo; Guo, Guang-Can
2010-12-01
We study the effect of interaction on the temperature change in the process of adiabatic mixing of two components of Fermi gases using the real-space Bogoliubov-de Gennes method. We find that in the process of adiabatic mixing, the competition between the adiabatic expansion and the attractive interaction makes it possible to cool or heat the system depending on the strength of the interaction and the initial temperature of the system. The changes of the temperature in a bulk system and in a trapped system are investigated.
NASA Astrophysics Data System (ADS)
Winney, Alexander H.; Lin, Yun Fei; Lee, Suk Kyoung; Adhikari, Pradip; Li, Wen
2016-03-01
We report state-resolved electron-momentum correlation measurement of strong-field nonsequential double ionization in benzene. With a novel coincidence detection apparatus, highly efficient triple coincidence (electron-electron dication) and quadruple coincidence (electron-electron-cation-cation) are used to resolve the final ionic states and to characterize three-dimensional (3D) electron-momentum correlation. The primary states associated with dissociative and nondissociative dications are assigned. A 3D momentum anticorrelation is observed for the electrons in coincidence with dissociative benzene dication states whereas such a correlation is absent for nondissociative dication states.
Piezoelectric control of the mobility of a domain wall driven by adiabatic and non-adiabatic torques
NASA Astrophysics Data System (ADS)
de Ranieri, E.; Roy, P. E.; Fang, D.; Vehsthedt, E. K.; Irvine, A. C.; Heiss, D.; Casiraghi, A.; Campion, R. P.; Gallagher, B. L.; Jungwirth, T.; Wunderlich, J.
2013-09-01
The rich internal degrees of freedom of magnetic domain walls make them an attractive complement to electron charge for exploring new concepts of storage, transport and processing of information. Here we use the tunable internal structure of a domain wall in a perpendicularly magnetized GaMnAsP/GaAs ferromagnetic semiconductor and demonstrate devices in which piezoelectrically controlled magnetic anisotropy yields up to 500% mobility variations for an electrical-current-driven domain wall. We observe current-induced domain wall motion over a wide range of current-pulse amplitudes and report a direct observation and the piezoelectric control of the Walker breakdown separating two regimes with different mobilities. Our work demonstrates that in spin-orbit-coupled ferromagnets with weak extrinsic domain wall pinning, the piezoelectric control allows one to experimentally assess the upper and lower boundaries of the characteristic ratio of adiabatic and non-adiabatic spin-transfer torques in the current-driven domain wall motion.
Invisible Electronic States and Their Dynamics Revealed by Perturbations
NASA Astrophysics Data System (ADS)
Merer, Anthony J.
2011-06-01
Sooner or later everyone working in the field of spectroscopy encounters perturbations. These can range in size from a small shift of a single rotational level to total destruction of the vibrational and rotational patterns of an electronic state. To some workers perturbations are a source of terror, but to others they are the most fascinating features of molecular spectra, because they give information about molecular dynamics, and about states that would otherwise be invisible as a result of unfavorable selection rules. An example of the latter is the essentially complete characterization of the tilde{b}^3A_2 state of SO_2 from the vibronic perturbations it causes in the tilde{a}^3B_1 state. The S_1-trans state of acetylene is a beautiful example of dynamics in action. The level patterns of the three bending vibrations change dramatically with increasing vibrational excitation as a result of the vibrational angular momentum and the approach to the isomerization barrier. Several vibrational levels of the S_1-cis isomer, previously thought to be unobservable, can now be assigned. They obtain their intensity through interactions with nearby levels of the trans isomer.
Differential cross sections for electron-impact excitation of the electronic states of N sub 2
Brunger, M.J.; Teubner, P.J.O. )
1990-02-01
Differential cross sections for the electron-impact excitation of the first ten electronic states of N{sub 2} have been determined at five incident energies ranging from 15 to 50 eV. These differential cross sections were obtained for the scattering range 10{degree}--90{degree} by analyzing electron-energy-loss spectra in N{sub 2} at a number of fixed scattering angles within that range. The present study represents a comprehensive remeasurement of the earlier work of Cartwright and co-workers (Phys. Rev. A 16, 1013 (1977)) and was undertaken with a view to resolving certain anomalies which have been reported in the literature when the earlier cross-section set has been applied to model calculations of swarm parameters.
Zhu, Xiaolei Yarkony, David R.
2014-11-07
For conical intersections of two states (I,J = I + 1) the vectors defining the branching or g-h plane, the energy difference gradient vector g{sup I,J}, and the interstate coupling vector h{sup I,J}, can be made orthogonal by a one parameter rotation of the degenerate electronic eigenstates. The representation obtained from this rotation is used to construct the parameters that describe the vicinity of the conical intersection seam, the conical parameters, s{sup I,J}{sub x} (R), s{sup I,J}{sub y} (R), g{sup I,J}(R), and h{sup I,J}(R). As a result of the orthogonalization these parameters can be made continuous functions of R, the internuclear coordinates. In this work we generalize this notion to construct continuous parametrizations of conical intersection seams of three or more states. The generalization derives from a recently introduced procedure for using non-degenerate electronic states to construct coupled diabatic states that represent adiabatic states coupled by conical intersections. The procedure is illustrated using the seam of conical intersections of three states in parazolyl as an example.
Sanz-Sanz, Cristina; Aguado, Alfredo; Roncero, Octavio; Naumkin, Fedor
2015-12-21
Analytical derivatives and non-adiabatic coupling matrix elements are derived for Hn (+) systems (n = 3-5). The method uses a generalized Hellmann-Feynman theorem applied to a multi-state description based on diatomics-in-molecules (for H3 (+)) or triatomics-in-molecules (for H4 (+) and H5 (+)) formalisms, corrected with a permutationally invariant many-body term to get high accuracy. The analytical non-adiabatic coupling matrix elements are compared with ab initio calculations performed at multi-reference configuration interaction level. These magnitudes are used to calculate H2(v(')=0,j(')=0)+H2 (+)(v,j=0) collisions, to determine the effect of electronic transitions using a molecular dynamics method with electronic transitions. Cross sections for several initial vibrational states of H2 (+) are calculated and compared with the available experimental data, yielding an excellent agreement. The effect of vibrational excitation of H2 (+) reactant and its relation with non-adiabatic processes are discussed. Also, the behavior at low collisional energies, in the 1 meV-0.1 eV interval, of interest in astrophysical environments, is discussed in terms of the long range behaviour of the interaction potential which is properly described within the triatomics-in-molecules formalism. PMID:26696058
Sanz-Sanz, Cristina; Aguado, Alfredo; Roncero, Octavio; Naumkin, Fedor
2016-01-01
Analytical derivatives and non-adiabatic coupling matrix elements are derived for Hn+ systems (n=3, 4 and 5). The method uses a generalized Hellmann-Feynman theorem applied to a multi-state description based on diatomics-in-molecules (for H3+) or triatomics-in-molecules (for H4+ and H5+) formalisms, corrected with a permutationally invariant many-body term to get high accuracy. The analytical non-adiabatic coupling matrix elements are compared with ab initio calculations performed at multi-reference configuration interaction level. These magnitudes are used to calculate H2(v′=0,j′=0)+H2+(v,j=0) collisions, to determine the effect of electronic transitions using a molecular dynamics method with electronic transitions. Cross sections for several initial vibrational states of H2+ are calculated and compared with the available experimental data, yielding an excellent agreement. The effect of vibrational excitation of H2+ reactant, and its relation with non-adiabatic processes are discussed. Also, the behavior at low collisional energies, in the 1 meV-0.1 eV interval, of interest in astrophysical environments, are discussed in terms of the long range behaviour of the interaction potential which is properly described within the TRIM formalism. PMID:26696058
NASA Astrophysics Data System (ADS)
Sanz-Sanz, Cristina; Aguado, Alfredo; Roncero, Octavio; Naumkin, Fedor
2015-12-01
Analytical derivatives and non-adiabatic coupling matrix elements are derived for H n+ systems (n = 3-5). The method uses a generalized Hellmann-Feynman theorem applied to a multi-state description based on diatomics-in-molecules (for H 3+ ) or triatomics-in-molecules (for H 4+ and H 5+ ) formalisms, corrected with a permutationally invariant many-body term to get high accuracy. The analytical non-adiabatic coupling matrix elements are compared with ab initio calculations performed at multi-reference configuration interaction level. These magnitudes are used to calculate H 2 ( v ' = 0 , j ' = 0 ) + H2 + ( v , j = 0 ) collisions, to determine the effect of electronic transitions using a molecular dynamics method with electronic transitions. Cross sections for several initial vibrational states of H 2+ are calculated and compared with the available experimental data, yielding an excellent agreement. The effect of vibrational excitation of H 2+ reactant and its relation with non-adiabatic processes are discussed. Also, the behavior at low collisional energies, in the 1 meV-0.1 eV interval, of interest in astrophysical environments, is discussed in terms of the long range behaviour of the interaction potential which is properly described within the triatomics-in-molecules formalism.
Multisurface Adiabatic Reactive Molecular Dynamics.
Nagy, Tibor; Yosa Reyes, Juvenal; Meuwly, Markus
2014-04-01
Adiabatic reactive molecular dynamics (ARMD) simulation method is a surface-crossing algorithm for modeling chemical reactions in classical molecular dynamics simulations using empirical force fields. As the ARMD Hamiltonian is time dependent during crossing, it allows only approximate energy conservation. In the current work, the range of applicability of conventional ARMD is explored, and a new multisurface ARMD (MS-ARMD) method is presented, implemented in CHARMM and applied to the vibrationally induced photodissociation of sulfuric acid (H2SO4) in the gas phase. For this, an accurate global potential energy surface (PES) involving 12 H2SO4 and 4 H2O + SO3 force fields fitted to MP2/6-311G++(2d,2p) reference energies is employed. The MS-ARMD simulations conserve total energy and feature both intramolecular H-transfer reactions and water elimination. An analytical treatment of the dynamics in the crossing region finds that conventional ARMD can approximately conserve total energy for limiting cases. In one of them, the reduced mass of the system is large, which often occurs for simulations of solvated biomolecular systems. On the other hand, MS-ARMD is a general approach for modeling chemical reactions including gas-phase, homogeneous, heterogeneous, and enzymatic catalytic reactions while conserving total energy in atomistic simulations. PMID:26580356
MRCI study on electronic spectrum of 13 electronic states of SiP molecule
NASA Astrophysics Data System (ADS)
Shi, Deheng; Xing, Wei; Liu, Hui; Sun, Jinfeng; Zhu, Zunlue
2012-11-01
The potential energy curves (PECs) of the X2Π, A2Σ+, a4Σ+, B2Π, c4Δ, C2Σ+, d4Σ-, D2Φ, E2Σ-, G2Δ, H2Π, I2Σ+ and f4Δ electronic states of the SiP molecule are calculated employing an ab initio quantum chemical method. The PEC calculations are performed for internuclear separations from 0.10 to 1.10 nm using the complete active space self-consistent field (CASSCF) method, which is followed by the internally contracted multireference configuration interaction (MRCI) approach in combination with a correlation-consistent aug-cc-pV6Z basis set. To improve the quality of the PECs, core-valence correlation and scalar relativistic corrections are included. Scalar relativistic correction calculations are carried out using the third-order Douglas-Kroll Hamiltonian approximation at the level of a cc-pV5Z basis set. Core-valence correlation corrections are included using a cc-pCVQZ basis set. The PECs obtained by the MRCI calculations are corrected for size-extensivity errors by means of the Davidson modification. The PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are obtained by fitting the vibrational levels, which are calculated by solving the ro-vibrational Schrödinger equation. The spectroscopic results are compared in detail with those reported in previous literature. Excellent agreement is found between the present spectroscopic results and the experimental ones. Using the Breit-Pauli operator, the spin-orbit (SO) coupling effect on the spectroscopic parameters is included in the X2Π, D2Φ and H2Π electronic states at the level of a cc-pCVTZ basis set. The energy separation of the X2Π and A2Σ+ electronic states is accurately determined by including the Davidson modification, SO coupling and core-valence correlation and scalar relativistic corrections. Using the PECs determined by the MRCI + Q/CV + DK + 56 calculations, the G(υ), Bυ and Dυ are calculated for each vibrational state of each electronic state, and those
MRCI study on electronic spectrum of 13 electronic states of SiP molecule.
Shi, Deheng; Xing, Wei; Liu, Hui; Sun, Jinfeng; Zhu, Zunlue
2012-11-01
The potential energy curves (PECs) of the X(2)Π, A(2)Σ(+), a(4)Σ(+), B(2)Π, c(4)Δ, C(2)Σ(+), d(4)Σ(-), D(2)Φ, E(2)Σ(-), G(2)Δ, H(2)Π, I(2)Σ(+) and f(4)Δ electronic states of the SiP molecule are calculated employing an ab initio quantum chemical method. The PEC calculations are performed for internuclear separations from 0.10 to 1.10nm using the complete active space self-consistent field (CASSCF) method, which is followed by the internally contracted multireference configuration interaction (MRCI) approach in combination with a correlation-consistent aug-cc-pV6Z basis set. To improve the quality of the PECs, core-valence correlation and scalar relativistic corrections are included. Scalar relativistic correction calculations are carried out using the third-order Douglas-Kroll Hamiltonian approximation at the level of a cc-pV5Z basis set. Core-valence correlation corrections are included using a cc-pCVQZ basis set. The PECs obtained by the MRCI calculations are corrected for size-extensivity errors by means of the Davidson modification. The PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are obtained by fitting the vibrational levels, which are calculated by solving the ro-vibrational Schrödinger equation. The spectroscopic results are compared in detail with those reported in previous literature. Excellent agreement is found between the present spectroscopic results and the experimental ones. Using the Breit-Pauli operator, the spin-orbit (SO) coupling effect on the spectroscopic parameters is included in the X(2)Π, D(2)Φ and H(2)Π electronic states at the level of a cc-pCVTZ basis set. The energy separation of the X(2)Π and A(2)Σ(+) electronic states is accurately determined by including the Davidson modification, SO coupling and core-valence correlation and scalar relativistic corrections. Using the PECs determined by the MRCI+Q/CV+DK+56 calculations, the G(υ), B(υ) and D(υ) are calculated for each
Topology and quantum states: The electron-monopole system
NASA Astrophysics Data System (ADS)
Di Cosmo, F.; Marmo, G.; Zampini, A.
2016-09-01
This paper starts by describing the dynamics of the electron-monopole system at both classical and quantum level by a suitable reduction procedure. This suggests, in order to realise the space of states for quantum systems which are classically described on topologically non-trivial configuration spaces, to consider Hilbert spaces of exterior differential forms. Among the advantages of this formulation, we present--in the case of the group SU(2) , how it is possible to obtain all unitary irreducible representations on such a Hilbert space, and how it is possible to write scalar Dirac-type operators, following an idea by Kähler.
NASA Astrophysics Data System (ADS)
Beyer, Maximilian; Merkt, Frédéric
2016-03-01
Although the existence of quasibound rotational levels of the X+ 2Σg+ ground state of H2+ was predicted a long time ago, these states have never been observed. Calculated positions and widths of quasibound rotational levels located close to the top of the centrifugal barriers have not been reported either. Given the role that such states play in the recombination of H (1 s ) and H+ to form H2+, this lack of data may be regarded as one of the largest unknown aspects of this otherwise accurately known fundamental molecular cation. We present measurements of the positions and widths of the lowest-lying quasibound rotational levels of H2+ and compare the experimental results with the positions and widths we calculate using a potential model for the X+ state of H2+ which includes adiabatic, nonadiabatic, relativistic, and radiative corrections to the Born-Oppenheimer approximation.
Cage electron-hydroxyl complex state as electron donor in mayenite
NASA Astrophysics Data System (ADS)
Hiraishi, M.; Kojima, K. M.; Miyazaki, M.; Yamauchi, I.; Okabe, H.; Koda, A.; Kadono, R.; Matsuishi, S.; Hosono, H.
2016-03-01
It is inferred from the chemical shift of muon spin rotation (μ SR ) spectra that muons implanted in pristine (fully oxidized) mayenite, [Ca12Al14O32] 2 +[□5O2 -] (C12A7, with □ referring to the vacant cage), are bound to O2 - at the cage center to form OMu- (where Mu represents muonium, a muonic analog of the H atom). However, an isolated negatively charged state (Mu-, an analog of H-) becomes dominant when the compound approaches the state of electride [Ca12Al14O32] 2 +[□42 e-] as a result of the reduction process. Moreover, the OMu- state in the pristine specimen exhibits depolarization of paramagnetic origin at low temperatures (below ˜30 K), indicating that OMu- accompanies a loosely bound electron in the cage that can be thermally activated. This suggests that interstitial muons (and hence H) forming a "cage electron-hydroxyl" complex can serve as electron donors in C12A7.
Semiclassical Dynamics of Electron Wave Packet States with Phase Vortices
Bliokh, Konstantin Yu.; Bliokh, Yury P.; Savel'ev, Sergey; Nori, Franco
2007-11-09
We consider semiclassical higher-order wave packet solutions of the Schroedinger equation with phase vortices. The vortex line is aligned with the propagation direction, and the wave packet carries a well-defined orbital angular momentum (OAM) ({Dirac_h}/2{pi})l (l is the vortex strength) along its main linear momentum. The probability current coils around the momentum in such OAM states of electrons. In an electric field, these states evolve like massless particles with spin l. The magnetic-monopole Berry curvature appears in momentum space, which results in a spin-orbit-type interaction and a Berry/Magnus transverse force acting on the wave packet. This brings about the OAM Hall effect. In a magnetic field, there is a Zeeman interaction, which, can lead to more complicated dynamics.
Adiabatic limits on Riemannian Heisenberg manifolds
Yakovlev, A A
2008-02-28
An asymptotic formula is obtained for the distribution function of the spectrum of the Laplace operator, in the adiabatic limit for the foliation defined by the orbits of an invariant flow on a compact Riemannian Heisenberg manifold. Bibliography: 21 titles.
Experimental demonstration of composite adiabatic passage
NASA Astrophysics Data System (ADS)
Schraft, Daniel; Halfmann, Thomas; Genov, Genko T.; Vitanov, Nikolay V.
2013-12-01
We report an experimental demonstration of composite adiabatic passage (CAP) for robust and efficient manipulation of two-level systems. The technique represents a altered version of rapid adiabatic passage (RAP), driven by composite sequences of radiation pulses with appropriately chosen phases. We implement CAP with radio-frequency pulses to invert (i.e., to rephase) optically prepared spin coherences in a Pr3+:Y2SiO5 crystal. We perform systematic investigations of the efficiency of CAP and compare the results with conventional π pulses and RAP. The data clearly demonstrate the superior features of CAP with regard to robustness and efficiency, even under conditions of weakly fulfilled adiabaticity. The experimental demonstration of composite sequences to support adiabatic passage is of significant relevance whenever a high efficiency or robustness of coherent excitation processes need to be maintained, e.g., as required in quantum information technology.
An Adiabatic Architecture for Linear Signal Processing
NASA Astrophysics Data System (ADS)
Vollmer, M.; Götze, J.
2005-05-01
Using adiabatic CMOS logic instead of the more traditional static CMOS logic can lower the power consumption of a hardware design. However, the characteristic differences between adiabatic and static logic, such as a four-phase clock, have a far reaching influence on the design itself. These influences are investigated in this paper by adapting a systolic array of CORDIC devices to be implemented adiabatically. We present a means to describe adiabatic logic in VHDL and use it to define the systolic array with precise timing and bit-true calculations. The large pipeline bubbles that occur in a naive version of this array are identified and removed to a large degree. As an example, we demonstrate a parameterization of the CORDIC array that carries out adaptive RLS filtering.
Adiabatic invariance of oscillons/I -balls
NASA Astrophysics Data System (ADS)
Kawasaki, Masahiro; Takahashi, Fuminobu; Takeda, Naoyuki
2015-11-01
Real scalar fields are known to fragment into spatially localized and long-lived solitons called oscillons or I -balls. We prove the adiabatic invariance of the oscillons/I -balls for a potential that allows periodic motion even in the presence of non-negligible spatial gradient energy. We show that such a potential is uniquely determined to be the quadratic one with a logarithmic correction, for which the oscillons/I -balls are absolutely stable. For slightly different forms of the scalar potential dominated by the quadratic one, the oscillons/I -balls are only quasistable, because the adiabatic charge is only approximately conserved. We check the conservation of the adiabatic charge of the I -balls in numerical simulation by slowly varying the coefficient of logarithmic corrections. This unambiguously shows that the longevity of oscillons/I -balls is due to the adiabatic invariance.
Experimental implementation of adiabatic passage between different topological orders.
Peng, Xinhua; Luo, Zhihuang; Zheng, Wenqiang; Kou, Supeng; Suter, Dieter; Du, Jiangfeng
2014-08-22
Topological orders are exotic phases of matter existing in strongly correlated quantum systems, which are beyond the usual symmetry description and cannot be distinguished by local order parameters. Here we report an experimental quantum simulation of the Wen-plaquette spin model with different topological orders in a nuclear magnetic resonance system, and observe the adiabatic transition between two Z(2) topological orders through a spin-polarized phase by measuring the nonlocal closed-string (Wilson loop) operator. Moreover, we also measure the entanglement properties of the topological orders. This work confirms the adiabatic method for preparing topologically ordered states and provides an experimental tool for further studies of complex quantum systems. PMID:25192080
Adiabatic and diabatic process of sum frequency conversion.
Liqing, Ren; Yongfang, Li; Baihong, Li; Lei, Wang; Zhaohua, Wang
2010-09-13
Based on the dressed state formalism, we obtain the adiabatic criterion of the sum frequency conversion. We show that this constraint restricts the energy conversion between the two dressed fields, which are superpositions of the signal field and the sum frequency field. We also show that the evolution of the populations of the dressed fields, which in turn describes the conversion of light photons from the seed frequency to the sum frequency during propagation through the nonlinear crystal. Take the quasiphased matched (QPM) scheme as an example, we calculate the expected bandwidth of the frequency conversion process, and its dependence on the length of the crystal. We demonstrate that the evolutionary patterns of the sum frequency field's energy are similar to the Fresnel diffraction of a light field. We finally show that the expected bandwidth can be also deduced from the evolution of the adiabaticity of the dressed fileds. PMID:20940935
Fastest Effectively Adiabatic Transitions for a Collection of Harmonic Oscillators.
Boldt, Frank; Salamon, Peter; Hoffmann, Karl Heinz
2016-05-19
We discuss fastest effectively adiabatic transitions (FEATs) for a collection of noninteracting harmonic oscillators with shared controllable real frequencies. The construction of such transitions is presented for given initial and final equilibrium states, and the dependence of the minimum time control on the interval of achievable frequencies is discussed. While the FEAT times and associated FEAT processes are important in their own right as optimal controls, the FEAT time is an added feature which provides a measure of the quality of a shortcut to adiabaticity (STA). The FEAT time is evaluated for a previously reported experiment, wherein a cloud of Rb atoms is cooled following a STA recipe that took about twice as long as the FEAT speed limit, a time efficiency of 50%. PMID:26811863
Steam bottoming cycle for an adiabatic diesel engine
NASA Technical Reports Server (NTRS)
Poulin, E.; Demier, R.; Krepchin, I.; Walker, D.
1984-01-01
Steam bottoming cycles using adiabatic diesel engine exhaust heat which projected substantial performance and economic benefits for long haul trucks were studied. Steam cycle and system component variables, system cost, size and performance were analyzed. An 811 K/6.90 MPa state of the art reciprocating expander steam system with a monotube boiler and radiator core condenser was selected for preliminary design. The costs of the diesel with bottoming system (TC/B) and a NASA specified turbocompound adiabatic diesel with aftercooling with the same total output were compared, the annual fuel savings less the added maintenance cost was determined to cover the increase initial cost of the TC/B system in a payback period of 2.3 years. Steam bottoming system freeze protection strategies were developed, technological advances required for improved system reliability are considered and the cost and performance of advanced systes are evaluated.
Nenov, Artur Giussani, Angelo; Segarra-Martí, Javier; Jaiswal, Vishal K.; Rivalta, Ivan; Cerullo, Giulio; Mukamel, Shaul; Garavelli, Marco E-mail: marco.garavelli@ens-lyon.fr
2015-06-07
Pump-probe electronic spectroscopy using femtosecond laser pulses has evolved into a standard tool for tracking ultrafast excited state dynamics. Its two-dimensional (2D) counterpart is becoming an increasingly available and promising technique for resolving many of the limitations of pump-probe caused by spectral congestion. The ability to simulate pump-probe and 2D spectra from ab initio computations would allow one to link mechanistic observables like molecular motions and the making/breaking of chemical bonds to experimental observables like excited state lifetimes and quantum yields. From a theoretical standpoint, the characterization of the electronic transitions in the visible (Vis)/ultraviolet (UV), which are excited via the interaction of a molecular system with the incoming pump/probe pulses, translates into the determination of a computationally challenging number of excited states (going over 100) even for small/medium sized systems. A protocol is therefore required to evaluate the fluctuations of spectral properties like transition energies and dipole moments as a function of the computational parameters and to estimate the effect of these fluctuations on the transient spectral appearance. In the present contribution such a protocol is presented within the framework of complete and restricted active space self-consistent field theory and its second-order perturbation theory extensions. The electronic excited states of adenine have been carefully characterized through a previously presented computational recipe [Nenov et al., Comput. Theor. Chem. 1040–1041, 295-303 (2014)]. A wise reduction of the level of theory has then been performed in order to obtain a computationally less demanding approach that is still able to reproduce the characteristic features of the reference data. Foreseeing the potentiality of 2D electronic spectroscopy to track polynucleotide ground and excited state dynamics, and in particular its expected ability to provide
Nenov, Artur; Giussani, Angelo; Segarra-Martí, Javier; Jaiswal, Vishal K; Rivalta, Ivan; Cerullo, Giulio; Mukamel, Shaul; Garavelli, Marco
2015-06-01
Pump-probe electronic spectroscopy using femtosecond laser pulses has evolved into a standard tool for tracking ultrafast excited state dynamics. Its two-dimensional (2D) counterpart is becoming an increasingly available and promising technique for resolving many of the limitations of pump-probe caused by spectral congestion. The ability to simulate pump-probe and 2D spectra from ab initio computations would allow one to link mechanistic observables like molecular motions and the making/breaking of chemical bonds to experimental observables like excited state lifetimes and quantum yields. From a theoretical standpoint, the characterization of the electronic transitions in the visible (Vis)/ultraviolet (UV), which are excited via the interaction of a molecular system with the incoming pump/probe pulses, translates into the determination of a computationally challenging number of excited states (going over 100) even for small/medium sized systems. A protocol is therefore required to evaluate the fluctuations of spectral properties like transition energies and dipole moments as a function of the computational parameters and to estimate the effect of these fluctuations on the transient spectral appearance. In the present contribution such a protocol is presented within the framework of complete and restricted active space self-consistent field theory and its second-order perturbation theory extensions. The electronic excited states of adenine have been carefully characterized through a previously presented computational recipe [Nenov et al., Comput. Theor. Chem. 1040-1041, 295-303 (2014)]. A wise reduction of the level of theory has then been performed in order to obtain a computationally less demanding approach that is still able to reproduce the characteristic features of the reference data. Foreseeing the potentiality of 2D electronic spectroscopy to track polynucleotide ground and excited state dynamics, and in particular its expected ability to provide
NASA Astrophysics Data System (ADS)
Nenov, Artur; Giussani, Angelo; Segarra-Martí, Javier; Jaiswal, Vishal K.; Rivalta, Ivan; Cerullo, Giulio; Mukamel, Shaul; Garavelli, Marco
2015-06-01
Pump-probe electronic spectroscopy using femtosecond laser pulses has evolved into a standard tool for tracking ultrafast excited state dynamics. Its two-dimensional (2D) counterpart is becoming an increasingly available and promising technique for resolving many of the limitations of pump-probe caused by spectral congestion. The ability to simulate pump-probe and 2D spectra from ab initio computations would allow one to link mechanistic observables like molecular motions and the making/breaking of chemical bonds to experimental observables like excited state lifetimes and quantum yields. From a theoretical standpoint, the characterization of the electronic transitions in the visible (Vis)/ultraviolet (UV), which are excited via the interaction of a molecular system with the incoming pump/probe pulses, translates into the determination of a computationally challenging number of excited states (going over 100) even for small/medium sized systems. A protocol is therefore required to evaluate the fluctuations of spectral properties like transition energies and dipole moments as a function of the computational parameters and to estimate the effect of these fluctuations on the transient spectral appearance. In the present contribution such a protocol is presented within the framework of complete and restricted active space self-consistent field theory and its second-order perturbation theory extensions. The electronic excited states of adenine have been carefully characterized through a previously presented computational recipe [Nenov et al., Comput. Theor. Chem. 1040-1041, 295-303 (2014)]. A wise reduction of the level of theory has then been performed in order to obtain a computationally less demanding approach that is still able to reproduce the characteristic features of the reference data. Foreseeing the potentiality of 2D electronic spectroscopy to track polynucleotide ground and excited state dynamics, and in particular its expected ability to provide
Electron Microscopy: an Analytical Tool for Solid State Physicists
NASA Astrophysics Data System (ADS)
van Tendeloo, Gustaaf
2013-03-01
For too long the electron microscope has been considered as ``a big magnifying glass.'' Modern electron microscopy however has evolved into an analytical technique, able to provide quantitative data on structure, composition, chemical bonding and magnetic properties. Using lens corrected instruments it is now possible to determine atom shifts at interfaces with a precision of a few picometer; chemical diffusion at these interfaces can be imaged down to atomic scale. The chemical nature of the surface atoms can be visualized and even the bonding state of the elements (e.g. Mn2+ versus Mn3+) can be detected on an atomic scale. Electron microscopy is by principle a projection technique, but the final dream is to obtain atomic info of materials in three dimensions. We will show that this is no longer a dream, but that it is possible using advanced microscopy. We will show evidence of determining the valence change Ce4+ versus Ce3+ at the surface of a CeO2 nanocrystal; the atomic shifts at the interface between LaAlO3 and SrTiO3 and the 3D relaxation of a Au nanocrystal.
Precursor anion states in dissociative electron attachment to chlorophenol isomers
NASA Astrophysics Data System (ADS)
Kossoski, F.; Varella, M. T. do N.
2016-07-01
We report a theoretical study on low-energy (<10 eV) elastic electron scattering from chlorophenol isomers, namely, para-chlorophenol (pCP), meta-chlorophenol (mCP), and ortho-chlorophenol (oCP). The calculations were performed with the Schwinger multichannel method with pseudopotentials, and analysis of the computed integral cross sections and virtual orbitals revealed one σCCl ∗ , one σOH ∗ , and three π∗ shape resonances. We show that electron capture into the two lower lying π∗ orbitals initiates dissociative processes that lead to the elimination of the chloride ion, accounting for the two overlapping peaks where this fragment was observed. Despite the relatively small differences on the energetics of the π∗ resonances, a major isomeric effect was found on their corresponding autodetachment lifetimes, which accounts for the observed increasing cross sections in the progression pCP < mCP < oCP. In particular, dissociation from the π1 ∗ anion of pCP is largely suppressed because of the unfavorable mixing with the σCCl ∗ state. We found the intramolecular hydrogen bond present in oCP to have the opposite effects of stabilizing the σCCl ∗ resonance and destabilizing the σOH ∗ resonance. We also suggest that the hydrogen abstraction observed in chlorophenols and phenol actually takes place by a mechanism in which the incoming electron is directly attached to the dissociative σOH ∗ orbital.
Electronic spectrum of 17 electronic states of BN molecule: a theoretical study.
Shi, Deheng; Xing, Wei; Liu, Hui; Sun, Jinfeng; Zhu, Zunlue; Liu, Yufang
2012-07-01
The potential energy curves (PECs) of the X(3)Π, a(1)Σ(+), b(1)Π, A(3)Σ(+), B(3)Σ(-), c(1)Δ, D(3)Π, 1(5)Π, 3(1)Σ(+), 3(3)Π, 2(1)Π, 2(3)Σ(+), 1(3)Δ, 1(5)Σ(+), 4(3)Π, 2(3)Σ(-) and 1(5)Σ(-) electronic states of the BN molecule are calculated using an ab initio quantum chemical method. The PEC calculations have been made for internuclear separations from 0.06 to 1.20 nm using the complete active space self-consistent field (CASSCF) method, which is followed by the valence internally contracted multireference configuration interaction (MRCI) approach in combination with a correlation-consistent aug-cc-pV5Z basis set. To improve the quality of PECs, core-valence correlation and relativistic corrections are included. Relativistic correction calculations are carried out using the third-order Douglas-Kroll Hamiltonian (DKH3) approximation. Core-valence correlation corrections are included using a cc-pCVQZ basis set. Relativistic corrections are calculated at the level of a cc-pVQZ basis set. To obtain more reliable results, the PECs determined by the MRCI calculations are corrected for size-extensivity errors by means of the Davidson modification (MRCI+Q). These PECs are extrapolated to the complete basis set limit by the total-energy extrapolation scheme. The spectroscopic parameters are determined by fitting the vibrational levels, which are calculated in a direct forward manner from the analytic potential by solving the ro-vibrational Schrödinger equation using Numerov's method. The spectroscopic results have been compared in detail with those reported in the literature. Excellent agreement has been found between the present spectroscopic results and the experimental ones. Using the Breit-Pauli operator, the spin-orbit coupling effect on the spectroscopic parameters is included in the X(3)Π and D(3)Π electronic states. The vibrational level, inertial rotation and centrifugal distortion constants are calculated for each vibrational state of each
Symmetry of the Adiabatic Condition in the Piston Problem
ERIC Educational Resources Information Center
Anacleto, Joaquim; Ferreira, J. M.
2011-01-01
This study addresses a controversial issue in the adiabatic piston problem, namely that of the piston being adiabatic when it is fixed but no longer so when it can move freely. It is shown that this apparent contradiction arises from the usual definition of adiabatic condition. The issue is addressed here by requiring the adiabatic condition to be…
NASA Astrophysics Data System (ADS)
Krix, David; Nienhaus, Hermann
2014-08-01
Thin potassium films grown on Si(001) substrates are used to measure internal chemicurrents and the external emission of exoelectrons simultaneously during adsorption of molecular oxygen on K surfaces at 120 K. The experiments clarify the dynamics of electronic excitations at a simple metal with a narrow valence band. X-ray photoemission reveals that for exposures below 5 L almost exclusively peroxide K2O2 is formed, i.e., no dissociation of the molecule occurs during interaction. Still a significant chemicurrent and a delayed exoelectron emission are detected due to a rapid injection of unoccupied molecular levels below the Fermi level. Since the valence band width of potassium is approximately equal to the potassium work function (2.4 eV) the underlying mechanism of exoemission is an Auger relaxation whereas chemicurrents are detected after resonant charge transfer from the metal valence band into the injected level. The change of the chemicurrent and exoemission efficiencies with oxygen coverage can be deduced from the kinetics of the reaction and the recorded internal and external emission currents traces. It is shown that the non-adiabaticity of the reaction increases with coverage due to a reduction of the electronic density of states at the surface while the work function does not vary significantly. Therefore, the peroxide formation is one of the first reaction systems which exhibits varying non-adiabaticity and efficiencies during the reaction. Non-adiabatic calculations based on model Hamiltonians and density functional theory support the picture of chemicurrent generation and explain the rapid injection of hot hole states by an intramolecular motion, i.e., the expansion of the oxygen molecule on the timescale of a quarter of a vibrational period.
Krix, David; Nienhaus, Hermann
2014-08-21
Thin potassium films grown on Si(001) substrates are used to measure internal chemicurrents and the external emission of exoelectrons simultaneously during adsorption of molecular oxygen on K surfaces at 120 K. The experiments clarify the dynamics of electronic excitations at a simple metal with a narrow valence band. X-ray photoemission reveals that for exposures below 5 L almost exclusively peroxide K2O2 is formed, i.e., no dissociation of the molecule occurs during interaction. Still a significant chemicurrent and a delayed exoelectron emission are detected due to a rapid injection of unoccupied molecular levels below the Fermi level. Since the valence band width of potassium is approximately equal to the potassium work function (2.4 eV) the underlying mechanism of exoemission is an Auger relaxation whereas chemicurrents are detected after resonant charge transfer from the metal valence band into the injected level. The change of the chemicurrent and exoemission efficiencies with oxygen coverage can be deduced from the kinetics of the reaction and the recorded internal and external emission currents traces. It is shown that the non-adiabaticity of the reaction increases with coverage due to a reduction of the electronic density of states at the surface while the work function does not vary significantly. Therefore, the peroxide formation is one of the first reaction systems which exhibits varying non-adiabaticity and efficiencies during the reaction. Non-adiabatic calculations based on model Hamiltonians and density functional theory support the picture of chemicurrent generation and explain the rapid injection of hot hole states by an intramolecular motion, i.e., the expansion of the oxygen molecule on the timescale of a quarter of a vibrational period. PMID:25149810
Krix, David; Nienhaus, Hermann
2014-08-21
Thin potassium films grown on Si(001) substrates are used to measure internal chemicurrents and the external emission of exoelectrons simultaneously during adsorption of molecular oxygen on K surfaces at 120 K. The experiments clarify the dynamics of electronic excitations at a simple metal with a narrow valence band. X-ray photoemission reveals that for exposures below 5 L almost exclusively peroxide K{sub 2}O{sub 2} is formed, i.e., no dissociation of the molecule occurs during interaction. Still a significant chemicurrent and a delayed exoelectron emission are detected due to a rapid injection of unoccupied molecular levels below the Fermi level. Since the valence band width of potassium is approximately equal to the potassium work function (2.4 eV) the underlying mechanism of exoemission is an Auger relaxation whereas chemicurrents are detected after resonant charge transfer from the metal valence band into the injected level. The change of the chemicurrent and exoemission efficiencies with oxygen coverage can be deduced from the kinetics of the reaction and the recorded internal and external emission currents traces. It is shown that the non-adiabaticity of the reaction increases with coverage due to a reduction of the electronic density of states at the surface while the work function does not vary significantly. Therefore, the peroxide formation is one of the first reaction systems which exhibits varying non-adiabaticity and efficiencies during the reaction. Non-adiabatic calculations based on model Hamiltonians and density functional theory support the picture of chemicurrent generation and explain the rapid injection of hot hole states by an intramolecular motion, i.e., the expansion of the oxygen molecule on the timescale of a quarter of a vibrational period.
NASA Astrophysics Data System (ADS)
Samala, Nagaprasad Reddy; Mahapatra, S.
2014-06-01
Polycyclic aromatic hydrocarbons (PAHs), in particular, their radical cation (PAH^+), have long been postulated to be the important molecular species in connection with the spectroscopic observations in the interstellar medium. Motivated by numerous important observations by stellar as well as laboratory spectroscopists, we undertook detailed quantum mechanical studies of the structure and dynamics of electronically excited PAH^+ in an attempt to establish possible synergism with the recorded data In this study, we focus on the quantum chemistry and dynamics of the doublet ground (X) and low-lying excited (A, B and C) electronic states of the radical cation of tetracene (Tn), pentacene (Pn), and hexacene (Hn) molecule. This study is aimed to unravel photostability, spectroscopy, and time-dependent dynamics of their excited electronic states. In order to proceed with the theoretical investigations, we construct suitable multistate and multimode Hamiltonian for these systems with the aid of extensive ab initio calculations of their electronic energy surfaces. The diabatic coupling surfaces are derived from the calculated adiabatic electronic energies. First principles nuclear dynamics calculations are then carried out employing the constructed Hamiltonians and with the aid of time-independent and time-dependent quantum mechanical methods. We compared our theoretical results with available photoelectron spectroscopy, zero kinetic energy photoelectron (ZEKE) spectroscopy and matrix isolation spectroscopy (MIS) results. A peak at 8650 Å in the B state spectrum of Tn^+ is in good agreement with the DIB at 8648 Å observed by Salama et al. Similarly in Pn^+, a peak at 8350 Å can be correlated to the DIB at 8321 Å observed by Salama et al. J. Zhang et al., J. Chem. Phys., 128,104301 (2008).; F. Salama, Origins of Life Evol. Biosphere, 28, 349 (1998).; F. Salama et al., Planet. Space Sci., 43, 1165 (1995).; F. Salama et al., Astrophys. J., 526, 265 (1999).; J
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Electronic structure of the unoccupied electron energy states in FeSe1-xTex
NASA Astrophysics Data System (ADS)
Mishra, Pramita; Lohani, Himanshu; Maniraj, M.; Nayak, Jayita; Zargar, R. A.; Awana, V. P. S.; Barman, Sudipta Roy; Sekhar, Biju Raja
2015-10-01
Inverse photoemission spectroscopic (IPES) measurements along with LDA based band structure calculations have been used to investigate the unoccupied electronic structure of FeSe1-xTex system. The observed doping and temperature dependent pseudogap in this system is found to be linked to the change in the chalcogen height in their geometric structure. The depletion in spectral weight from the near EF states at low temperature in IPES has been correlated with the enhancement of the 3z2-r2 orbitals in the photoemission spectroscopy (PES). The Coulomb correlation energy U, estimated from the combined PES and IPES spectra, signifies the enhancement in electron correlations in FeSe1-xTex, with doping. The formation of pseudogap in PES and IPES confirms the importance of correlations in the 11 family of Fe superconductors.
Electron excitation from ground state to first excited state: Bohmian mechanics method
NASA Astrophysics Data System (ADS)
Yang, Song; Shuang, Zhao; Fu-Ming, Guo; Yu-Jun, Yang; Su-Yu, Li
2016-03-01
The excitation process of electrons from the ground state to the first excited state via the resonant laser pulse is investigated by the Bohmian mechanics method. It is found that the Bohmian particles far away from the nucleus are easier to be excited and are excited firstly, while the Bohmian particles in the ground state is subject to a strong quantum force at a certain moment, being excited to the first excited state instantaneously. A detailed analysis for one of the trajectories is made, and finally we present the space and energy distribution of 2000 Bohmian particles at several typical instants and analyze their dynamical process at these moments. Project supported by the Doctoral Research Start-up Funding of Northeast Dianli University, China (Grant No. BSJXM-201332), the National Natural Science Foundation of China (Grant Nos. 11547114, 11534004, 11474129, 11274141, 11447192, and 11304116), and the Graduate Innovation Fund of Jilin University, China (Grant No. 2015091).
Two dimensional electron systems for solid state quantum computation
NASA Astrophysics Data System (ADS)
Mondal, Sumit
Two dimensional electron systems based on GaAs/AlGaAs heterostructures are extremely useful in various scientific investigations of recent times including the search for quantum computational schemes. Although significant strides have been made over the past few years to realize solid state qubits on GaAs/AlGaAs 2DEGs, there are numerous factors limiting the progress. We attempt to identify factors that have material and design-specific origin and develop ways to overcome them. The thesis is divided in two broad segments. In the first segment we describe the realization of a new field-effect induced two dimensional electron system on GaAs/AlGaAs heterostructure where the novel device-design is expected to suppress the level of charge noise present in the device. Modulation-doped GaAs/AlGaAs heterostructures are utilized extensively in the study of quantum transport in nanostructures, but charge fluctuations associated with remote ionized dopants often produce deleterious effects. Electric field-induced carrier systems offer an attractive alternative if certain challenges can be overcome. We demonstrate a field-effect transistor in which the active channel is locally devoid of modulation-doping, but silicon dopant atoms are retained in the ohmic contact region to facilitate low-resistance contacts. A high quality two-dimensional electron gas is induced by a field-effect that is tunable over a density range of 6.5x10 10cm-2 to 2.6x1011cm-2 . Device design, fabrication, and low temperature (T=0.3K) characterization results are discussed. The demonstrated device-design overcomes several existing limitations in the fabrication of field-induced 2DEGs and might find utility in hosting nanostructures required for making spin qubits. The second broad segment describes our effort to correlate transport parameters measured at T=0.3K to the strength of the fractional quantum Hall state observed at nu=5/2 in the second Landau level of high-mobility GaAs/AlGaAs two dimensional
Electron and Hole States in Low Dimensional Structures
NASA Astrophysics Data System (ADS)
Edwards, Gerard
Available from UMI in association with The British Library. In this thesis results from microscopic calculations for the electron and hole states in low dimensional heterostructures are presented. The basis for the calculation is the local empirical pseudopotential technique which is used to generate the bulk semiconductor bandstructure. Then an S matrix approach, which is numerically stable, is employed to propagate the solution through the layered structure. The technique is essentially a scattering approach and hence is suitable to describe the experimental situation of finite samples. The fact that a finite system is treated allows the formalism to be naturally extended to include an external E field. The calculations that have been done are for the (001) growth direction. In chapter 1 the basic concepts of semiconductor physics relevant to the material of this thesis are introduced. In Chapter 2 the theoretical technique used in this thesis, for conduction band states, is reviewed and compared and contrasted with alternative methods. The emergence of miniband states and Stark ladders in coupled GaAs/AlAs quantum well structures are dealt with in chapter 3. In Chapter 4 the bound state problem, relevant to optical properties, of the energy versus k_parallel subband dispersion of a AlGaAs-GaAs-AlGaAs quantum well is examined. Chapter 5 contains the extension of the theoretical technique to incorporate the spin-orbit interaction so that heterostructure hole states can be tackled. The validity of the effective mass theory treatment of the semiconductor interface and the Luttinger model of the bulk valence band is questioned and the microscopic nature of the GaAs-AlAs interface scattering investigated. In chapter 6 hole states in GaAs/AlAs double barrier structures and coupled multiple quantum well (MQW) structures are calculated. The anomalous formation of contact interface states instead of heavy hole minibands is observed in MQW structures. In chapter 7 In
Electronic states and spectra of BiH
NASA Astrophysics Data System (ADS)
Setzer, Klaus-Dieter; Fink, Ewald H.; Hill, Christian; Brown, John M.
2015-06-01
Emission spectra of bismuth monohydride (BiH) radicals excited by energy transfer from O2(a1Δg) or NF(a1Δ) or by a DC discharge in a mixture of bismuth vapor and hydrogen in a fast-flow system were studied in the wavenumber range from 4000 to 25 000 cm-1 with a Fourier-transform spectrometer. The X21 → X10+ transition between the spin components of the X3Σ- ground state was remeasured at high spectral resolution and signal/noise. Six bands of the Δv = 0 and +1 sequences near 4950 and 6600 cm-1 have been observed. The low-J lines of these bands are split into up to 10 hfs components due to magnetic hyperfine structure splitting of the X21 levels. In addition to the previously observed electric dipole lines, weak magnetic dipole lines show up in the Δv = 0 but not in the Δv = +1 bands. The intensities of the Δv = +1 bands are about a factor of 10 higher than expected from Franck-Condon factors indicating that the electric dipole transition moment μX2-X1 shows a strong dependence on internuclear distance. Near 5450 cm-1, the 0-0 and 1-1 bands of the transition a2 → X21 from the hitherto unknown first excited state a1Δ(a2) to the upper component of the ground state have been observed. The lines in these bands show the magnetic hfs splitting of both the a2 and X21 states. In the visible range near 21 300 and 16 300 cm-1, the 0-0 and 1-1 bands of the b0+ → X10+ system and the 0-0 band of the b0+ → X21 transition likewise have been measured at high resolution. The lines of the latter band also show the hfs splitting of the X21 state. Least-squares fits have yielded rotational and vibrational constants of the X10+, X21, a2, and b0+ states as well as hfs parameters of the X21 and a2 states and the electronic energy of the hitherto unknown a1Δ(a2) level.
Steam bottoming cycle for an adiabatic diesel engine
Poulin, E.; Demler, R.; Krepchin, I.; Walker, D.
1984-03-01
A study of steam bottoming cycles using adiabatic diesel engine exhaust heat projected substantial performance and economic benefits for long haul trucks. A parametric analysis of steam cycle and system component variables, system cost, size and performance was conducted. An 811 K/6.90 MPa state-of-the-art reciprocating expander steam system with a monotube boiler and radiator core condenser was selected for preliminary design. When applied to a NASA specified turbo-charged adiabatic diesel the bottoming system increased the diesel output by almost 18%. In a comparison of the costs of the diesel with bottoming system (TC/B) and a NASA specified turbocompound adiabatic diesel with after-cooling with the same total output, the annual fuel savings less the added maintenance cost was determined to cover the increased initial cost of the TC/B system in a payback period of 2.3 years. Also during this program steam bottoming system freeze protection strategies were developed, technological advances required for improved system reliability were considered and the cost and performance of advanced systems were evaluated.
Electron impact excitation and assignment of the low-lying electronic states of CO2
NASA Technical Reports Server (NTRS)
Hall, R. I.; Trajmar, S.
1973-01-01
Electron scattering spectra of CO2 are reported in the 7 to 10 eV energy-loss range, at energies of 0.2, 0.35, 0.6, 0.7, and 7.0 eV above threshold, and at a scattering angle of 90 deg. Several new distinct overlapping continua with weak, diffuse bands superimposed are observed to lie in this energy-loss range. The experimental spectra are discussed in the light of recent ab initio configuration-interaction calculations of the vertical transition energies of CO2. The experimental spectra are shown to be consistent with the excitation states of CO2.
Measurement of the electronic momentum distributions of Rydberg Stark states
Murray-Krezan, J.; Jones, R. R.
2007-06-15
Approximate momentum distributions of Rydberg electrons in static electric fields have been obtained using an improved impulsive momentum retrieval (IMR) technique. An imaging detector enables the measurement of half-cycle pulse (HCP) ionization probability across the spatial profile of a focused half-cycle pulse beam. By modulating the HCP amplitude we directly measure the derivative of the ionization vs HCP impulse curve, enabling the recovery of momentum distributions with better resolution than previously demonstrated with IMR. For example, for Stark states with small dipole moments, we observe predicted fine-structure in the projection of the momentum distribution along the Stark field axis. We use a semiclassical model to simulate the effect that the nonzero HCP duration has on our measurements. Good agreement between simulated and measured momentum distributions is obtained.
Electronic states of cuprate superconductors containing halogen or carbon
NASA Astrophysics Data System (ADS)
Tohiyama, Takami; Shibata, Yasumasa; Maekawa, Sadamichi
1996-12-01
The electronic states of the halo-oxocuprate and oxycarbonate superconductors are examined by means of the ionic and cluster models. The oxycarbonates examined contain the CO3 group on one side of the CuO2 plane. The superconducting critical temperature Tc is found to be correlated with the stability of the Zhang-Rice local singlet in the CuO2 plane. The stability is generally determined by two factors: (1) the energy-level separation between apical ion and in-plane oxygen and (2) the hybridization between apical pz and in-plane orbitals. The former is dominant for the oxycarbonates. It is also found that the CO3 group has no effect on the stabilization. For the halo-oxocuprates, the latter is crucial to stabilize the singlet.
NASA Astrophysics Data System (ADS)
Okhrimenko, Albert N.
Metallo-tetrapyrroles (MTP) are highly stable macrocyclic pi-systems that display interesting properties that make them potential candidates for various applications. Among these applications are optoelectronics, magnetic materials, photoconductive materials, non-linear optical materials and photo tumor therapeutic drugs. These applications are generally related to their high stability and efficient light absorption ability in the visible and near-infrared region of the optical spectrum. Metallo porphyrins are well known and widely studied representatives of metallotetrapyrroles. Electron deficient substituents in the meso positions are well known to greatly influence the interaction between the metal d-orbitals and the nitrogen orbitals of the tetrapyrrole macrocycle. In this work, a series of electron deficient porphyrins has been studied to gain some knowledge about the change in the excited state dynamics with structural and electronic modifications. Among these porphyrins is nickel and iron modified species bearing perfluoro-, perprotio-, p-nitrophenyl- and perfluorophenyl-meso substituents. Ultrafast transient absorption spectrometry has been used as the main research instrument along with other spectroscopic and electrochemical methods. A new technique has been employed to study the photophysical properties of zinc (II) tetraphenylporphine cation radical. It employs a combination of controlled potential coulometry and femtosecond absorption spectrometry. The fast transient lifetime of 17 ps of the pi-cation species originates in very efficient mixing of the a2u HOMO cation orbital that places electronic density mainly on pyrrolic nitrogens and metal d-orbitals. That explains the lack of any emission of the cationic species. This non-radiative decay process might elucidate the processes taking place in photosynthetic systems when electron is removed from porphyrinic moiety and the hole is produced. In this work zinc(II) meso-tetraphenylporphine radial cation
Xie, Changjian; Zhu, Xiaolei; Yarkony, David R. E-mail: yarkony@jhu.edu E-mail: hguo@unm.edu; Ma, Jianyi E-mail: yarkony@jhu.edu E-mail: hguo@unm.edu; Xie, Daiqian E-mail: yarkony@jhu.edu E-mail: hguo@unm.edu; Guo, Hua E-mail: yarkony@jhu.edu E-mail: hguo@unm.edu
2015-03-07
Non-adiabatic processes play an important role in photochemistry, but the mechanism for conversion of electronic energy to chemical energy is still poorly understood. To explore the possibility of vibrational control of non-adiabatic dynamics in a prototypical photoreaction, namely, the A-band photodissociation of NH{sub 3}(X{sup ~1}A{sub 1}), full-dimensional state-to-state quantum dynamics of symmetric or antisymmetric stretch excited NH{sub 3}(X{sup ~1}A{sub 1}) is investigated on recently developed coupled diabatic potential energy surfaces. The experimentally observed H atom kinetic energy distributions are reproduced. However, contrary to previous inferences, the NH{sub 2}(A{sup ~2}A{sub 1})/NH{sub 2}(X{sup ~2}B{sub 1}) branching ratio is found to be small regardless of the initial preparation of NH{sub 3}(X{sup ~1}A{sub 1}), while the internal state distribution of the preeminent fragment, NH{sub 2}(X{sup ~2}B{sub 1}), is found to depend strongly on the initial vibrational excitation of NH{sub 3}(X{sup ~1}A{sub 1}). The slow H atoms in photodissociation mediated by the antisymmetric stretch fundamental state are due to energy sequestered in the internally excited NH{sub 2}(X{sup ~2}B{sub 1}) fragment, rather than in NH{sub 2}(A{sup ~2}A{sub 1}) as previously proposed. The high internal excitation of the NH{sub 2}(X{sup ~2}B{sub 1}) fragment is attributed to the torques exerted on the molecule as it passes through the conical intersection seam to the ground electronic state of NH{sub 3}. Thus in this system, contrary to previous assertions, the control of electronic state branching by selective excitation of ground state vibrational modes is concluded to be ineffective. The juxtaposition of precise quantum mechanical results with complementary results based on quasi-classical surface hopping trajectories provides significant insights into the non-adiabatic process.
Precursor anion states in dissociative electron attachment to chlorophenol isomers.
Kossoski, F; Varella, M T do N
2016-07-28
We report a theoretical study on low-energy (<10 eV) elastic electron scattering from chlorophenol isomers, namely, para-chlorophenol (pCP), meta-chlorophenol (mCP), and ortho-chlorophenol (oCP). The calculations were performed with the Schwinger multichannel method with pseudopotentials, and analysis of the computed integral cross sections and virtual orbitals revealed one σCCl (∗), one σOH (∗), and three π(∗) shape resonances. We show that electron capture into the two lower lying π(∗) orbitals initiates dissociative processes that lead to the elimination of the chloride ion, accounting for the two overlapping peaks where this fragment was observed. Despite the relatively small differences on the energetics of the π(∗) resonances, a major isomeric effect was found on their corresponding autodetachment lifetimes, which accounts for the observed increasing cross sections in the progression pCP < mCP < oCP. In particular, dissociation from the π1 (∗) anion of pCP is largely suppressed because of the unfavorable mixing with the σCCl (∗) state. We found the intramolecular hydrogen bond present in oCP to have the opposite effects of stabilizing the σCCl (∗) resonance and destabilizing the σOH (∗) resonance. We also suggest that the hydrogen abstraction observed in chlorophenols and phenol actually takes place by a mechanism in which the incoming electron is directly attached to the dissociative σOH (∗) orbital. PMID:27475364
Optical Properties and Electronic States Specific to Solid Fullerene
NASA Astrophysics Data System (ADS)
Minami, Nobutsugu; Kazaoui, Said; Wen, Ching-Ju; Byrne, Hugh J.
1996-03-01
One of the most intriguing aspects of the fullerene research is to ask what specific phenomena will occur when the soccer-ball shaped molecules aggregate and make a solid. Seeking this question is crucial for the realization of any photonic and electronic application of this new type of carbon allotrope. We have been working on this theme by the study of optical and electrical properties of C60 thin film. An important result is the demonstration of a distinct intermolecular charge transfer excited state (CT exciton) originating from intermolecular electronic interaction specific to the spherical pai conjugation system. This has been shown by the coincidence in the threshold energy of 2.3eV for absorption, luminescence efficiency, field induced luminescence quenching, and photoconductivity. We also found an evidence of the interconnection between optical properties and the structural phase transition at 260K. Moreover, a composite film containing C60 is demonstrated to show intense luminescence under 10mW laser irradiation.
Adiabatic response and quantum thermoelectrics for ac-driven quantum systems
NASA Astrophysics Data System (ADS)
Ludovico, María Florencia; Battista, Francesca; von Oppen, Felix; Arrachea, Liliana
2016-02-01
We generalize the theory of thermoelectrics to include coherent electron systems under adiabatic ac driving, accounting for quantum pumping of charge and heat, as well as for the work exchanged between the electron system and driving potentials. We derive the relevant response coefficients in the adiabatic regime and show that they obey generalized Onsager reciprocity relations. We analyze the consequences of our generalized thermoelectric framework for quantum motors, generators, heat engines, and heat pumps, characterizing them in terms of efficiencies and figures of merit. We illustrate these concepts in a model for a quantum pump.
NASA Astrophysics Data System (ADS)
Zhang, Changhua; Krasnokutski, Serge A.; Zhang, Bing; Yang, Dong-Sheng
2009-08-01
Scandium (Sc) complexes of fluorobenzene (C6H5F), toluene (C6H5CH3), phenol (C6H5OH), and benzonitrile (C6H5CN) are produced in a laser-vaporization molecular beam source. These complexes are studied with pulsed-field-ionization zero-electron-kinetic-energy (ZEKE) spectroscopy and density functional theory calculations. Adiabatic ionization energies and low-frequency metal-ligand and ligand-based vibrational modes are measured from the ZEKE spectra. Metal binding sites and strengths and electronic states are obtained by comparing the ZEKE spectra with the theoretical calculations. The ionization energies of Sc-C6H5X (X=F, CH3, OH, and CN) follow the trend of CN>F>OH>CH3, whereas the bond energies are in the order of CN>CH3˜OH>F. The metal-ligand stretching frequency of Sc+-C6H5CN is nearly twice as those of the other three complexes. All neutral complexes are in low-spin doublet ground states and singly-charged cations are in singlet states. The preferred Sc binding site in these complexes are the phenyl ring with X=F, CH3, and OH and the nitrile group with CN. For the phenol complex, two rotational conformers are identified in different OH orientations.
Copan, Andreas V.; Wiens, Avery E.; Nowara, Ewa M.; Schaefer, Henry F.; Agarwal, Jay
2015-02-07
Peroxyacetyl radical [CH{sub 3}C(O)O{sub 2}] is among the most abundant peroxy radicals in the atmosphere and is involved in OH-radical recycling along with peroxyacetyl nitrate formation. Herein, the ground (X{sup ~}) and first (A{sup ~}) excited state surfaces of cis and trans peroxyacetyl radical are characterized using high-level ab initio methods. Geometries, anharmonic vibrational frequencies, and adiabatic excitation energies extrapolated to the complete basis-set limit are reported from computations with coupled-cluster theory. Excitation of the trans conformer is found to induce a symmetry-breaking conformational change due to second-order Jahn-Teller interactions with higher-lying excited states. Additional benchmark computations are provided to aid future theoretical work on peroxy radicals.
Ab initio study of low-lying electronic states of SnCl2+.
Lee, Edmond P F; Dyke, John M; Chow, Wan-ki; Mok, Daniel K W; Chau, Foo-tim
2007-12-20
Complete active space self-consistent field (CASSCF), multireference configuration interaction (MRCI), and restricted-spin coupled-cluster singles-doubles with perturbative triples [RCCSD(T)] calculations have been carried out on low-lying doublet and quartet states of SnCl2+, employing basis sets of up to aug-cc-pV5Z quality. Effects of core correlation and off-diagonal spin-orbit interaction on computed vertical ionization energies were investigated. The best theoretical estimate of the adiabatic ionization energy (including zero-point vibrational energy correction) to the X2A1 state of SnCl2+ is 10.093+/-0.010 eV. The first photoelectron band of SnCl2 has also been simulated by employing RCCSD(T)/aug-cc-pV5Z potential energy functions and including Duschinsky rotation and anharmonicity. PMID:18034464
Electronic States of Nickel Effected By Magnetic Doping
NASA Astrophysics Data System (ADS)
Podolak, Ken; Smith, Jamie
2012-02-01
Spin currents have a great potential to replace charge currents. This would revolutionize how we read/write information. The generation and switching of spin currents however must be well understood. Transport measurements suggest that magnetic impurities can alter the mean free path of carriers and thereby create spin currents. Angle-resolved photoemission is used to determine the change in the electronic states of Ni induced by doping with iron, chromium, and manganese near the Fermi Energy. The samples were single crystals of nickel(110) with variable amounts of dopant diffused into it. Alloy single crystals were used over epitaxial thin films due to the sharper features at the Fermi Energy that they produced. The mean free path, magnetic splitting, and carrier density are affected by a few percent of each of the dopants. Iron suppresses the mean free path of minority spins only, while chromium and manganese suppresses both spins and decreases the magnetic splitting. The strong variation of these affects from one impurity to the other supports the concept of tailoring spin transport by magnetic doping. [1] K. N. Altmann et al., Phys. Rev. Lett. 87, 137201 (2001) [2] K.R. Podolak, Ph.D. Thesis, Penn. State (2008)
Symmetry-Protected Quantum Adiabatic Transistors
NASA Astrophysics Data System (ADS)
Williamson, Dominic J.; Bartlett, Stephen D.
2014-03-01
An essential development in the history of computing was the invention of the transistor as it allowed logic circuits to be implemented in a robust and modular way. The physical characteristics of semiconductor materials were the key to building these devices. We aim to present an analogous development for quantum computing by showing that quantum adiabatic transistors (as defined by Flammia et al.) are built upon the essential qualities of symmetry-protected (SP) quantum ordered phases in one dimension. Flammia et al. and Renes et al. have demonstrated schemes for universal adiabatic quantum computation using quantum adiabatic transistors described by interacting spin chain models with specifically chosen Hamiltonian terms. We show that these models can be understood as specific examples of the generic situation in which all SP phases lead to quantum computation on encoded edge degrees of freedom by adiabatically traversing a symmetric phase transition into a trivial symmetric phase. This point of view is advantageous as it allows us to readily see that the computational properties of a quantum adiabatic transistor arise from a phase of matter rather than due to carefully tuned interactions.
NASA Astrophysics Data System (ADS)
Morini, Filippo; Watanabe, Noboru; Kojima, Masataka; Deleuze, Michael Simon; Takahashi, Masahiko
2015-10-01
The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b1, 6a1, 4b2, and 1a2 orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point out in particular the most appreciable role which is played by a few specific molecular vibrations of A1, B1, and B2 symmetries, which correspond to C-H stretching and H-C-H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing.
Morini, Filippo; Watanabe, Noboru; Kojima, Masataka; Deleuze, Michael Simon; Takahashi, Masahiko
2015-10-01
The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b1, 6a1, 4b2, and 1a2 orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point out in particular the most appreciable role which is played by a few specific molecular vibrations of A1, B1, and B2 symmetries, which correspond to C-H stretching and H-C-H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing. PMID:26450316
Morini, Filippo; Deleuze, Michael Simon; Watanabe, Noboru; Kojima, Masataka; Takahashi, Masahiko
2015-10-07
The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b{sub 1}, 6a{sub 1}, 4b{sub 2}, and 1a{sub 2} orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point out in particular the most appreciable role which is played by a few specific molecular vibrations of A{sub 1}, B{sub 1}, and B{sub 2} symmetries, which correspond to C–H stretching and H–C–H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing.