Vibrational Degrees Of Freedom Research Articles

Entangling quantum gate in trapped ions via Rydberg blockade

We present a theoretical analysis of the implementation of an entangling quantum gate between two trapped Ca$^+$ ions which is based on the dipolar interaction among ionic Rydberg states. In trapped ions the Rydberg excitation dynamics is usually strongly affected by mechanical forces due to the strong couplings between electronic and vibrational degrees of freedom in inhomogeneous electric fields. We demonstrate that this harmful effect can be overcome by using dressed states that emerge from the microwave coupling of nearby Rydberg states. At the same time these dressed states exhibit long range dipolar interactions which we use to implement a controlled adiabatic phase gate. Our study highlights a route towards a trapped ion quantum processor in which quantum gates are realized independently of the vibrational modes.

A rotamer energy level study of sulfuric acid

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

Emission Rate, Vibronic Entanglement, and Coherence in Aggregates of Conjugated Polymers

Here we have studied a dimer model of conjugated polymer aggregates based on the traditional J and H structures, with the extension in treating the electronic and vibrational degrees of freedom at par. We have considered various exchange symmetries corresponding to the parameters of the excited state Hamiltonian in assigning the symmetry of the vibronic states of the aggregate, going beyond the homodimer case. The emission rates are determined as a function of system parameters at low temperature for both types of aggregates. We have also determined the vibronic entanglement as a measure of the coupled electronic and vibrational motion as well as the exciton coherence number in the emitting state. As a function of interchain interaction strength, emission rate and entanglement grossly follow similar trends for the J-aggregate and opposite trends for the H-aggregate in totally symmetric as well as asymmetric cases. Variation of other system parameters, like electronic excitation energy and electron-vibration coupling parameter are also thoroughly investigated in governing these quantities. The role of symmetry of the wave function in governing the spectra and the exciton coherence are also analyzed thoroughly, which offers a way to realize the connection between such macroscopic and microscopic quantum features.

Vortex source flowing into vacuum under thermal crisis

Thermal crisis of a stationary vortex source flowing to vacuum is considered for air on the basis of the model of a diatomic gas with variable heat capacities due to the excitation of vibrational degrees of freedom of molecules. The versions with different heat supply laws are compared. The effect of the size of the heat-release region (from close-to-zero value to that exceeding the minimal radius of the vortex source by tens of times) as well as the effect of the circulation of the flow on the critical parameters determining thermal crisis are considered. A qualitative difference from the thermal crisis in a perfect (ideal) gas with constant heat capacities is demonstrated.

Long-lived oscillatory incoherent electron dynamics in molecules: trans-polyacetylene oligomers

We identify an intriguing feature of the electron–vibrational dynamics of molecular systems via a computational examination of trans-polyacetylene oligomers. Here, via the vibronic interactions, the decay of an electron in the conduction band resonantly excites an electron in the valence band, and vice versa, leading to oscillatory exchange of electronic population between two distinct electronic states that lives for up to tens of picoseconds. The oscillatory structure is reminiscent of beating patterns between quantum states and is strongly suggestive of the presence of long-lived molecular electronic coherence. Significantly, however, a detailed analysis of the electronic coherence properties shows that the oscillatory structure arises from a purely incoherent process. These results were obtained by propagating the coupled dynamics of electronic and vibrational degrees of freedom in a mixed quantum-classical study of the Su–Schrieffer–Heeger Hamiltonian for polyacetylene. The incoherent process is shown to occur between degenerate electronic states with distinct electronic configurations that are indirectly coupled via a third auxiliary state by vibronic interactions. A discussion of how to construct electronic superposition states in molecules that are truly robust to decoherence is also presented.

Transition fission states for heated nuclei

Induced fission reactions of fissioning compound nuclei that result from the capture of various incident particles (nucleons, γ rays, multiply charged ions) by target nuclei are investigated using the generalized nucleus model and the Wigner random matrix method. The effect produced on the fission widths of the compound nucleus by the competition between the excitation energies of its collective vibrational degrees of freedom that lead to its scission into fission fragments and its rotational and multi-quasiparticle states is analyzed. Bohr’s concept of transition fission states developed for near-barrier nuclear fission is generalized to the induced fission of nuclei with the excitation energies noticeably higher than the fission barriers. The temperature of the fissioning nucleus in the vicinity of the point of its scission into fission fragments is estimated.

Strong electron correlations stabilize paramagnetic cubic Cr1−xAlxN solid solutions

The stability of rock salt structure cubic Cr1−xAlxN solid solutions at high Al content and high temperature has made it one of the most important materials systems for protective coating applications. We show that the strong electron correlations in a material with dynamic magnetic disorder is the underlying reason for the observed stability against isostructural decomposition. This is done by using the first-principles disordered local moments molecular dynamics technique, which allows us to simultaneously consider electronic, magnetic, and vibrational degrees of freedom.

Collision-induced dissociation mechanisms of [Li(uracil)

The collision-induced dissociation (CID) of the [Li(uracil)](+) complex with Xe is studied by means of quasi-classical trajectory calculations. The potential energy surface is obtained "on the fly" from AM1 semiempirical calculations, supplemented with two-body analytical potentials to model the intermolecular interactions. The simulations show that Li(+) production is the primary channel, in agreement with a previous experimental study [M. T. Rodgers and P. B. Armentrout, J. Am. Chem. Soc., 2000, 122, 8548]. Collision-induced isomerization of [Li(uracil)](+) was found to be very important as well in the 2.5-10 eV collision energy range. Three minor channels are also identified: complex formation between Xe and [Li(uracil)](+), ligand exchange to form LiXe(+), and fragmentations of the uracil ring, which are strongly nonstatistical. Additional quasi-classical trajectory calculations carried out to investigate in more detail the fragmentations of the uracil ring reveal the presence of bifurcations in the potential energy surface, as trajectories starting from a transition state give rise to four different product channels. The integral cross sections for Li(+) production calculated in this work agree well with those obtained in the experiments only for the lowest collision energies, being ∼20 times greater than the experimental values for a collision energy of 10 eV. Finally, the initial translational energy is transferred preferentially to the [Li(uracil)](+) vibrational degrees of freedom, with energy transfer to rotation being modest. The amount of energy transfer to the different degrees of freedom as a function of the collision energy follows quite nicely a model recently proposed by our group.

Cooling molecules the optoelectric way

In a newly implemented technique, the complex rotational and vibrational motions of molecules are not a hindrance but a help.

Publisher's Note: “Coriolis coupling as a source of non-RRKM effects in triatomic near-symmetric top molecules: Diffusive intramolecular energy exchange between rotational and vibrational degrees of freedom” [J. Chem. Phys. 132, 224304 (2010)

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Vibrational-rotational behavior of diatomic heteronuclear molecular systems in intense laser pulses

The dynamics of diatomic heteronuclear molecules in the low-frequency intense laser pulses is studied by numerical solution of the time-dependent Schrodinger equation and both rotational and vibrational degrees of freedom are taken into account. The interference stabilization against the dissociation process is found to take place in a strong field and is shown to result in trapping of population in different rotational-vibrational bound states due to efficient Raman V- and Λ-type transitions. The interplay between the vibrational and rotational dynamics of a molecule is investigated. The dissociation suppression due to the interference mechanism and all its attributes are established in the case of multiphoton coupling between the initial state and dissociation continuum.

Raman Scattering Study of Hydrogen Storage Material LiNH2

Raman scattering spectra of LiNH 2 have been measured from 3.4 to 673 K. Precise polarization dependence of the single crystalline LiNH 2 and first principles calculation have successfully assigned all observed peaks. Li vibration with the lowest energy at 133 cm -1 shows the anomaly, where its energy decreases with decreasing temperature. This anomaly shows that the Li vibration is highly anharmonic with large amplitude. In addition, the energy of 133 cm -1 gives the very small force constant of 0.05 mdyn/Å between Li and NH 2 in the diatomic model. This weak interaction suggests that LiNH 2 easily decomposes to Li and NH 2 . Below 100 K, we have found new peaks in the energy range from 100 to 700 cm -1 . No additional degrees of freedom for vibrations conclude that rotational motion of NH 2 molecule freezes below 100 K. With increasing temperature, the bond angle of H–N–H and bond length N–H in NH 2 become narrow and long, respectively. At the reaction temperature region, the correlation between the integrated intensity of N–H vibration in Li 2 NH and back ground slope has been observed and the background change is originated from the desorption of NH 3 molecules. Final materials due to chemical reactions are different between single crystal and powder samples. In the single crystal, the spectrum similar with that at room temperature appears at 673 K and this suggests that the reaction finishes only at the thin surface layer, not entire volume. However, the powder sample of LiNH 2 decomposes to Li 2 NH and finally change to the Li 3 N for the sake of NH 3 desorption.

Photoionization of tris(2-phenylpyridine)iridium

The photoionization of gas-phase tris(2-phenylpyridine)iridium (Ir(ppy)3) has been examined. One- and two-photon studies yield a conservative estimate for the upper bound to the ionization energy of 6.4 eV. The one-photon experiment used 193 nm radiation. The latter experiments used tunable UV radiation to excite the ligand-centered 1LC state, which is followed by radiationless decay and photoionization. An accompanying paper presents a theoretical study of excited singlets and triplets and low-energy states of . The calculated ionization energy is ∼5.9 eV. The experimental and calculated results together indicate an ionization energy of ∼6 eV. An undulation in the ion yield spectrum (∼270 cm−1 spacing) was observed. It is due to structure in the transition that originates from T1, which is populated through radiationless decay of 1LC. At low fluence, is produced without fragmentation, despite the fact that a large amount of vibrational energy is present in T1. Specifically, this vibrational energy is the sum of and the thermal energy due to the 177 Ir(ppy)3 vibrational degrees of freedom at 500 K, i.e. the temperature at which the experiments were carried out. This vibrational energy is transported efficiently to the cation.

A nanosecond surface dielectric barrier discharge at elevated pressures: time-resolved electric field and efficiency of initiation of combustion

We study a nanosecond surface dielectric barrier discharge (SDBD) initiated by negative or positive polarity pulses 10–15 kV in amplitude in a cable, 25–30 ns FWHM, 5 ns rise time, in the regime of a single shot or 3 Hz repetitive frequency. Discharge parameters, namely spatial structure of the discharge and time- and space-resolved electric field are studied in a N2 : O2 = 4 : 1 mixture for P = 1–5 atm. The possibility of igniting a combustible mixture with the help of an SDBD is demonstrated using the example of a stoichiometric C2H6 : O2 mixture at ambient initial temperature and at 1 atm pressure. Flame propagation and ignited volume as a function of time are compared experimentally for two discharge geometries: SDBD and pin-to-pin configurations at the same shape and amplitude of the incident pulse. It is shown that the SDBD can be considered as a multi-point ignition system with maximum energy release near the high-voltage electrode. Numerical modeling of the discharge and subsequent combustion kinetics for the SDBD conditions is performed. The discharge action leads to the production of atoms and radicals as well as to fast gas heating, due to the relaxation of electronic and vibrational degrees of freedom. The calculated ignition delay time is in reasonable agreement with the experimental results.

Vibrational energy relaxation of large-amplitude vibrations in liquids

Given the limited intermolecular spaces available in dense liquids, the large amplitudes of highly excited, low frequency vibrational modes pose an interesting dilemma for large molecules in solution. We carry out molecular dynamics calculations of the lowest frequency ("warping") mode of perylene dissolved in liquid argon, and demonstrate that vibrational excitation of this mode should cause identifiable changes in local solvation shell structure. But while the same kinds of solvent structural rearrangements can cause the non-equilibrium relaxation dynamics of highly excited diatomic rotors in liquids to differ substantially from equilibrium dynamics, our simulations also indicate that the non-equilibrium vibrational energy relaxation of large-amplitude vibrational overtones in liquids should show no such deviations from linear response. This observation seems to be a generic feature of large-moment-arm vibrational degrees of freedom and is therefore probably not specific to our choice of model system: The lowest frequency (largest amplitude) cases probably dissipate energy too quickly and the higher frequency (more slowly relaxing) cases most likely have solvent displacements too small to generate significant nonlinearities in simple nonpolar solvents. Vibrational kinetic energy relaxation, in particular, seems to be especially and surprisingly linear.

Temperature and pressure effects on phase stabilities in the Ca–Ge system from first-principles calculations and Debye-Gruneisen model

We present a study of phase stabilities of intermetallics in the Ca–Ge system including finite temperature and pressure effects based on density functional theory (DFT) within the projector augmented wave (PAW) method. Temperature effects, mainly represented by vibrational degrees of freedom, were taken into account within the Debye-Gruneisen model. The results predict the existence of two new polymorphs of the CaGe2 compound. The pressure-temperature phase diagram of this polymorphism is calculated. The stabilization by both temperature and pressure of a new compound of the Ca3Si4-type is also predicted in this system.

Electronic coherence dynamics in trans-polyacetylene oligomers

Electronic coherence dynamics in trans-polyacetylene oligomers are considered by explicitly computing the time dependent molecular polarization from the coupled dynamics of electronic and vibrational degrees of freedom in a mean-field mixed quantum-classical approximation. The oligomers are described by the Su-Schrieffer-Heeger Hamiltonian and the effect of decoherence is incorporated by propagating an ensemble of quantum-classical trajectories with initial conditions obtained by sampling the Wigner distribution of the nuclear degrees of freedom. The electronic coherence of superpositions between the ground and excited and between pairs of excited states is examined for chains of different length, and the dynamics is discussed in terms of the nuclear overlap function that appears in the off-diagonal elements of the electronic reduced density matrix. For long oligomers the loss of coherence occurs in tens of femtoseconds. This time scale is determined by the decay of population into other electronic states through vibronic interactions, and is relatively insensitive to the type and class of superposition considered. By contrast, for smaller oligomers the decoherence time scale depends strongly on the initially selected superposition, with superpositions that can decay as fast as 50 fs and as slow as 250 fs. The long-lived superpositions are such that little population is transferred to other electronic states and for which the vibronic dynamics is relatively harmonic.

Nonlinear pulse propagation phenomena in ion-doped dielectric crystals

We theoretically analyze pulse propagation in a medium of inhomogeneously broadened two-level quantum systems, which have a vibrational degree of freedom with respect to the center-of-mass coordinate. This system mimics local mode oscillations of rare-earth-metal-ion dopants in dielectric crystals that are coupled to electronic transitions. We show the emergence of various nonlinear optical phenomena, such as self-induced transparency or the nonlinear interaction between two pulses coupling to different electrovibrational transitions. Interaction between the pulses makes it possible to generate various Raman sidebands of the incident fields and to tune the location where they are generated. We also demonstrate controlled population transfer between electrovibrational states of the ions at specific points along the propagation axis. Similarities and differences between our results and other pulse propagation phenomena of few-level quantum systems are discussed.

An Understanding of the Modulation of Photophysical Properties of Curcumin inside a Micelle Formed by an Ionic Liquid: A New Possibility of Tunable Drug Delivery System

The present study reveals the modulation of photophysical properties of curcumin, an important drug for numerous reasons, inside a micellar environment formed by a surfactant-like ionic liquid (IL-micelle) in aqueous solution. Higher stability of the drug inside IL-micelle in the absence and presence of a simple salt (sodium chloride) as well as considerably large partition coefficient (K(p) = 8.59 × 10(3)) to the micellar phase from water make this system a well behaved drug loading vehicle. Remarkable change in fluorescence intensity with a strong blue-shift implies the gradual perturbation of intramolecular hydrogen bond (H-bond) present within the keto-enol group of curcumin along with considerable formation of intermolecular H-bond between curcumin and the headgroup of surfactant-like IL. Very fast nonradiative decay channels in curcumin mainly caused by the excited state intramolecular proton transfer (ESIPT) are thus depleted remarkably in the presence of IL-micelle of reduced polarity and as a result of restricted rotational and vibrational degrees of freedom when bound to the micelle. Moreover, time-resolved results confirm that not only the keto-enol group of curcumin is playing here but also the phenolic hydroxyl groups are also responsible for such modulation in photophysical properties. From a thermodynamic point of view, our system shows good correlation with its stability parameters (higher binding constant with very less hydrolytic degradation rate ~1%) and higher negative value of binding enthalpy of interaction (-ΔH) than total free energy change (-ΔG) implies that the nature of binding interaction is enthalpy driven not entropy alone. Summarizing all the above observations, we have concluded that the modulation of the intramolecular proton transfer is due to the presence of both intermolecular proton transfer as well as strong hydrophobic interaction between curcumin and the IL-micelle.

Vibrational Relaxation in Several Derivatives of Benzene

Acoustical spectroscopy at frequencies up to 10 GHz gives the possibility of the investigation of liquid substances, where the relaxation process observed is caused by energy transfer between translational and vibrational degrees of freedom. The compounds presented in this article belong to this group of liquids. The acoustic investigations in the group of benzene derivatives, particularly research of the dependencies of acoustic parameters and the structure of organic liquids, demonstrated some interesting regularities in the group of these compounds in gas and liquid states. In this article, the results of research on five cyclic liquids: bromo-, chloro-, fluoro-, iodo-, and nitrobenzene as well as toluene and aniline are discussed and compared to benzene. The acoustic relaxation observed in all these compounds was found to result from Kneser’s processes (vibrational relaxation). Based on investigations reported in this article, as well as by other authors, and taking into account experimental and literature data concerning a great number of compounds, one can draw a conclusion that almost all acoustic relaxation (Kneser-type) processes in liquids can be described using a single relaxation time. It also seems that all vibrational degrees of freedom of the molecule take part in this process. It is known that the appearance of differences in transition probabilities could be caused by additional attraction in interactions of molecules having dipole moments. Halogen derivatives have higher values of dipole moments than benzene. This difference could be responsible for the difference of transition probabilities and changes in the relaxation times. However, benzene derivatives with amino, nitro, and methyl groups and halides show the other type of relaxation.