Effect of diatomic molecular properties on binary laser pulse optimizations of quantum gate operations

The importance of the ro-vibrational state energies on the ability to produce high fidelity binary shaped laser pulses for quantum logic gates is investigated. The single frequency 2-qubit ACNOT(1) and double frequency 2-qubit NOT(2) quantum gates are used as test cases to examine this behaviour. A range of diatomics is sampled. The laser pulses are optimized using a genetic algorithm for binary (two amplitude and two phase parameter) variation on a discretized frequency spectrum. The resulting trends in the fidelities were attributed to the intrinsic molecular properties and not the choice of method: a discretized frequency spectrum with genetic algorithm optimization. This is verified by using other common laser pulse optimization methods (including iterative optimal control theory), which result in the same qualitative trends in fidelity. The results differ from other studies that used vibrational state energies only. Moreover, appropriate choice of diatomic (relative ro-vibrational state arrangement) is critical for producing high fidelity optimized quantum logic gates. It is also suggested that global phase alignment imposes a significant restriction on obtaining high fidelity regions within the parameter search space. Overall, this indicates a complexity in the ability to provide appropriate binary laser pulse control of diatomics for molecular quantum computing.     

Isotope selective photoionization of NaK by optimal control: theory and experiment

We present a joint theoretical and experimental study of the maximization of the isotopomer ratio (23)Na(39)K(23)Na(41)K using tailored phase-only as well as amplitude and phase modulated femtosecond laser fields obtained in the framework of optimal control theory and closed loop learning (CLL) technique. A good agreement between theoretically and experimentally optimized pulse shapes is achieved which allows to assign the optimized processes directly to the pulse shapes obtained by the experimental isotopomer selective CLL approach. By analyzing the dynamics induced by the optimized pulses we show that the mechanism involving the dephasing of the wave packets between the isotopomers (23)Na (39)K and (23)Na (41)K on the first excited state is responsible for high isotope selective ionization. Amplitude and phase modulated pulses, moreover, allow to establish the connection between the spectral components of the pulse and corresponding occupied vibronic states. It will be also shown that the leading features of the theoretically shaped pulses are independent from the initial conditions. Since the underlying processes can be assigned to the individual features of the shaped pulses, we show that optimal control can be used as a tool for analysis.     

Quantum control of molecular vibrational and rotational excitations in a homonuclear diatomic molecule: a full three-dimensional treatment with polarization forces

The optimal control of the vibrational excitation of the hydrogen molecule [Balint-Kurti et al., J. Chem. Phys. 122, 084110 (2005)] utilizing polarization forces is extended to three dimensions. The polarizability of the molecule, to first and higher orders, is accounted for using explicit ab initio calculations of the molecular electronic energy in the presence of an electric field. Optimal control theory is then used to design infrared laser pulses that selectively excite the molecule to preselected vibrational-rotational states. The amplitude of the electric field of the optimized pulses is restricted so that there is no significant ionization during the process, and a new frequency sifting method is used to simplify the frequency spectrum of the pulse. The frequency spectra of the optimized laser pulses for processes involving rotational excitation are more complex than those relating to processes involving only vibrational excitation.     

Optimal control methods applied on the ionization processes of alkali dimers

We present two novel optimization methods by employing shaped fs-laser pulses in a closed feedback loop. The first describes control pulse cleaning where extraneous features were removed by applying genetic pressure on certain pulse components. The second reports parametric optimization with intuitive parameters such as subpulse distances, chirps, phase differences, and spectral peak patterns. These methods were conducted on the ionization process of alkali dimers produced in a molecular beam and improved the performances of the optimized pulses compared with short pulses at the same pulse energy. Moreover, we attempt to analyze the obtained pulse shapes regarding the underlying optimized processes. Further investigations concerning isotope selective fragmentation and optimal control of excitation processes of ultracold rubidium dimers in a magneto-optical trap (MOT) are also shown.     

Absorption and velocity of ultrasonic waves in thiophene, o-, p-xylenes and their mixtures

The results of acoustic measurements of velocity and absorption in three pure liquids: thiophene, p-and m-xylenes and their mixtures are presented. The experiments for the mixtures of thiophene were carried out by Eggers' method at frequencies 0.3–5 MHz, and for pure liquids by the pulse method in the frequency range 10 MHz–10 GHz, all at 293.15 K except for thiophene (at 281 and 333 K).

The absorption in thiophene shows that all vibrational degrees of freedom take part in the observed relaxation, caused by the Kneser processes. This process can be described as a vibrational relaxation with one relaxation time. Absorption in the mixtures decreased when increasing the amount of xylenes, as predicted by theory of gases, thus suggesting that the absorption is probably due to the same phenomenon as in gases.     

A semi-empirical and ab initio combined approach for the full conformational searches of gaseous lysine and lysine–H2O complex

A full structural search of the canonical, zwitterionic, protonated and deprotonated lysine conformers in gas phase is presented. A total of 17,496 canonical, 972 zwitterionic, 11,664 protonated and 1458 trial deprotonated structures were generated by allowing for all combinations of internal single-bond rotamers. All the trial structures were initially optimized at the AM1 level, and the resulting structures were determined at the B3LYP/6-311G^* level. A total of 927 canonical, 730 protonated and 193 deprotonated conformers were found, but there were no stable zwitterionic structures in the gas phase. The most stable conformers of the canonical, protonated and deprotonated lysine were further optimized at the B3LYP/6-311++G^** level. The energies of the most stable structures were determined at the MP2/6-311G(2df,p) level and the vibrational frequencies were calculated at the B3LYP/6-311++G^** level. The rotational constants, dipole moments, zero-point vibrational energies, harmonic frequencies, vertical ionization energies, enthalpies, Gibbs free energies and conformational distributions of gaseous lysine were presented. Numerous new structures are found and the lowest-energy lysine conformer is more stable than the existing one by 1.1 kcal/mol. Hydrogen bonds are classified and may cause significant red-shifts to the associated vibrational frequencies. The calculated proton affinity/dissociation energy and gas-phase basicity/acidity are in good agreement with the experiments. Calculations are also presented for the canonical lysine–H₂O and zwitterionic lysine–H₂O clusters. Interaction between lysine and H₂O significantly affects the relative conformational stabilities. Only one water molecule is sufficient to produce the stable zwitterionic structures in gas phase. The lowest-energy structure is found to be zwitterions when applying the conductor-like polarized continuum solvent model (CPCM) to the lysine–H₂O complexes.     

Design of an infrared laser pulse to control the multiphoton dissociation of the Fe-CO bond in CO-heme compounds

Optimal control theory is used to design a laser pulse for the multiphoton dissociation of the Fe-CO bond in the CO-heme compounds. The study uses a hexacoordinated iron-porphyrin-imidazole-CO complex in its ground electronic state as a model for CO liganded to the heme group. The potential energy and dipole moment surfaces for the interaction of the CO ligand with the heme group are calculated using density functional theory. Optimal control theory, combined with a time-dependent quantum dynamical treatment of the laser-molecule interaction, is then used to design a laser pulse capable of efficiently dissociating the CO-heme complex model. The genetic algorithm method is used within the mathematical framework of optimal control theory to perform the optimization process. This method provides good control over the parameters of the laser pulse, allowing optimized pulses with simple time and frequency structures to be designed. The dependence of photodissociation yield on the choice of initial vibrational state and of initial laser field parameters is also investigated. The current work uses a reduced dimensionality model in which only the Fe-C and C-O stretching coordinates are explicitly taken into account in the time-dependent quantum dynamical calculations. The limitations arising from this are discussed in Sec. IV.     

Deconstructing Desorption Electrospray Ionization: Independent Optimization of Desorption and Ionization by Spray Desorption Collection

Spray desorption collection (SDC) and reflective electrospray ionization (RESI) were used to independently study the desorption and ionization processes that together comprise desorption electrospray ionization (DESI). Both processes depend on several instrumental parameters, including the nebulizing gas flow rate, applied potential, and source geometries. Each of these parameters was optimized for desorption, as represented by the results obtained by SDC, and ionization, as represented by the results obtained by RESI. The optimized conditions were then compared to the optimization results for DESI. Our results confirm that optimal conditions for desorption and ionization are different and that in some cases the optimized DESI conditions are a compromise between both sets. The respective results for DESI, RESI, and SDC for each parameter were compared across the methods to draw conclusions about the contribution of each parameter to desorption and ionization separately and then combined within DESI. Our results indicate that desorption efficiency is (1) independent of the applied potential and (2) the impact zone to inlet distance, and that (3) gas pressure settings and (4) sprayer to impact zone distances above optimal for DESI are detrimental to desorption but beneficial for ionization. In addition, possible interpretations for the observed trends are presented.     

Overtone spectroscopy of isobutane at cryogenic temperatures

The spectra of the fundamental and overtones of the C---H stretches of (CH₃)₃CH have been measured in liquid argon solutions at 90 K and for the pure liquid sample at 135 K. Absorptions in the visible were obtained with a low temperature cell and a resonant continuous wave laser technique with acoustic detection. Absorptions in the IR and near-IR were observed with a Fourier transform spectrophotometer. Comparison is made between the absorption bands in gas phase, liquid argon solution, and liquid phase isobutane. The spectra of isobutane in solution show improved resolution of the vibrational bands with respect to the room temperature gas phase bands and the pure liquid bands at 135 K. To interpret the experimental results, overtone transitions are described in terms of the local mode model. A harmonically coupled anharmonic oscillator (HCAO) model was used to determine the overtone energy levels and assign the absorption bands to vibrational transitions. Ab initio molecular orbital calculations of geometries and vibrational frequencies were also performed.     

Optical control of excited-state vibrational coherences of a molecule in solution: The influence of the excitation pulse spectrum and phase in LD690

Spectral and phase shaping of femtosecond laser pulses is used to selectively excite vibrational wave packets on the ground (S0) and excited (S1) electronic states in the laser dye LD690. The transient absorption signals observed following excitation near the peak of the ground-state absorption spectrum are characterized by a dominant 586 cm(-1) vibrational mode. This vibration is assigned to a wave packet on the S0 potential energy surface. When the excitation pulse is tuned to the blue wing of the absorption spectrum, a lower frequency 568 cm(-1) vibration dominates the response. This lower frequency mode is assigned to a vibrational wave packet on the S1 electronic state. The spectrum and phase of the excitation pulse also influence both the dephasing of the vibrational wave packet and the amplitude profiles of the oscillations as a function of probe wavelength. Excitation by blue-tuned, positively chirped pulses slows the apparent dephasing of the vibrational coherences compared with a transform-limited pulse having the same spectrum. Blue-tuned negatively chirped excitation pulses suppress the observation of coherent oscillations in the ground state.     

Normal Spectral Emissivity at 684.5 nm of the Liquid Binary System Fe–Ni

Summary. Normal spectral emissivity at 684.5 nm of the liquid binary system Fe–Ni was measured by means of a fast ohmic pulse heating technique combined with fast ellipsometry. The experimental values observed of all liquid alloys are dependent on composition and temperature in the entire range of mixing. Spectral emissivity was measured for pure iron, Fe90Ni10, Fe80Ni20, Fe64Ni36, Fe50Ni50, Fe40Ni60, Fe30Ni70, Fe20Ni80, and pure nickel. Emissivity data as a function of temperature (at melting and in the liquid phase up to 2300 K) and as a function of the mixing ratio are presented and compared to the few existing literature-values.     

Ab initio studies of aspartic acid conformers in gas phase and in solution

Systematic and extensive conformational searches of aspartic acid in gas phase and in solution have been performed. For the gaseous aspartic acid, a total of 1296 trial canonical structures and 216 trial zwitterionic structures were generated by allowing for all combinations of internal single-bond rotamers. All the trial structures were optimized at the B3LYP/6-311G* level and then subjected to further optimization at the B3LYP/6-311++G** level. A total of 139 canonical conformers were found, but no stable zwitterionic structure was found. The rotational constants, dipole moments, zero-point vibrational energies, harmonic frequencies, and vertical ionization energies of the canonical conformers were determined. Single-point energies were also calculated at the MP2/6-311++G** and CCSD/6-311++G** levels. The equilibrium distributions of the gaseous conformers at various temperatures were calculated. The proton affinity and gas phase basicity were calculated and the results are in excellent agreement with the experiments. The conformations in the solution were studied with different solvation models. The 216 trial zwitterionic structures were first optimized at the B3LYP/6-311G* level using the Onsager self-consistent reaction field model (SCRF) and then optimized at the B3LYP/6-311++G** level using the conductorlike polarized continuum model (CPCM) SCRF theory. A total of 22 zwitterions conformers were found. The gaseous canonical conformers were combined with the CPCM model and optimized at the B3LYP/6-311++G** level. The solvated zwitterionic and canonical structures were further examined by the discrete/SCRF model with one and two water molecules. The incremental solvation of the canonical and zwitterionic structures with up to six water molecules in gas phase was systematically examined. The studies show that combining aspartic acid with at least six water molecules in the gas phase or two water molecules and a SCRF solution model is required to provide qualitatively correct results in the solution.     

One-photon mass-analyzed threshold ionization spectroscopy of CH2BrI: extensive bending progression, reduced steric effect, and spin-orbit effect in the cation

One-photon mass-analyzed threshold ionization (MATI) spectrum of CH2BrI was obtained using coherent vacuum-ultraviolet radiation generated by four-wave difference-frequency mixing in Kr. Unlike CH2ClI investigated previously, a very extensive bending (Br-C-I) progression was observed. Vibrational frequencies of CH2BrI+ were measured from the spectra and the vibrational assignments were made by utilizing frequencies calculated by the density-functional-theory (DFT) method using relativistic effective core potentials with and without the spin-orbit terms. A noticeable spin-orbit effect on the vibrational frequencies was observed from the DFT calculations, even though its influence was not so dramatic as in CH2ClI+. A simple explanation based on the bonding characteristics of the molecular orbitals involved in the ionization is presented to account for the above differences between the MATI spectra of CH2BrI and CH2ClI. The 0-0 band of the CH2BrI spectrum could be identified through the use of combined data from calculations and experiments. The adiabatic ionization energy determined from the position of this band was 9.5944+/-0.0006 eV, which was significantly smaller than the vertical ionization energy reported previously.     

Packed Column SFC of Gas Oils. Part II: Experimental Design Optimization of the Group-Type Analysis using CO2-SF6 as the Mobile Phase

An optimization procedure is presented for group-type analysis of diesel fuel by supercritical fluid chromatography using packed silica column and a mixed mobile phase. A set of five responses, four values of resolution of a performance mixture and analysis time, was modeled using a Doehlert matrix for experimental design. Optimized experimental conditions for the five responses were obtained from a response surfaces optimization, taking into account various constraints on SF₆ content in mobile phase and analysis time. The predicted and experimental resolutions were in good agreement for the different optimized conditions and one of them was selected to for application to a given diesel fuel for comparison with the results obtained by SFC using pure CO₂ and by HPLC. The conditions found in this study provide an alternative method for the determination of mono-, di-, and polyaromatic compounds in middle distillates.     

Suppression of phase and amplitude J(HH) modulations in HSQC experiments

The amplitude and the phase of cross peaks in conventional 2D HSQC experiments are modulated by both proton–proton, J(HH), and proton–carbon, ¹J(CH), coupling constants. It is shown by spectral simulation and experimentally that J(HH) interferences are suppressed in a novel perfect‐HSQC pulse scheme that incorporates perfect‐echo INEPT periods. The improved 2D spectra afford pure in‐phase cross peaks with respect to ¹J(CH) and J(HH), irrespective of the experiment delay optimization. In addition, peak volumes are not attenuated by the influence of J(HH), rendering practical issues such as phase correction, multiplet analysis, and signal integration more appropriate. Copyright © 2014 John Wiley & Sons, Ltd.     

Solvent effect of aqueous media on properties of glycine: Significance of specific and bulk solvent effects,and geometry optimization in aqueous media

Geometries of the normal (N) and zwitterionic (Z) forms of glycine (gly) and their complexes gly.(H₂O)_n, n = 0–2, were fully optimized in gas phase and aqueous media, and transition states located between the corresponding N and Z forms. The geometry was also optimized and vibrational spectra calculated for the gly.(H₂O)₃ complex of Z glycine. Density functional theory at the B3LYP/AUG‐cc‐pVDZ level was employed for the geometry optimization calculations in gas phase and aqueous media while single point energy calculations were performed at the MP2/AUG‐cc‐pVDZ level in each case. Solvation in bulk water was treated using the polarizable continuum model (PCM). Zero‐point energy correction to total energy and thermal energy correction to enthalpy were obtained at the B3LYP/AUG‐cc‐pVDZ level of theory in both gas phase and bulk aqueous media and these corrections were also considered to be valid for the corresponding single point energy calculations performed at the MP2/AUG‐cc‐pVDZ level of theory. When geometries of the complexes of glycine with water molecules are optimized in aqueous media, the calculated properties are found to be appreciably modified with respect to those obtained by gas phase geometry optimization followed by solvation in aqueous media. For several vibrational frequencies, the agreement between the calculated and experimentally observed results is improved appreciably when both the specific and bulk solvent effects are considered in combination with full geometry optimization in aqueous media. For certain vibrational frequencies, mode assignments have also been modified. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Quantum control of a molecular system in an intense field via the selective population of dressed states

We theoretically investigate the physical mechanism of quantum control on a K(2) molecule with an ultrafast strong laser pulse by solving the time-dependent Schr?dinger equation exactly using a wave packet approach. The structures of the triple splitting in the 3-photon ionization spectra of a K(2) molecule are presented to analyze the information of a selective population of dressed states. In this work, it is found that the tunability of the dressed states energies is achieved by regulating the laser intensity and the high selectivity of the dressed state population is attained by altering the envelope and wavelength of the intense laser pulse.     

Probing vibrational wave packets in molecular excited states

A time-dependent theoretical method is used to describe a UV pump?CUV probe strategy to trace, at a femtosecond time scale, the motion of vibrational wave packets created in excited states of the hydrogen molecule by measuring single ionization probabilities. We use a spectral method to solve the time-dependent Schr?dinger equation in full dimensionality, including correlation and all electronic and vibrational degrees of freedom. A pump pulse initially creates a vibrational wave packet in the intermediate electronic excited states of $\hbox{H}_2$ . The frequency of the probe is chosen to ionize the target leaving the ion in a bound vibrational state. By varying the time delay between pulses, non-dissociative single ionization is enhanced or suppressed. Energy differential ionization probabilities are reported and compared with a model based on the Franck?CCondon approximation.     

Vibrational energy transfer in hydrogen liquid and its isotopes

The transfer of vibrational energy (V-V) from H₂ to isotopic impurities (HD or D₂) has been studied in the liquid state, between 15 and 30 K. The subsequent relaxation (V-T) of the excited impurity by the H₂ liquid host has also been measured and contrasted with the vibrational relaxation behaviour of pure H₂ and D₂ liquids. The isothermal density dependence of both V-V and V-T transfer has been investigated in the fluid state at 30 K. High density relaxation rates are also compared to our data in the pure gases and to other available gas phase results. Measurements in the solid, near the triple point temperature, are equally reported for each process studied.     

Femtosecond laser pulse control of multidimensional vibrational dynamics: Computational studies on the pyrazine molecule

The multiconfiguration time-dependent Hartree (MCTDH) method is combined with the optimal control theory (OCT) to study femtosecond laser pulse control of multidimensional vibrational dynamics. Simulations are presented for the widely discussed three-electronic-level vibronic coupling model of pyrazine either in a three or four vibrational coordinate version. Thus, for the first time OCT is applied to a four-coordinate system. Different control tasks are investigated and also some general aspects of the OCT-MCTDH method combination are analyzed.