Alex Brown

The beta- and betadn- decays of neutron-rich ^134Sn and ^135Sn were studied at CERN/ISOLDE using elemental and mass selectivity achieved by the use of a resonance ionization laser ion source and a mass separator, respectively. Both gamma-ray singles and gamma-gamma coincidence spectra were collected as a function of time. These data were used to establish the positions of new low-energy

... Stephanie YY Wong, a Pierre-Nicholas Roy, b Alex Brown a. ... Chem. 21(2): 79-85 CrossRef. (28) Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su SJ, Windus TL, Dupuis M, Montgomery J A. 1993. J. Comput. ...

ABSTRACT The nuclear quadrupole coupling and spin-rotation constants of aluminum in AlH and AlD have been determined using coupled cluster theory with single and double excitations as well as perturbative inclusion of triples [CCSD(T)] combined with large correlation-consistent basis sets, cc-pCVXZ (X = T, Q and 5) and aug-cc-pCVXZ (X = T, Q). The anharmonic vibrational frequencies have been computed using second-order vibrational perturbation theory and the effects of vibrational averaging on the hyperfine constants have been determined. The ground state dipole moment has been determined for both isotopologues (AlH and AlD) and shown to depend critically on vibrational averaging. For completeness, the isotropic and anisotropic nuclear magnetic shielding tensors are also reported. All the results agree well with the best available experimental measurements, and in some cases (spin-rotation constants and dipole moments) refine the known data. The present computational results for the vibrationally averaged electric field gradients suggest that the currently accepted nuclear quadruple moment for 27Al of 146.6±1.0mb may be slightly underestimated. Based on the experimental measurements of the nuclear quadrupole coupling for AlH (AlD) and best computational determinations of the vibrationally averaged electric field gradients, the quadruple moment of 27Al is determined to be 149±2mb(148±3mb). However, this conclusion would be further strengthened with more precise experimental measurement of the 27Al nuclear quadrupole coupling for AlH and AlD.

ABSTRACT A brief introduction to quantum computing is provided and the potential use of molecules as the platform is discussed. The basic building blocks (quantum bits, quantum gates, and quantum algorithms) are described in order to emphasize the requirements for realizing a quantum computer, and, the advantages quantum computation has over its classical counterpart. We outline the three key steps to quantum computation: (1) initialization, (2) manipulation, and (3) readout. The possible use of internal molecular states as quantum bits and shaped laser fields to implement the quantum gates is introduced. The application to molecular quantum computing is connected to the more general problem of the control of quantum dynamics using tailored laser fields determined theoretically with optimal control theory or genetic algorithms.

Several centers have established that off-pump, multivessel coronary artery bypass grafting performed via a small thoracotomy (MVST) is feasible. However, this procedure can be challenging when posterolateral coronary targets need to be grafted. We hypothesized that use of cardiopulmonary bypass via peripheral access (MVST-PA) would improve outcomes compared with a completely off-pump approach (OP-MVST). This was a prospective observational study of patients undergoing OP-MVST (n = 46) versus MVST-PA (n = 45) using bilateral internal mammary artery grafts onto the left anterior descending coronary artery and circumflex/right coronary artery distribution. Hemostasis was quantified by measuring platelet function (aggregometry), chest tube output, thrombolysis in myocardial infarction bleeding score (%hematocrit change at 24 hours), and transfusion requirements. The rate of mortality and major morbidity at 30 days was defined according to The Society of Thoracic Surgeons criteria. Estimated glomerular filtration rate (normalized to baseline levels) was determined daily until discharge. The OP-MVST versus MVST-PA groups had similar risk factors at baseline and risks of composite morbidity/mortality at 30 days. However, renal failure was significantly increased after OP-MVST (10.87 vs 0%, P = 0.05), and MVST-PA affected hemostasis as evidenced by inhibition of platelet function (latency to response on aggregometry, 29.9 vs 17.9 seconds; P = 0.04) and higher transfusion requirement (2.31 vs 0.85 units of red blood cells/patient, P = 0.04; 55.6% vs 34.8% transfused; P = 0.059). However, 24-hour chest tube output was similar (645 vs 750 mL; P = 0.53). In comparison with a completely off-pump strategy, use of cardiopulmonary bypass to assist MVST reduced the risk of renal dysfunction with only modest tradeoffs in other morbidities, for example, altered coagulation and higher transfusion requirements. These data justify further study of the effect of MVST-PA on renal complications.

The resonance Raman spectrum of uracil is simulated using the Herzberg-Teller short-time dynamics formalism. The ground-state geometry is optimized at the levels of PBE0/aug-cc-pVTZ and B3LYP/aug-cc-pVTZ, respectively. The gradient of the bright excited state is computed using time-dependent density functional theory and spin-flip time-dependent density functional theory. The excited-state calculations are carried out in both the gas phase and implicit water using the conductor-like polarizable continuum model. The ground-state equilibrium structure is found to impact the resulting resonance Raman spectrum significantly. The simulated resonance Raman spectrum using the long-range corrected functionals, that is, CAMB3LYP and LC-BLYP, and based on the PBE0/aug-cc-pVTZ optimized ground-state structure shows better agreement with the experimental spectrum than using standard hybrid functionals, that is, PBE0 and B3LYP. The solvation effect leads to a change in the energetic order of the n → π* and π → π* excited states, and it improves the agreement with the experimental spectrum, especially with regard to the relative intensities of the peaks with frequencies greater than 1600 cm(-1).

The nuclear quadrupole coupling constants (NQCCs) for the nitrogen and oxygen nuclei in N(2)O have been determined using a variety of computational methods (MP2, QCISD, DFT with B3LYP, PBE0, and B3PW91 functionals, CCSD, CCSD(T), CASSCF, and MRCI) combined with correlation-consistent basis sets. When compared to the available experimental determinations, the results demonstrate that only CCSD(T) and MRCI methods are capable of accurately predicting the NQCCs of the central and terminal nitrogen atoms. The spin-rotation and magnetic shielding tensors have also been determined and compared to experimental measurements where available. (14)N and (17)O NMR relaxation data for N(2)O in the gas phase and a variety of solvents is reported. The increase in the ratio of (14)N spin-lattice relaxation times in solvent for the central and terminal nitrogens supports previous reports of the modification of the electric field gradients at these nuclei in van der Waals complexes. Ab initio computations for the linear FH···N(2)O complex confirm the large change in EFGs imposed by a single perturber.

Two-photon spectroscopy of fluorescent proteins is a powerful bioimaging tool. Considerable effort has been made to measure absolute two-photon absorption (TPA) for the available fluorescent proteins. Being a technically involved procedure, there is significant variation in the published experimental measurements even for the same protein. In this work, we present a time-dependent density functional theory (TDDFT) study on isolated chromophores comparing the ability of four functionals (PBE0, B3LYP, CAM-B3LYP, and LC-BLYP) combined with the 6-31+G(d,p) basis set to reproduce averaged experimental TPA energies and cross sections. The TDDFT energies and TPA cross sections are also compared to corresponding CC2/6-31+G(d,p) results for excitation to S1 for the five smallest chromophores. In general, the computed TPA energies are less functional dependent than the TPA cross sections. The variation between functionals is more pronounced when higher-energy transitions are studied. Changes to the conformation of a chromophore are shown to change the TPA cross-section considerably. This adds to the difficulty of comparing an isolated chromophore to the one embedded in the protein environment. All functionals considered give moderate agreement with the corresponding CC2 results; in general, the TPA cross sections determined by TDDFT are 1.5-10 times smaller than the corresponding CC2 values for excitation to S1. LC-BLYP and CAM-B3LYP give erroneously large TPA cross sections in the higher-energy regions. On the other hand, B3LYP and PBE0 yield values that are of the same order of magnitude and in some cases very close to the averaged experimental data. Thus, based on the results reported here, B3LYP and PBE0 are the preferred functionals for screening chromphores for TPA. However, at best, TDDFT can be used to semiquantitatively scan chromophores for potential TPA probes and highlight spectroscopic peaks that could be present in the mature protein.

A general and computationally efficient method for averaging both the time-dependent and the steady-state atomic or molecular state populations over the phases, delta1 and delta2, of two continuous-wave laser fields involved in an excitation process is developed based on the Floquet formalism. Explicit calculations are presented for the coherent one- and three-photon electronic excitation of a two-level model molecule in order to illustrate the importance of phase averaging in situations where the relative phase difference between the two fields is fixed. While the explicit results involve electronic excitation, they are presented in reduced form so that they can be scaled to other regions of the electromagnetic spectrum and to other field strengths. The results have important implications in situations where the relative phase difference between two intense continuous-wave laser fields is used to control the excitation process.

ABSTRACT DOBr photoabsorption cross-sections and product rotational state distributions of the OD fragment resulting from excitation to the two lowest-lying excited singlet electronic states, 11A″ and 21A′, are computed using time-dependent wavepacket dynamics. The dynamical calculations are based on two-dimensional ab initio potential energy and transition dipole moment surfaces, in which the OD bond length is held fixed. The computed absorption band for DOBr is very similar to that of HOBr for excitation from the ground vibrational state. For vibrationally mediated photofragmentation spectra in which the initial state is a vibrationally excited state, the absorption line shape for DOBr differs markedly from the corresponding HOBr absorption. For all initial vibrational states, the resulting OD fragments are produced more rotationally “hot” than their OH counterparts. The resulting OD and OH rotational distributions agree qualitatively with experimental measurements at 266 nm, where the excitation is dominated by the parallel 2 1A′←1A′ transition. Predictions are also made for the rotational distributions at 355 nm, where the perpendicular transition 11A″←1A′ is dominant and no experimental product state distributions are as yet available.