Biological and Chemical Physics Commons^™

Angular Distributions For Near-Threshold (E,2E) Processes For H, He, And Other Rare-Gas Targets, Cheng Pan, Anthony F. Starace

Anthony F. Starace Publications

Distorted-wave calculations of the triply differential cross sections for electron-impact ionization of H, He, Ne, Ar, Kr, and Xe are presented for final-state electrons sharing ≤4 eV excess energy and for the coplanar, θ₁₂=π geometry. Results for H and He targets, presented briefly elsewhere [C. Pan and A. F. Starace, Phys. Rev. Lett. 67, 185 (1991)], are analyzed in greater detail and compared with available experimental and other theoretical results. In particular, for He targets the effects of exchange and of second-order capture processes are exhibited. These are shown to be of lesser importance than other short-range effects …

A Theoretical Investigation Of The Ground And Low‐Lying Excited States Of Butadiene Radical Cation, Robert J. Cave, Michael G. Perrott '90

All HMC Faculty Publications and Research

Results are presented from ab initio calculations on the ground and several low‐lying excited states of the butadiene radical cation. In particular, we have calculated geometries for the ground and several excited states at the multiconfiguration self‐consistent field level and characterized the planar stationary points. The vertical ionization potentials from the neutral molecule ground state and vertical excitation energies at the computed equilibrium geometry of the cation were also examined. A variety of methods were tested for the calculation of ionization potentials and excitation energies, including multiconfiguration self‐consistent field, multireference singles and doubles configuration interaction (with and without size‐consistency correction), …

Surface Structure Of √3x√3r 30 Cl/Ni(111) Determined Using Low-Temperature Angle-Resolved-Photoemission Extended Fine Structure, Li-Qiong Wang, Z. Hussain, Z. Q. Huang, A. E. Schach Von Wittenau, Dennis W. Lindle, D. A. Shirley

Chemistry and Biochemistry Faculty Research

A surface structural study of the √3 × √3 R30° Cl/Ni(111) adsorbate system was made using low-temperature angle-resolved photoemission extended fine structure. The experiments were performed along two emission directions, [111] and [110], and at two temperatures, 120 and 300 K. The multiple-scattering spherical-wave analysis determined that the Cl atom adsorbs in the fcc threefold hollow site, 1.837(8) Å above the first nickel layer, with a Cl-Ni bond length of 2.332(6) Å, and an approximate 5% contraction between the first and the second nickel layers (the errors in parentheses are statistical standard deviations only).

Measurement Of The Ratio Of Double-To-Single Photoionization Of Helium At 2.8 Kev Using Synchrotron Radiation, Jon C. Levin, Dennis W. Lindle, N. Keller, R. D. Miller, Y. Azuma, N. Berrah Mansour, H. G. Berry, Ivan A. Sellin

Chemistry and Biochemistry Faculty Research

We report the first measurement of the ratio of double-to-single photoionization of helium well above the double-ionization threshold. Using a time-of-flight technique, we find He⁺⁺/He⁺=1.6±0.3% at hν=2.8 keV. This value lies between calculations by Amusia (2.3%) and by Samson, who predicts 1.2% by analogy with electron-impact ionization cross sections of singly charged ions. Good agreement is obtained with older shake calculations of Byron and Joachain, and of Åberg, who predict 1.7%.

Anisotropy Of Polarized X-Ray Emission From Molecules, S. H. Southworth, Dennis W. Lindle, R. Mayer, P. L. Cowan

Chemistry and Biochemistry Faculty Research

Strongly anisotropic, polarized Cl K-V x-ray emission from gas-phase CF₃Cl has been observed following resonant excitation with a linearly polarized x-ray beam. Distinctively different angular distributions are observed for x-ray emission involving molecular orbitals of different symmetries. A classical model of the x-ray absorption-emission process accurately describes the observed radiation patterns.

Removal Of Chlorine From Chlorine-Nitrogen Mixture In A Film Of Liquid Water, Sarwan S. Sandhu

Chemical and Materials Engineering Faculty Publications

In industry there are many examples of absorption of a gas with or without chemical reaction in the liquid phase. In physical absorption, a particular gaseous component is removed from a gas mixture due to its larger solubility in the liquid phase solvent. The removal of butane and pentane from a refinery gas mixture by a heavy oil in the liquid phase is an example of physical absorption. In absorption with chemical reaction, the gaseous component to be removed transfers across the gas-liquid interface due to a difference in the bulk chemical potentials or concentrations in the two phases. The …

Molecular-Orbital Studies Via Satellite-Free X-Ray Fluorescence: Cl-K Absorption And K–Valence-Level Emission Spectra Of Chlorofluoromethanes, Rupert C. Perera, P. L. Cowan, Dennis W. Lindle, R. E. Lavilla, T. Jach, R. D. Deslattes

Chemistry and Biochemistry Faculty Research

X-ray absorption and emission measurements in the vicinity of the chlorine K edge of the three chlorofluoromethanes have been made using monochromatic synchrotron radiation as the source of excitation. By selectively tuning the incident radiation to just above the Cl 1s single-electron ionization threshold for each molecule, less complex x-ray-emission spectra are obtained. This reduction in complexity is attributed to the elimination of multielectron transitions in the Cl K shell, which commonly produce satellite features in x-ray emission. The resulting "satellite-free" x-ray-emission spectra exhibit peaks due only to electrons in valence molecular orbitals filling a single Cl 1s vacancy. These …

Polarized X-Ray-Emission Studies Of Methyl Chloride And The Chlorofluoromethanes, Dennis W. Lindle, P. L. Cowan, T. Jach, R. E. Lavilla, R. D. Deslattes, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

A new technique sensitive to molecular orientation and geometry, and based on measuring the polarization of x-ray emission, has been applied to the Cl-containing molecules methyl chloride (CH₃Cl) and the chlorofluoromethanes (CF₃Cl, CF₂Cl₂, and CFCl₃) in the gas phase. Upon selective excitation using monochromatic synchrotron radiation in the Cl K-edge (Cl 1s) near-threshold region, polarization-selective x-ray emission studies reveal highly polarized molecular valence x-ray fluorescence for all four molecules. The degree and the orientation of the polarized emission are observed to be sensitive to the incident excitation energy near …

Fine‐Structure Mixing Within The Zn(43pj) Multiplet By Collisions With The Noble Gases, Xianming Han, J. F. Kelly

Scholarship and Professional Work - LAS

Measurements of rate coefficients for intramultiplet state transfer of Zn(4 ³ P ₁→4 ³ P _J’) by collisions with the rare gases are presented. The state‐to‐state binary rate coefficients are derived from least‐squares fittings of the time‐resolved triexponential behavior of the 4 ³ P ₁fluorescence. These rate coefficients were studied systematically over a temperature range of 690–1100 K in order to characterize the velocity dependence of the collisional coupling. The systematic behavior of the rate coefficients with varying temperature and noble gas species is qualitatively consistent with a nearly adiabatic coupling limit for noncrossing levels.

Direct Determination Of Molecular-Orbital Symmetry Of H2s Using Polarized X-Ray Emission, R. Mayer, Dennis W. Lindle, S. H. Southworth, P. L. Cowan

Chemistry and Biochemistry Faculty Research

X-ray emission from the molecule H₂S is strongly polarized following excitation of a sulfur K-shell electron to an unoccupied subthreshold molecular orbital with a polarized x-ray beam. Changes in the polarization of the emission spectrum are observed as the incident beam's energy is swept across the subthreshold absorption resonance. The previously unresolved absorption resonance is shown experimentally to be primarily associated with a molecular orbital of b₂ symmetry, but with a high-excitation-energy component due to an orbital with a₁ symmetry. Satellite emission intensity is shown to depend on the primary photon energy and is therefore associated …

Collisional Excitation Of Co By 2.3 Ev H Atoms, George C. Mcbane, Scott H. Kable, Paul L. Houston, George C. Schatz

Peer Reviewed Articles

Vibrational and rotational distributions of CO excited by collisions with 2.3 eV H atoms have been obtained by monitoring the products with vacuum ultraviolet (VUV) laser induced fluorescence. Translational-to-vibrational (T→V) transfer is dominated by the dynamics of collisions occurring in the two wells on the H+CO potential energy surface, one characterizing the HCO radical and the other characterizing COH. The measured vibrational distributions agree well with the results of trajectory calculations performed on the ab initio potential energy surface of Bowman, Bittman, and Harding (BBH). The measured rotational distributions show two significant differences from the calculated ones. First, for v …

Argon-Photoion–Auger-Electron Coincidence Measurements Following K-Shell Excitation By Synchrotron Radiation, Jon C. Levin, C. Biedermann, N. Keller, L. Liljeby, C.-S. O, R. T. Short, Ivan A. Sellin, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Argon photoion spectra have been obtained for the first time in coincidence with K-LL and K-LM Auger electrons, as a function of photon energy. The simplified charge distributions which result exhibit a much more pronounced photon-energy dependence than do the more complicated noncoincident spectra. In the near-K-threshold region, Rydberg shakeoff of np levels, populated by resonant excitation of K electrons, occurs with significant probability, as do double-Auger processes and recapture of the K photoelectron through postcollision interaction.

Size‐Inconsistency Effects In Molecular Properties For States With Valence‐Rydberg Mixing: The Low‐Lying Π→Π∗ States Of Ethylene And Butadiene, Robert J. Cave

All HMC Faculty Publications and Research

Ab initio results for the low‐lying 1B1u states of ethylene are used to discuss size‐inconsistency effects on calculated molecular properties for states where valence‐Rydberg mixing is important. Results for the expectation value of x2, x being the coordinate perpendicular to the plane of the molecule, are presented from quasidegenerate variational perturbation theory and multireference configuration‐interaction calculations. These results are compared with values from previous studies. It is argued that size inconsistency in configuration‐interaction studies can have a significant effect on estimated molecular properties. Calculations on several low‐lying states of butadiene are also reported where similar size‐inconsistency effects are found.

The 157 Nm Photodissociation Of Ocs, C. E. Strauss, George C. Mcbane, P. L. Houston, I. Burak, J. W. Hepburn

Peer Reviewed Articles

The photodissociation of OCS at 157 nm has been investigated by using tunable vacuum ultraviolet radiation to probe the CO and S photoproducts. Sulfur is produced almost entirely in the ¹S state, while CO is produced in its ground electronic state and in vibrational levels from v=0-3 in the appropriate ratio (v=0):(v=1):(v=2):(v=3) = (1.0):(1.0):(0.5):(0.3). The rotational distribution for each vibrational level is found to be near Boltzmann, with temperatures that decrease from 1350 K for v=0 to 780 K for v=3. Measurements of the CO Doppler profiles demonstrate that the dissociation takes place from …

Quasidegenerate Variational Perturbation Theory And The Calculation Of First‐Order Properties From Variational Perturbation Theory Wave Functions, Robert J. Cave, Ernest R. Davidson

All HMC Faculty Publications and Research

In previous work on the treatment of correlation in molecular systems we have applied a multireference version of second‐order Hylleraas variational perturbation theory. The choice made for the partitioning of H treated the interactions between the correlating functions to infinite order and gave the corrections to the wave function to first order. The method was shown to be accurate in many cases, but became less so when near degeneracies occurred between the reference energy and other eigenvalues of H0. In this article we introduce an effective Hamiltonian method that is analogous to variational perturbation theory, but which is significantly more …

Hylleraas Variational Perturbation Theory: Application To Correlation Problems In Molecular Systems, Robert J. Cave, Ernest R. Davidson

All HMC Faculty Publications and Research

Hylleraas variational perturbation theory is applied through second order in energy to estimate the correlation energy in several molecular systems. The specific choices for H₀ and V which are made lead to equations nearly identical to the multireference linearized coupled‐cluster method of Laidig and Bartlett. The results obtained are in virtually exact agreement where comparisons have been made. Results from test calculations are presented for BeH₂, CH₂, and C₂H₄. In addition, the utility of perturbation theory for selecting correlating configurations is examined. This procedure is found to be quite accurate while …

The Spectroscopy And Molecular Dynamics Of The High Frequency Ν1 6 Intermolecular Vibrations In Hcn‐‐‐Hf And Dcn‐‐‐Df, B. A. Wofford, M. W. Jackson, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Gas phase rovibrational analysis of the high frequency intermolecular hydrogen bonded bending overtone 2ν⁰ ₆ [ν₀=1132.4783(2) cm^{− 1}] in HCN‐‐‐HF and its corresponding perdeuterated fundamental ν¹ ₆ [ν₀=409.1660(2) cm^{− 1}] are reported. Evaluated rovibrational parameters provide the basis for quantitative modeling of the molecular dynamics associated with this vibration. A quantum mechanical calculation permits determination of the quadratic and quartic force constants K _{6 6}=537(17) and K _{6 6 6 6}=4.98(12) cm^{− 1} which in turn are used to estimate the pertinent cubic band stretching interaction constants …

Erratum: Determination Of Dissociation Energies And Thermal Functions Of Hydrogen Bond Formation Using High Resolution Ftir Spectroscopy [J. Chem. Phys. 8 7, 5674 (1987)], B. A. Wofford, M. E. Eliades, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Erratum

State-Selective Studies Of T→R, V Energy Transfer: The H+Co System, G. K. Chawla, George C. Mcbane, P. L. Houston, G. C. Schatz

Peer Reviewed Articles

Collisional energy transfer from H atoms to CO(v=0, J≈2) has been studied at a collision energy of 1.58±0.07 eV by photolyzing H₂S at 222 nm in a nozzle expansion with CO and probing the CO(v", J") levels using tunable VUV laser-induced fluorescence. The ratio CO(v"=1)/CO(v"=0) is found to be 0.1±0.008. The rotational distribution of CO(v"=0) peaks at J"gradually; population is still observed at J">45. The rotational distribution of CO(v"=1) is broad and peaks near J"=20. The experimental results are compared to …

Theoretical Studies Of Electron Transfer In Metal Dimers: Xy+→X+Y, Where X, Y=Be, Mg, Ca, Zn, Cd, Robert J. Cave, David V. Baxter, William A. Goddard Iii, John D. Baldeschwieler

All HMC Faculty Publications and Research

The electronic matrix element responsible for electron exchange in a series of metal dimers was calculated using ab initio wave functions. The distance dependence is approximately exponential for a large range of internuclear separations. A localized description, where the two nonorthogonal structures characterizing the electron localized at the left and right sites are each obtained self‐consistently, is found to provide the best description of the electron exchange process. We find that Gaussian basis sets are capable of predicting the expected exponential decay of the electronic interactions even at quite large internuclear distances.

Determination Of Dissociation Energies And Thermal Functions Of Hydrogen‐Bond Formation Using High Resolution Ftir Spectroscopy, B. A. Wofford, M. E. Eliades, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A technique which employs high resolution Fourier transform infrared spectroscopy is demonstrated for evaluation of hydrogen bonddissociation energiesD ₀ and D _e . Results for HCN‐‐HF give a D ₀=20.77(22) and D _e =28.77(45) kJ/mol which are compared with previously determined values obtained from microwave absolute intensity measurements and a b i n i t i o molecular orbital calculations. Rovibrational band information available for HCN‐‐HF also permits evaluation of thermal functions of dimer formation in kJ/mol: ΔU ^○ _298.2 =20.1(2), ΔH ^○ _298.2 =22.6(2), ΔG ^○ _298.2 =59.4(2), ΔS ^○ _298.2 =−0.1235.

Molecular Dynamics In Hydrogen‐Bonded Interactions: A Preliminary Experimentally Determined Harmonic Stretching Force Field For Hcn‐‐‐Hf, B. A. Wofford, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Observation of the 2ν₁ overtone band in the hydrogen‐bonded complex HCN‐‐‐HF permits evaluation of the anharmonicity constant X _{1 1}=−116.9(1) cm^{− 1} and determination of the anharmonicity corrected fundamental frequency ω₁. This information, and available data from previous rovibrational analyses in the common and perdeuterated isotopic species of HCN‐‐‐HF, offer an opportunity for calculation of an approximate stretching harmonic force field. With the assumptions f _{1 2}=f _{2 4}=0.0, the remaining force constants (in mdyn/Å) are evaluated as: f _{1 1}=8.600(20), f _{2 2}=6.228(9), f _{3 3}=19.115(40), f _{4 …}

Experimental Fine-Structure Branching Ratios For Na-Rare-Gas Optical Collisions, Mark D. Havey, F. T. Delahanty, Linda L. Vahala, Gary E. Copeland

Electrical & Computer Engineering Faculty Publications

Experimental ratios for branching into the fine-structure levels of the Na 3p multiplet, as a consequence of an optical collision with He, Ne, Ar, Kr, or Xe, are reported. The process studied is Na(3s²S_1/2)+R+nhNNa(3^p2P_j)+R+(n-1)_hN, where R represents a rare-gas atom and where the laser frequency N is tuned in the wings of the Na resonance transitions. The branching ratios are defined as I(D1)/I(D2) where I(D1) and I(D2) are measured intensities of the atomic Na D1 and D2 lines. The ratios are determined for detunings ranging from about 650 …

Further Studies On Purification Of A Mannitol Binding Protein: Use Of Ph Gradients For Elution From Cation Exchange Resin, Kristyne Ann Baumgarten

Masters Theses

Studies on the purification of a mannitol binding protein (MBP) from Pseudomonas aeruginosa PAO were performed. Utilizing the alkaline isoelectric point (pi 8.3) of MBP, pH gradients were used to elute MBP from carboxymethylcellulose cation exchange resins. Purification of MBP was monitored by sodium dodecyl sulfate-polyacrylam ide gel electrophoresis (SDS-PAGE). Only one protein band was seen on SDS-PAGE from MBP fractions elutedat pH 7-8 and 8 .2. Although pH gradients appear to give good purification from cation exchange resins, these procedures lead to loss of MBP activity.

A Semiclassical Model For Orientation Effects In Electron Transfer Reactions, Robert J. Cave, Stephen J. Klippenstein, R.A. Marcus

All HMC Faculty Publications and Research

An approximate solution to the single‐particle Schrödinger equation with an oblate spheroidal potential well of finite depth is presented. The electronic matrix element H_BA for thermal electron transfer is calculated using these wave functions, and is compared with values of H_BA obtained using the exact solution of the same Schrödinger equation. The present method yields accurate results for H_BA, within the oblate spheroidal potential well model, and is useful for examining the orientational effects of the two centers on the rate of electron transfer.

Copper Electrodeposition In A Magnetic Field, Hiroshi Takeo

Dissertations and Theses

The effect of a magnetic field on copper electrodeposition was investigated. Copper was electrodeposited onto square copper cathodes 1 sq cm in area from an aqueous solution (0.5 M CuSO₄, 0.5 M H₂SO₄. A glass cell was placed between the pole pieces of an electromagnet, and the magnetic fields applied were in the range from 0 to 12.5 kG. The current density was in the range from 80 mA/sq cm to 880 mA/sq cm. In each of the experiments, cell current, cell voltage, and cell temperature were monitored with a microcomputer. The weight …

A Model For Orientation Effects In Electron‐Transfer Reactions, Paul Siders, Robert J. Cave, R.A. Marcus

All HMC Faculty Publications and Research

A method for solving the single‐particle Schrödinger equation with an oblate spheroidal potential of finite depth is presented. The wave functions are then used to calculate the matrix element T_BA which appears in theories of nonadiabatic electron transfer. The results illustrate the effects of mutual orientation and separation of the two centers on T_BA. Trends in these results are discussed in terms of geometrical and nodal structure effects. Analytical expressions related to T_BA for states of spherical wells are presented and used to analyze the nodal structure effects for T_BA for the spheroidal wells.

Alternating Current Studies And Kinetic Analysis Of Valinomycin Mediated Charge-Transport Through Lipid Bilayer Membranes, Kenneth Lee Cox

Dissertations and Theses

In this study we have investigated the frequency dependence of bilayer lipid membranes for a series of glycerylmonoolein/n-decane bilayers in various aqueous ionic solutions containing the ionophore valinomycin. Reliable values of membrane capacitance and conductance were obtained over the frequency range 0.2 - 200 KHz using an automatic balancing bridge under the control of a microprocessor unit. The admittance data was then normalized and curve-fitted to produce relaxation times and amplitudes from which the kinetic rate parameters, as deduced from a single slab dielectric membrane model, were calculated. These ac experimental rate constants were then compared with those obtained from …

The Effects On Plant Growth, W M. Porter, J. S. Yeates

Journal of the Department of Agriculture, Western Australia, Series 4

The level of acidity of a soil reflects its chemical and sometimes its biological condition. Changes in acidity mean changes in the availability to plants of some soil elements, and modifications to the biological processes in the soil.

Some elements become more available to plants in acis soils, and in some soils particular elements can reach toxic levels. Other elements can be effected in the opposite way: deficiencies can develop in acid conditions.

It is important to realise, however, that the chemical nature of all soils varies. Beccause of these variations, acidity can affect each soil differently and thus influence …

Preliminary Rovibrational Analysis Of The Nν6+Ν1−Nν6 Vibration In Hcn⋅⋅⋅Hf, E. Kyrö, K. Mcmillan, M. Eliades, D. Danzeiser, P. Shoja-Chaghervand, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A preliminary rotation‐vibration analysis of the n=0 and n=1 subbands associated with the nν₆+ν₁−nν₆ hydrogen‐bonded vibration in HCN⋅⋅⋅HF has been completed. The following excited staterotational constantsB′ and band origin frequencies ν₀ have been determined for the complex. The results are consistent with a rotation‐vibration interaction constant α₁=−68.3±1 MHz which correlates with an excited stater(N⋅⋅⋅F) internuclear distance of 2.762 Å, a decrease of 0.034 Å relative to the ground state.Excited state lifetimes associated with assigned transitions are demonstrated to be …