Tina Marie Briere

First-Principles Theory of Muon and Muonium Trapping in the Protein Chain of Cytochrome c and Associated Hyperfine Interactions

The microscopic details of the electron transfer in cytochrome c (cyt c) are being investigated by the Muon Spin Relaxation (μSR) technique. We are using the Hartree–Fock Cluster Procedure to determine the most likely trapping sites for μ+ and muonium (Mu) in the protein chain, and have performed extensive calculations in single amino acid molecules of the protein chain of cyt c. The double-bonded oxygen atom of the carboxyl group was identified as the trapping site for both μ+ and Mu. Utilizing the wave functions we obtained from the Hartree–Fock calculations, we have determined the hyperfine field that the μ+ in Mu experiences while the latter is trapped at the oxygen.

LOCATION OF MUONIUM AND HYDROGEN IN C60 FULLERENE AND ASSOCIATED ELECTRONIC STRUCTURE AND HYPERFINE PROPERTIES

The unrestricted Hartree-Fock (UHF) procedure is used to investigate the locations, associated electronic structures and hyperfine interactions for muonium and hydrogen in C60 fullerene. Our results indicate that from total energy considerations, in keeping with earlier investigations, the exohedral model has the lowest energy. However, the energies of the endohedral model involving the muonium (hydrogen) inside the fullerene and bonded to one of the carbon atoms, and of the muon at the center are found to be almost equal, contrary to earlier results. The hyperfine interaction constant for the endohedral site is in good agreement with that required to explain the lower observed muon spin-rotation (μSR) frequency in the C60-muonium system. The same appears to be the case for the exohedral model. However, there seems to be some uncertainty about the theoretical result in the latter case due to significant admixtures of higher spin states in the UHF wave-function. Additionally, in solid fullerene, the calculated location of the muonium for the exohedral model is such that it could be bonded to two fullerene molecules and therefore a muonium attached to a simple fullerene may not be representative of the exohedral state. This feature as well as the difficulty for the exohedral model of explaining the observed equality of the correlation times for relaxation effects associated with both μSR and13C relaxation times in nuclear magnetic resonance (NMR) experiments suggests that the endohedral model for muonium cannot at present be ruled out as a viable model in favor of the exohedral model. Possible avenues for future investigations to resolve some of the problems for both exohedral and endohedral models are discussed. Results obtained for muonium at the center of fullerene are presented and compared to the features of the observed high frequency μSR signal, and possible improvements in theory are discussed.

Theory for position of muonium in α-quartz and associated hyperfine interaction

The electronic structures and hyperfine interactions of muonium and hydrogen in α-quartz are investigated by the unrestricted Hartree-Fock cluster procedure. The muonium is found to be trapped near the center of the line joining two silicon atoms. On including vibrational effects, the muon hyperfine constant comes out as 1.09 times that for free muonium, this ratio being larger than unity and smaller than for protons in trapped hydrogen, both features being in agreement with experiment.

Theoretical investigation of muon and muonium trapping and hyperfine interactions in the chemical ferromagnet p-NPNN (β-phase)

The trapping sites for muon and muonium in β-phase ferromagnetic p-NPNN have been determined by the first-principles Unrestricted Hartree–Fock procedure. Four trapping sites are found for the muon near the two nitrogen and two oxygen atoms of the two NO groups. For the singlet state of trapped muonium, two trapping sites are found near the two oxygens of two NO groups and for the triplet state two trapping sites are found near the two oxygens of the NO2 group. The observed μSR signal at zero field with frequency 2.1 MHz is assigned to the singlet muonium sites near the two oxygens of the two NO groups and the high frequency signal ascribed to an isotropic hyperfine constant of 400 MHz is assigned to the two trapped muon sites near the two nitrogen atoms of the two NO groups.

Determination of Easy Axis in a Chemical Ferromagnet, 4-(p-Chlorobenzylideneamino)–TEMPO (TEMPO=2,2,6,6-Tetramethylpiperidin-1-Oxyl)

The trapping sites for muon and muonium in ferromagnetic p-Cl–Ph–CH=N–TEMPO [(4-(p-chlorobenzylideneamino)–TEMPO (TEMPOu2009=u20092,6,6-tetramethyl-piperidin-1-yloxyl)] and the hyperfine interaction tensors for these sites are obtained using first-principles Unrestricted Hartree–Fock theory. The calculated hyperfine interactions are used to compare the calculated zero field muon spin rotation (μSR) frequencies for different choices for the easy axis and the observed frequency. It has been concluded that the two trapping centers that can best explain the observed μSR frequency are a trapped singlet muonium near the radical oxygen and a trapped muon site near the chlorine. The direction of the easy axis also is determined to be the b-axis of the monoclinic lattice. This direction for the easy axis is confirmed by determining the direction of the distributed magnetization in the molecular solid which leads to a minimum dipole–dipole interaction energy. The consequences of this agreement for the easy axis direction by two independent procedures are discussed.

Theoretical study of trapping sites for muon in the heme group of cytochrome c and associated shifts in muon Spin Relaxation frequencies

Muon Spin Relaxation (μSR) experiments are currently being conducted on the important electron transfer molecule cytochrome c (cyt c) with the goal to find out about microscopic details of the path the moving electron is taking. Simultaneously we are using the Unrestricted Hartree–Fock Cluster Procedure to determine the trapping sites for muon (μ+) and muonium (Mu) in the heme unit of cyt c and the associated hyperfine interactions. For the trapping sites with the highest binding energies for μ+, namely the nitrogen and the carbon of the pyrrole rings, we have used the available magnetic susceptibility data together with our calculated hyperfine fields to predict the Knight-shifts. At room-temperature we found 88.4 ppm and 79.0 ppm for the most attractive N- and adjacent C-site, respectively. At 150 K, these shifts increase to 172.7 ppm for the N-site and 153.7 ppm for the C-site.

Theory of Nuclear Quadrupole Interactions in Solid Fluoromethanes with Implanted 19F Nuclei. Coupling of HF* and Host Molecule*

Abstract The Quadrupole Coupling Constant e2qQ and Asymmetry Parameter η of fluorine for fluorine-substitute methane compounds are calculated using the Hartree-Fock Roothaan procedure. Our results are compared with experimental data from measurements by the Time Differential Perturbed Angular Distribution (TDPAD) technique using excited 19F* (spin 5/2) nuclei. The theoretical e2qQ’s for the 19F* nuclei in the fluoromethanes are in good agreement with experimental results. For CH2F2 and CHClF2 molecules, where finite η are expected from symmetry considerations, our results for η are small, 0.12 and 0.05 respectively, in agreement with experimental observation. Besides the 19F* coupling constants associated with the C-F bonds in fluoromethanes, additional interesting NQI parameters, close to those in solid hydrogen fluoride, are observed in the TDPAD measurements. It is demonstrated through investigations of the total energies and electric field gradients that these additional NQI parameters for the fluoromethanes can be explained by a HF* molecule hydrogen-bonded through the hydrogen to a fluorine atom in the host molecular systems. This complexing of an ionic molecule to the host molecules in organic solids containing strongly electronegative atoms is expected to be a general feature in both implantation and conventional techniques.

First principles investigation of19F* nuclear quadrupole interaction in fourth group tetrafluorides

Using the Hartree-Fock-Roothaan procedure the nuclear quadrupole interactions of the19F (spin 5/2) nucleus in CF4, SiF4 and GeF4 are studied. The theoretical results explain within 10% the observed experimental measurements by the time-differential perturbed angular distribution technique, including the important feature of sharp decrease of the19F* nuclear quadrupole coupling constant in going from CF4 to SiF4, followed by an increase in going to GeF4, while a simple consideration of the ionic characters of the C-F, Si-F and Ge-F bonds together with Townes and Dailey theory would lead to a continuous decrease from CF4 to GeF4. The dependence of the results on the choice of basis sets and the role of many-body effects is discussed.

Investigation of expected location of muonium in normal state in III–V semiconductors and associated muon hyperfine interaction

The location and hyperfine properties of muonium in AlP is investigated by the unrestricted Hartree-Fock cluster procedure. Two minima are found, one at the aluminium tetrahedral interstitial site, and the other at the corresponding phosphorus site. The former is deeper by 0.25 eV and separated from the other minimum by a steep maximum of 0.63 eV in the hexagonal region. Using the calculated electronic wave functions, the muon hyperfine constant, after vibrational averaging, comes out smaller than the value for free muonium, the ratio being 0.93. This value is, however, significantly higher than the experimental results in GaP and GaAs.