Lawrence Berkeley National Laboratory Recent Work

Title MATERIALS AND MOLECULAR RESEARCH DIVISION NEWSLETTER

Permalink https://escholarship.org/uc/item/9vg7w5vq

Author Lawrence Berkeley National Laboratory

Publication Date 2018-01-04

eScholarship.org Powered by the California Digital Library University of California DISCLAIMER

This document was prepared as an account of work sponsored by the Government. While this document is believed to contain correct information, neither the United States Government nor any agency thereof, nor the Regents of the University of California, nor any of their employees, makes any warranty, express or implied, or assumes any legal responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by its trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof, or the Regents of the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof or the Regents of the University of California. L"'-1~·--·~ILA--.

For Reference e"WSJette~~~~ _]) NoJ to be taken from this room LBL LIBRARY April1980 Volume 4, No.3

BULLETIN

ALAN SEARCY is the new Head of MMRD. Congratulations, ALAN! * * * GARETH THOMAS receives 1980 Distinguished Award for Physical Sciences from Electron Microscopy Society of America!

David A. Shirley RESEARCH PROFILE DIVISION HEAD MOVES UP! PHOTOCHEMISTRY AND DAVID SHIRLEY NEW LBL DIRECTOR REACTION KINETICS

by Harold S. Johnston DAVID SHIRLEY has been named Director of the Lawrence Berkeley Laboratory, Chemical Reactions and Theories succeeding ANDREW SESSLER in that of Reaction Kinetics demanding, yet challenging, position.

A chemical reaction encountered in SHIRLEY was once described in a everyday life, in an industrial Laboratory publication as a "young process, or in the atmosphere typi­ man in a hurry." The expression is cally consists of a complex set of apt. Beginning with an inveterate molecular steps, some acting in curiosity about how things work and an series and some in parallel. These early interest in , he quickly molecular processes include elementary exha.usted the experiments in the manual physical reactions involving energy accompanying a Gilbert chemistry set exchange and elementary chemical and then obtained permission to sit reactions involving the making and in on chemistry lectures at Kansas breaking of molecular bonds. Theories State University. He was then eleven! of chemical kinetics concern the rates of elementary chemical reactions. The He earned a B.S. in chemistry from the classic theories of gas-phase chemical University of Maine, a Ph.D. studying kinetics as developed in the 1930s and under Prof. W. F. GIAUQUE at UCB, and (continued on page 3) (continued on page 2) SHIRLEY (continued) HVEM INSTALLATION BEGINS shortly afterwards joined the UCB faculty. By 1967 he was a professor The installation phase of the High­ and four years later he became Chair­ Voltage Electron Microscope Project man of the Chemistry Department of has begun with the arrival of the the University. In 1975, DAVE was remaining parts of the instrument. appointed Head of a Division of the The temporary south side of the Laboratory - the Materials and Molecu­ Building 72 silo has been removed to lar Research Division, newly created allow the large pressure tanks that from elements of three former groups will house the high voltage genera­ on the Hill. After five strong years tor and electron accelerator to be as MMRD Head, SHIRLEY now moves to placed in position. The 3.5-ton leadership of the entire laboratory. viewing chamber and the accelerator support platform will be installed, followed by the tanks. In his introduction to the 1979 MMRD Annual Report, SHIRLEY notes with LBL personnel are helping the manu­ satisfaction some current projects facturer's engineers assemble and initiated in the Division during his install the accelerator and micro­ tenure, which are now moving toward scope column. Once the equipment is fruition: funding for construction of inside, construction personnel will a chemical and materials sciences complete installation of the perman­ laboratory devoted to atomic resolution ent south wall. microscopy and research in and ; a prdgram in By late May or early June a recogniz­ electrochemical synthesis and energy able electron microscope silo will storage with investigators from both add a new feature to the Berkeley MMRD and E&E; and joint sponsorship by skyline--but time-consuming subsystem DOE's Fossil Energy Division and the electronic testing will continue for Chemical Sciences Division of the Basic several additional months before Energy Sciences of a vigorous collabora­ final instrument acceptance tests and tive program in coal chemistry and mor­ calibration are completed. phology. This latter project represents a new approach for DOE in which basic --KEN WESTMACOTT researchers focus their talents on problems of specific interest in energy technologies.

There are other reasons for pride as well: the 1.5 MeV High Voltage Elec­ GERBER REPLACES WEBB tron Microscope is nearing completion, the Division staff has been strengthened, Steve Gerber of the Technical Information the annual budget has increased, and Department is the new coordinating several other large interactive programs editor with MMRD. He replaces Cathy of great promise have been set in motion. Webb, who has left LBL.

Steve has been with LBL since 1962 and In his final introduction to an MMRD will offer a combination of skills in annual, SHIRLEY expressed his apprecia­ publications and visual communications. tion to the scientific, technical, During his first 14 years at the Lab he administrative and support staff and was a photographer. added, "I shall enjoy stepping aside and watching the new ideas and develop­ Since 1977, Steve has worked at TID in ments that will be brought in by the a combined role as a technical editor, next Division Head. I have served with associate audio-visual producer, and pleasure and I look forward to partici­ cinematographer. You may contact Steve pating in the Division's future at Bldg 62, Rm 249, Ext. 5842 on activities." Tuesdays and Wednesdays. Welcome, STEVE.

2 RESEARCH PROFILE (continued) ozone and haze and eye irritation. I was attracted to this problem and tried 1940s were tested against the rates of to figure out a set of elementary reactions measured up to that time, chemical reactions that would be suffi­ and it is a droll fact that most of cient to explain his results. At first these test cases were complex chemical it seemed that the process might be reactions, unsuitable for direct explained by 10 or so reactions. As theoretical analysis. As late as time went on, hundreds of elementary 1950 there were few tests of these reactions were implicated. At present theories against valid experimental there appear to be thousands of elemen­ data. tary reactions involved, rate constants are known for only a small fraction of During the 1950s and 1960s my field them, and complete modeling of photo­ was searching out elementary chemical chemical smog seems out of reach at this reactions in the gas phase to measure time. their rates in the laboratory and to subject these measurements to the theories of reaction kinetics. In The National Bureau of Standards the early 1950s reliable rate constants published successful and useful books had been measured for only a few of critically evaluated thermodynamic elementary reactions, but this situa­ data in the 1950s. With this work as tion changed rapidly with the intro­ a model, NBS set out to do a similar duction of flash photolysis, shock service for the field of chemical waves in chemical reactors, fast-flow kinetics. Experts in various fields systems, and improved optical and mass were urged to collaborate with NBS in spectrometers. My graduate students producing a series of monographs, each and I studied elementary unimolecular a critical evaluation for a portion of reactions for several years; we the field. I agreed to produce a review branched out to study elementary of the chemical kinetics of the oxides bimolecular reactions. For a time we of nitrogen and of ozone. As part of were interested in the phenomenon of this agreement, NBS sent me Xerox copies reaction rates at high temperatures, of all publications since 1900 in English, and we became especially interested in French, and German that concerned the kinetic isotope effects, which are kinetics of ozone and the nitrogen primarily of quantum mechanical origin. oxides. I spent two summers and many It didn't really matter to us what weekends in the mid-1960s going through substances were used to test :r-eaction­ this material, recalculating the data rate theories for these various types wherever possible, and putting all of reactions. However, we got in the studies in the same units. The job habit of following reactions of the was such a large one that NBS and I oxides of nitrogen because of the great agreed to do it as two books, one on variety of processes they exemplify, ozone and one on nitrogen oxides. The and we studied reactions of ozone, monograph on ozone and atomic oxygen fluorine, chlorine, and some simple was published in 1968, and although organic molecules. The systematic much work was devoted to it the book on testing of reaction rate theories nitrogen oxides was never completed. against appropriate laboratory data was summarized in a book, Gas Phase Reaction Rate Theory, published in Although the final book on ozone gave 1966. its results in terms of only six elementary reactions, the review of all the literature on ozone kinetics was Research in Photochemical Smog not an easy job. A conspicuous feature was the irreproducibility of most In the early 1950s A. J. Haagen-Smit studies. Different authors disagreed proposed his phenomenological mechanism strongly with one another. Sometimes for photochemical smog: gasoline plus a given author would report large day­ nitrogen oxides plus sunlight yield to-day variations in the rate of a

3 given reaction. In a number of these led to a broad program of stratospheric cases, I was able to track down the research that has continued over the source of these discrepancies and past nine years. It turned out that the assign them to catalytic reactions by stratosphere had been a largely neglected trace amounts of nitrogen oxides, part of the world, and this research was chlorine, or metal surfaces. About 90% overdue. of all the kinetic data taken with ozone since 1900 had to be thrown out because of the effect of uncontrolled catalysts on the measured rates. Chlorofluoromethanes and the Stratosphere

Ozone Research and the Stratosphere In the course of this atmospheric research, Rowland and Malina pointed out that man-made chlorofluoro­ My research unexpectedly took a new methanes (DuPont's "Freon" and trade direction in 1971. I was invited to names used by other companies) behaved Boulder, Colorado, in March 1971 to hear in the stratosphere very much the same a presentation by experts in atmospheric way as natural nitrous oxide. When sciences about the possibility that a far ultraviolet solar radiation breaks large fleet of supersonic transports down chlorofluoromethanes in the middle might adversely affect the stratosphere. stratosphere, they produce chlorine In the stratosphere, ozone and water atoms and chlorine oxide, which destroy vapor are each present at parts per ozone in a catalytic cycle that is the million, but the oxides of nitrogen are same in many respects as that for present only at parts per billion. At nitrogen oxides. After five years of the meeting we were told that the intensive study of this problem, the predicted fleet of supersonic transports original concerns have been confirmed would be expected to increase stratos­ that the current rate of release of pheric water vapor by 10% and stratos­ chlorofluoromethanes is expected over pheric nitrogen oxides by a factor of 10. a few decades to reduce global stratos­ Since the increased nitrogen oxides would pheric ozone i~ the order of magnitude still be about 100-fold less than ozone of 10%. itself, atmospheric scientists regarded the oxides of nitrogen as negligible in My graduate students and I have partici­ this context. At and after the meeting, pated in this research, and in the I pointed out the role of nitrogen oxides laboratory we have made several chemical as catalysts for ozone destruction, such and photochemical studies. The substances that trace amounts could be significant. have usually been selected for atmos­ One speaker at the meeting presented pheric applications, but we are also model calculations that this large interested in the physical-chemical increase in nitrogen oxides would reduce principles that they illustrate. A the vertical ozone column by only 2%. recent example is the photolysis of However, I spotted an error in his the nitrate-free,radical N03 . When it calculation; for one rate constant absorbs sunlight, it may break down to involving nitric oxide, which had been give NO+ o2 , which destroys ozone, or accurately measured in the 1920s, he it may give N02 + 0, which produces had used an estimated value that was ozone. In the laboratory we used a incorrect by a factor of 10,000. When pulsed tunable laser to photolyze N0 , 3 the speaker's calculation was repeated and we directly observed the nitric in Berkeley a month later using the oxide NO or atomic oxygen that was correct rate constant, the model formed. This study answered the question predicted a factor-of-2 reduction of about the role of N03 in the atmosphere, ozone by the oxides of nitrogen from but it also raised some interesting supersonic transports, as described by questions about state-to-state energy atmospheric scientists at the Boulder flow inside energetic N03 molecules meeting. The clash between chemists that further pure-science study will and meteorologists over this question have to answer.

4 Energy Production and Pollution techniques applicable to solar energy conversion. In the balance sheet for and against various methods of producing useful In addition, CARL will present a paper ehergy, one consideration is atmospheric to the International Conference on pollution. I'll conclude this research Metallurgical Coatings in San Diego profile with one recent example where this month. The paper is entitled considerations of stratospheric ozone "Metallurgical Analysis and High Temp­ were applicable to a DOE problem. At erature Degradation of Black Chrome present a solar power satellite system Solar Selective Absorbers." This will is being evaluated. Numerous large be followed by a presentation to the rockets would be needed to construct International Solar Energy Society and maintain such satellites, and these (ISES) in Phoenix, Arizona, in early rockets would be powered by hydrogen June. Title: "Short Term High Tempera­ and oxygen as fuels. A panel of stratos­ ture Degradation of Black Chrome." pheric scientists was asked if the water produced by these rockets would be It's clear why CARL elected to expected to reduce stratospheric ozone. specialize in materials for solar Current models predict that this injec­ energy conversion instead of energy tion of water would reduce ozone by only from photosynthesis -- no grass grows 0.01 ± 0.1%. Regardless of other under his feet! questions about the solar power satellite, stratospheric science has become mature enough to predict confidently that DR. HEINZ HEINEMANN presented an reduction of statospheric ozone is not invited lecture at the Rocky Mountain one of the satellite's disadvantages. Fuel Society Conference in Salt Lake A sufficiently complete set of elementary City, Utah, on February 22. His topic reactions can be used to predict complex, was "Conventional and Novel Methods real-world events. for Indirect Coal Liquefaction."

PEOPLE NEWS ROBERT BERGMAN has been appointed as a member of the advisory board of the CARL LAMPERT makes news: CARL has just Journal of Organic Chemistry, a publi­ been awarded a prize of $25.00 for one cation of the American Chemical Society. of five finalist logos for the Compo­ Other ACS publications with MMRD nents Hybrids and Manufacturing Tech­ researchers serving on their advisory nology (CHMT) of the Industrial Society boards are: with of Electrical and Electronics Engineers. EARL MUETTERTIES and KENNETH RAYMOND; Journal of Chemical & Engineering Data, On March 11, 1980, B. 0. Seraphin, LEO BREWER; Journal of the American general editor of Solar Energy Materials, Chemical Society, EARL MUETTERTIES; submitted the name of Dr. LAMPERT as a Journal of Physical Chemistry, JOHN new member of the editorial board of PRAUSNITZ; and Journal of Physical & that journal. In his letter of notifi­ Chemical Reference Data, LEO BREWER. cation to LAMPERT, Seraphin said, "you can now go out and actively solicit A excellent contributions that fit the Prof. JOHN PRAUSNITZ presented the key­ aims and scope of our journal." note lecture at the Second International Symposium on Phase Equilibria and Dr. LAMPERT has also been nominated as Physical Properties in the Chemical a member of the Solar Optical Materials Industry, held at West Berlin, Germany, Program Activity Committee (SOMPAC) March 17-21, 1980. formed to develop a national solar optical materials program plan for DOE. JOHN also lectured on recent phase­ The plan is expected to call for equilibrium research at Hoechst AG appropriate research and development (Frankfurt) and at the Technical of optical materials and measurement University of Denmark (Lyngby).

5 Prof. DIDIER DE FONTAINE, a participant Catalysis & Surface Science Conference Set to Go visiting scientist with MMRD, has been appointed Professor in the Department A conference on Catalysis and Surface of Materials Science and Mineral Science sponsored by MMRD is scheduled Engineering, UCB. Along with his repute for LBL July 16-18, 1980. The con­ as a noted metallurgist, DIDIER has ference offers a unique format: a quite a reputation as a public speaker, three-part examination of five major not only on the physics of metals, but areas in catalysis: ammonia synthesis, also on mythology and cosmology. Welcome ethylene oxidation, homogeneous cataly­ and congratulations, Professor! sis by transition metals, the hydrogena­ tion of carbon monoxide, and zeolite catalysis. The perspectives used to BEV CARTER, secretary for Dr. HEINEMANN investigate each are basic research, and Prof. DE JONGHE, is in training at exploratory research, and technology. the Botannical Gardens as a docent and tour director. "I'm especially inter­ Conference attendance will be limited ested in native plants and how the to 150 persons, so early registration Indians used them," she says. is important. For a copy of the final conference announcement and registration BEV is very enthusiastic about her new forms, contact Peggy Little, Conference interest and it really shows. Those Coordinator, LBL, Bldg 930, Berkeley, she guides through the Garden will be CA 94720, phone 486-6388. in for an exciting time! Program chairmen for this conference ... are HEINZ HEINEMANN and GABOR SOMORJAI. BARBARA KOMATSU has joined MMRD as secretary for Director-Designate DAVID The invited speakers are: SHIRLEY in his continuing role as Ammonia Synthesis researcher. BARBARA brings much M. Boudart (Stanford University) experience to the job: three years A. Nielsen (Halder Topsoe) of working for Dr. E. L. Alpen of the L. C. Axelrod (Pullman-Kellogg Co.) Biology and Medicine Division and five earlier years on a variety of other Homogeneous Catalysis by campus jobs. Transition Metals E. MUETTERTIES (LBL-UCB) BARBARA is a San Francisco-born Califor­ D. Forster (Monsanto Co.) nian, married, with a ten-year-old son, G. W. Parshall (E. I. DuPont) Robert, and a husband who works on campus in the Asian-American Studies Ethylene Oxidation component of Ethnic Studies. W. M. H. Sachtler (K Shell Lab, • Amsterdam) A home person is a good description of J. v. Porcelli (Halcon Research BARBARA. She likes to spend time with and Development Corp.) her family, enjoys cooking and reading, J. C. Zomerdijk (Shell Internat'l.) and is learning all about baseball by serving as a scorekeeper for the Pee Wee Hydrogenation of Carbon Monoxide League in which her son plays. BARBARA is upbeat, cheerful and involved- a very G. A. SOMORJAI (LBL-UCB) pleasant addition to our diversified A. T. BELL (LBL-UCB) J. A. Cusumano (Catalytica Division. Welcome. Associates) ... J. Hoogendoorn (Sasol) Energy Insider, a publication of the M. Dry (Sasol) DOE Editorial Services, Washington, DC, carried an article in its issue of Zeolite Catalysis 2/4/80 about the Meggards Award of the G. T. Kerr (Mobil Research & Optical Society of a~erica being Development Corp.) presented to MMRD researcher JOHN J. A. Rabo (Union Carbide) CONWAY. H. HEINEMANN (LBL-UCB)

6 [ I) I LBL REPORTS BY MMRD PERSONNEL I

To obtain a copy of any LBL/MMRD report listed below, write to the author or adviser whose name is underlined, c/o the Editors, MMRD Newsletter, Bldg. 62, Rm. 235, Lawrence Berkeley Laboratory, Berkeley, CA 94720. If several reports are requested, use separate 3 x 5 cards for each report.

LBL-6995: Design of Duplex Low Carbon w.s.w~~n., s.Sinton., V.P.w~~Qamp Steels for Improved Strength: an.d A. Pin.ea Weight Applications ... J.Y. Koo an.d G.Thomcu LBL-10067: The Formation of Subscales of Varying Compositions ... V.P. LBL-8015: Effect of Substructure on W~~, F.G~mu.n.do, B. V. Bcutow an.d the Mechanical Properties of Fe-Ni­ G.C.Wood Co-C Alloys ... M.Raghavan. an.d G.Thomcu LBL-10069: An Investigation of the Degradation of Propylene Carbonate LBL-8651: Platinum-Catalyzed Gasifi­ by Chlorine ... Su.~n.-Man. G. Yu., cation of Graphite by Hydrogen P.N.Ro~~ an.d C.W.Tob~ V.R.Oian.d~ an.d M.Balooeh LBL-10127: Coupled y• and y" Precipi­ LBL-8793: The Role of Environmental tation in Fe-Ni Base Austenites ... Conditions in In-Situ Experiments K.M.Chan.g, J.Y.Koo, J.W.Mo~,Jn. in the High-Voltage Electron Micro­ an.d G.Thomcu scope •.. G. Thomcu an.d K.H.Wea.tmaeo;t;t LBL-10153: Radiative Decay of the 2p 2 LBL-8880: The Effects of Lewis Acid P3/2,l/2 States of Lithium-like Krypton (Z=36) and the 2s2p 3P Catalysts on the Cleavage of Ali­ 1 phatic and Aryl-Aryl Linkages in State of Beryllium-like Krypton ... Coal-Related Structures ... N.V. V.V.Vi~eh, J.A.L~avitt, H.Gou.id Tayto~ an.d A.T.B~ an.d R.M~M

LBL-8956: Conformational Preferences LBL-10287: Effect of Grain Size on the and Electronic Structures of Acoustic Emission Generated During Ni(C2H4)2 and Ni(C2H4)3 R.M. Plastic Deformation of Aluminum ... Pitz~ an.d H.F.Seha~n~ III J.B~am an.d M.Ro~~n.

LBL-9351: Improved Ab Initio Effective LBL-10288: Vibrational Predissociation Core Potentials for Molecular Calcu­ Spectra of Small Clusters of H2o, lations ... P.A.C~tian6~n., Y.S. HF, NH3 , CH30H, CQH6 and C6H12 ... L~~, an.d K.S.P~z~ H.S.Kwok, V.J.K~aJn.ovieh, M.V~n.on., Y.R.Sh~n. an.d Y.T.L~~ LBL-9688: Molecular Beam Studies of Reaction Dynamics of F + H2, D2 ... LBL-10307: The Parity Non-Conserving R.K.Sp~~, C.C.Hayd~n., K.Shobatak~, Electron-Nucleon Interaction ... V.M.N~um~k an.d Y.T.L~~ E.V.Commin6 an.d P.H.Bu.e~baum

LBL-9740: Angular Distribution of LBL-10327: Specific Sequestering Xe 5s + Ep Photoelectrons near the Agents for the Actinides ... K.N. Cooper Minimum ... M.G.Whit~, S.H. Raymon.d, W.L.Smith, F.L.W~--,-­ Southwonth, P.Kob~n., E.V.Poliakonn, P.W.V~bin., E.S.Jon.~, K.Abu.-Vani, R.A.Ro~~n.b~g, an.d V.A.Shin£~y S.R.Son~n. an.d S.R.Coop~

LBL-9820: Selective Excitation of LBL-10341: Structural and Microstruc­ Multiple-Quantum Coherence in tural Design in Brittle Materials Nuclear Magnetic Resonance ... ••• A. G. Evan6

7 1

MMRD CALENDAR: Seminars, Conferences, Holidays I

SS&CS Surface Science and Catalysis May 26: Memorial Day Holiday Seminars May 28: SS&CS, Bldg 62, Rm 203, 1:00 PM. 1 April 30: SS&CS, Bldg 62, Rm 203, Prof. M. A. Vannice, Pennsylvania 1:00 PM. Prof. George W. Keulks, State University, Carbon Monoxide University of Wisconsin, Selective Hydrogenation over Carbon Supported Catalytic Oxidation of Propylene. Iron.

May 9: SS&CS, Bldg 62, Rm 203, 1:00 PM. July 16-18: First Berkeley Catalysis Prof. Bruce Gates, University of and Surface Science Conference, Delaware, A Hierarchy of Supported Bldg 50 Auditorium, LBL. See story Metal Catalysts, Complexes, Clusters, elsewhere in this issue. and Crystallites. July 28-30: International Conference May 14: SS&CS, Bldg 62, Rm 203, 1:00 PM. on Surfaces and Interfaces in Ceramics Prof. A. T. BELL, University of and Ceramic-Metallic Systems, Bldg 50 California, Application of Transient Auditorium, LBL. More details later. Response Techniques for the Study of Catalytic Reactions. August 1980: Second Chemical Congress of North America, San Francisco. May 21: SS&CS, Bldg 62, Rm 203, 1:00 PM. The Congress is a joint meeting of Dr. Malvina Farcasiu, Mobil Research the ACS, the Chemical Institute of & Development Corp., Coal Conversions Canada and the Mexican Chemical and Chemical Structure. Society. More details later.

SECOND CLASS MAlL

MATERIALS AND MOLECULAR RESEARCH DIVISION David Shirley, Head Lawrence Berkeley Laboratory 1 Cyclotron Road Berkeley, CA 94720

MMRD NEWSLETTER Editor: Stephen Compton Writer/Editor:- Roy McCollough Bldg. 62, Rm. 235 Phone ( 415) 48 6-6062 486-5842 FTS 451-6062

PUB-336 4/80/800 Prepared for US. Department of Energy under Contract W-7405-ENG-48