AN ABSTRACT OF THE DISSERTATION OF Lei Chen for the degree of Doctor of Philosophy in Chemistry presented on March 1, 2016. Title: Catching Ions in Superfluid Helium Droplets Abstract approved: ______________________________________________________ Wei Kong In this dissertation, I describe the experimental investigation of catching ions in superfluid helium droplets. The ultimate goal of our project is to build a coherent electron diffraction apparatus for atomic structure determination from oriented single macromolecules. This involves generating protein ions from electrospray ionization (ESI) and doping them in helium droplets. The doped droplets are then oriented by an elliptically polarized laser and exposed to a coherent electron beam for diffraction. The specific goal of my project is to explore the methods for sample preparation. I have started by exploring the doping conditions for continuous cesium ions from a thermionic emission source and then moved on to pulsed ions from an ESI source. I have also characterized the size and size distribution of the doped droplets. The relative ion doping efficiency of the continuous cesium ions is determined by both the kinetic energy of the ions and the size of the droplets. For reserpine and substance P from the ESI source, we have succeeded with a simple experimental setup by stopping the ions in the droplet beam with a DC bias. The resulting doping efficiency is observed to scale with the residence time of the ion beam in the droplet beam. To further control the size of the ion doped droplets for diffraction, I also have performed an exploratory experiment of collisional size reduction of ion doped droplets. These exercises and the resulting theoretical understanding of the doping mechanism of cations in superfluid helium droplets will be fundamental for the next stage of the overall project. ©Copyright by Lei Chen March 1, 2016 All Rights Reserved Catching Ions in Superfluid Helium Droplets by Lei Chen A DISSERTATION submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Presented March 1, 2016 Commencement June 2016 Doctor of Philosophy dissertation of Lei Chen presented on March 1, 2016 APPROVED: Major Professor, representing Chemistry Chair of the Department of Chemistry Dean of the Graduate School I understand that my dissertation will become part of the permanent collection of Oregon State University libraries. My signature below authorizes release of my dissertation to any reader upon request. Lei Chen, Author ACKNOWLEDGEMENTS During the past six years’ study for my Ph. D in chemistry, there are many people I would like to acknowledge for helping me to finish this difficult but invaluable challenge. Firstly, I would like to express my sincere appreciation to my advisor Professor Wei Kong for her patience, motivation and willingness to answer all my questions. She is always supportive and encouraging with my study, research as well as the writing of this thesis. Her advice on my research and my life has been invaluable. I also would like to thank Dr. Jie Zhang. She helped me to familiarize with the lab and guided me in research and problem solving. My special thanks also go to my lab mates: Dr. Colin Harthcock and Mr. Yunteng He. They are always willing to help. Specially, I would like to acknowledge Bill Freund who helped me design complicated parts and make functional electronic circuits. I also would like to thank Dr. Valery Voinov who supported and guided my research on mass spectrometry. Of course, without Larry’s help, I cannot have those delicate parts out of thin air. I would also like to thank my thesis committee: Dr. Chong Fang, Dr. Sean Burrows and Dr. William Warnes for their insightful comments and advice. Finally, I would like to acknowledge the support of my family. Thanks to my parents, my husband and my daughter. They have always encouraged me to pursue the difficult challenges and they brought the sunshine into my life. TABLE OF CONTENTS Page Chapter 1. Introduction ..................................................................................................1 1.1 Motivation ....................................................................................................1 1.2 Approach ......................................................................................................5 1.3 Mission of this thesis .................................................................................10 1.4 Reference ...................................................................................................12 Chapter 2. Superfluid Helium Droplets .......................................................................14 2.1 Properties of helium ...................................................................................14 2.2 Superfluidity ..............................................................................................15 2.3 Structure of helium droplets.......................................................................17 2.4 Collective elementary excitation in helium droplet ...................................17 2.5 Terminal temperature of a superfluid helium droplet beam ......................18 2.6 Droplet formation.......................................................................................19 2.6.1 Formation ....................................................................................19 2.6.2 Two theoretical treatments of droplet formation for regime I ....22 2.7 Velocity of droplet beam ...........................................................................24 2.7.1 General equation .........................................................................24 2.7.2 Beam velocities under different expansion conditions ...............25 2.8 Size and size distribution of a droplet beam ..............................................26 2.9 Beam flux ...................................................................................................29 2.10 Doping of helium droplet .........................................................................31 TABLE OF CONTENTS (Continued) Page 2.11 Structure of doped droplets ......................................................................35 2.12 Reference .................................................................................................37 Chapter 3. Characterization of helium droplets ...........................................................40 3.1 Detection of pure droplets ..........................................................................40 3.2 Velocity measurements ..............................................................................42 3.3 Droplet size distribution .............................................................................44 3.4 Reference ...................................................................................................49 Chapter 4. ESI source ..................................................................................................50 4.1 Electrospray ionization ..............................................................................51 4.2 Quadrupole mass filter and/or ion trap ......................................................53 4.3 Electrostatic focusing with an Einzel lens .................................................58 4.4 Characterization of the ESI source: absolute ion count .............................59 4.5 Reference ...................................................................................................61 Chapter 5. Experimental setup .....................................................................................62 5.1 General description ....................................................................................62 5.2 Pulsed superfluid helium droplet source ....................................................64 5.3 Ion detectors ...............................................................................................72 5.3.1 A metal target for absolute ion count ..........................................72 5.3.2 Daly-type dynode detector ..........................................................75 5.4 Cesium ion sources ....................................................................................76 5.5 Reference ...................................................................................................80 TABLE OF CONTENTS (Continued) Page Chapter 6. Effect of kinetic energy on the doping efficiency of cesium cations into superfluid helium droplets ..........................................................................81 6.1Introduction .................................................................................................83 6.2 Experimental setup.....................................................................................87 6.3 Experimental results...................................................................................90 6.3.1 Doping of cesium ions into helium droplets ...............................90 6.3.2 Effects of fringe fields and space charges...................................92 6.3.3 Droplet size distribution ..............................................................95 6.3.3.1 Deflector test ................................................................95 6.3.3.2 Energy filter experiment ..............................................99 6.4 Discussion ................................................................................................102 6.4.1 Size distribution of doped droplets