DOCSLIB.ORG

Developing a Model Chemistry for Multiconfiguration Pair-Density

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Developing a Model Chemistry for Multiconfiguration Pair-Density Developing a Model Chemistry for Multiconfiguration Pair-Density Functional Theory to Study Photochemistry and Molecular Interactions A THESIS SUBMITTED TO THE FACULTY OF THE GRADUATE SCHOOL OF THE UNIVERSITY OF MINNESOTA BY Jie Bao IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF PH.D. OF SCIENCE Donald G. Truhlar January, 2021 © Jie Bao 2021 ALL RIGHTS RESERVED Acknowledgements I would like to acknowledge my advisor, Dr. Donald Truhlar, for being a helpful and reliable advisor. I would like to acknowledge my collaborator, Dr. Laura Gagliardi, for her help in almost all my projects. I would like to acknowledge Dr. Junwei Lucas Bao, Dr. Shaohong Louis Li, Dr. Kamal Sharkas, Dr. Yinan Shu, Dr. Zoltán Varga, Dr. Chad Hoyer, and Dr. Pragya Verma for their help when I started work on theoretical chemistry. I would like to acknowledge Dr. Andrew Sand for his help in teaching me to code in OpenMolcas. I would like to thank Dr. Sijia Dong and Dr. Meagan Oakley for collaborations in two projects. I would like to thank Dr. Chen Zhou, Dr. Matthew Hermes and Thais Scott, for valuable and interesting discussions of some of my projects. At last, I would like to acknowledge Dr. Donald Truhlar, Dr. Laura Gagliardi, Dr. Jason Goodpaster, and Dr. Aaron Massari for serving on my committee for my thesis. i Dedication To my family who give me support. ii Abstract Photochemical reaction, which starts by exciting a system into an electronically excited state, is ubiquitous, for example, in the atmosphere. This has made photochemical reactions a very interesting topic. Multiconfigurational pair-density functional theory (MC-PDFT) is a powerful and efficient method for studying photochemical processes. This method has proved very efficient compared with other wave function methods, such as multi-state complete active space second order perturbation theory (MS-CASPT2), especially for large systems. Successful as MC-PDFT is, there are some limitations that stop MC-PDFT from being applied to studying photochemistry problems. The first limitation is that, like other multireference methods, the performance of MC-PDFT depends on the quality of the reference wave function, which by convention is optimized by an active-space method, such as complete active space self-consistent field (CASSCF). The second limitation is that MC-PDFT is a single-state method that does not include state interaction between reference states. This means that MC-PDFT gives wrong topologies of potential energy surfaces, which are important in studying photochemical reactions. My work is focused on resolving these two limitations. We proposed the ABC scheme and the ABC2 scheme to automatically generate the active space that gives good-quality reference wave functions thus successfully reproducing vertical excitation energies obtained from experiments or high-level calculations. We proposed the extended multi-state PDFT (XMS-PDFT) and compressed-state multi-state PDFT (CMS-PDFT) as two options to introduce state-interaction in pair-density functional theory. Among two methods, XMS-PDFT is more efficient, while CMS-PDFT is more robust. Both methods proved successful in providing correct topologies of potential energy surfaces for a variety of systems. iii Contents Acknowledgements i Dedication ii Abstract iii List of Tables viii List of Figures xii 1 Introduction 1 2 Multiconfiguration pair-density functional theory for doublet excitation ener- gies and excited state geometries: the excited states of CN 4 2.1 Introduction . 4 2.2 Computational Details . 7 2.3 Results and Discussion . 9 2.3.1 An Illustration of the Dominant Electron Configuration for Each State ofCN................................... 9 2.3.2 Multireference Diagnostic for CN . 9 2.3.3 Adiabatic Excitation Energy for Each of the States . 11 2.3.4 Equilibrium Distances . 15 iv 2.4 Conclusions . 19 3 Weak Interactions in Alkaline Earth Metal Dimers by Pair-Density Functional Theory 22 3.1 Introduction . 22 3.2 Computational Details . 24 3.3 Results and Discussion . 26 3.3.1 Multiconfigurational Character . 26 3.3.2 Binding Energies (De) for dimers from Be2 to Ba2 . 27 3.3.3 Equilibrium Internuclear Distances (re) for dimers from Be2 to Ba2 . 28 3.3.4 Larger Active Spaces . 28 3.3.5 Basis Set Dependence . 30 3.3.6 Comparison to KS-DFT . 31 3.3.7 Potential Energy Curves . 32 3.3.8 Performance of Other On-top Functionals . 33 3.3.9 MP2 vs. CASPT2 . 33 3.3.10 Core Correlation . 34 3.3.11 Diffuse Basis Functions and Core Polarization Basis Functions . 34 3.3.12 De and re for Ra2 ............................ 35 3.4 Conclusion . 35 4 Automatic selection of an active space for calculating electronic excitation spectra by MS-CASPT2 or MC-PDFT 36 4.1 Introduction . 36 4.2 ABC Scheme . 38 4.3 Computational Details . 43 4.4 Results and Discussion . 45 v 4.5 Conclusion . 49 5 Automatic Active Space Selection for Calculating Electronic Excitation Ener- gies Based on High-Spin Unrestricted Hartree-Fock Orbitals 56 5.1 Introduction . 56 5.2 ABC2 Sceheme . 59 5.3 Computational Details . 61 5.4 Systems Studied . 63 5.5 Computational Details . 63 5.6 Methods Compared . 66 5.7 Results and Discussion . 66 5.7.1 Doublet Excited States . 66 5.7.2 Singlet Excited States . 68 5.7.3 Comparison to the ABC scheme . 71 5.7.4 Comparison to other guess schemes . 74 5.7.5 Timing . 78 5.7.6 Active spaces in other methods . 79 5.8 Conclusion . 79 6 Extended multi-state Pair-Density Functional Theory 81 6.1 Introduction . 81 6.2 Theory . 83 6.2.1 MC-PDFT . 83 6.2.2 multi-state MC-PDFT . 84 6.2.3 XMS-PDFT . 85 6.3 Computational Details . 88 6.4 Results and Discussion . 89 vi 6.4.1 Lithium fluoride (LiF) . 89 6.4.2 Lithium hydride (LiH) . 90 6.4.3 Phenol (C6H5OH) . 92 6.5 Conclusion . 93 7 Compressed-State Multi-State Pair-Density Functional Theory 94 7.1 Introduction . 94 7.2 Theory . 97 7.2.1 MC-PDFT . 97 7.2.2 MS-PDFT . 98 7.2.3 CMS-PDFT . 99 7.3 Computational Details . 102 7.4 Results and Discussion . 103 7.4.1 LiF . 103 7.4.2 LiH . 104 7.4.3 HNCO . 105 7.4.4 CH3NH2 ................................. 105 7.4.5 Phenol . 108 7.4.6 Spiro . 109 7.4.7 Computational Cost of Using CMS-, XMS- and FMS- intermediate states111 7.5 Conclusion . 112 8 Concluding Remarks 115 References 116 vii List of Tables 2.1 The Dominant Configuration for the Ground State and the Orbitals with a Changed Number of Electrons in the Dominant Configurations for Excited States at re .................................... 8 2.2 Notations for Three Levels of CASSCF and MR Calculations . 8 2.3 M Diagnostic, Dominant Configurations and the Corresponding Weight of the Configuration in the Wave Function for Each State at the Experimental Equilibrium . 10 2.4 Signed Errors of Adiabatic Excitation Energies (in eV), the Mean Unsigned Error (MUE) Over First n Excitation Energies (MUE_n), and the Rank of MUE_n (rank_n)................................. 13 ˝ 2.5 Signed Errors of Equilibrium Distances (r e in A) . 17 2.6 MUE of re over First n States (MUE_n) and the Rank of MUE_n (Rank_n) . 18 3.1 M Diagnostics and Dominant Configurations at the Equilibrium Geometry As Calculated by FV-CASSCF Calculationsa ................... 26 3.2 Reference Values for Dissociation Energies (De, in kcal/mol) and Equilibrium ˝ Distances (re, in A)............................... 28 3.3 Dissociation Energy, Equilibrium Distance, Mean Signed Error (MSE), Mean Unsigned Error (MUE), and Standard Deviation (StdDev) for Calculations with the Large AR Basis Seta ............................ 29 viii 3.4 Dissociation Energy, Equilibrium Distance, Mean Signed Error (MSE), Mean Unsigned Error (MUE), and Standard Deviation (StdDev) for Calculations with the Large AR Basis Seta ............................ 31 3.5 Dissociation Energy, Equilibrium Distance, Mean Signed Error (MSE), Mean Unsigned Error (MUE), and Standard Deviation (StdDev) for Calculations with KS-DFT Using the PBE Exchange–Correlation Functionala . 32 ˝ 4.1 Geometries in Terms of Bond Lengths (A) and Bond Angles (degree) . 44 4.2 Details of the SA-CASSCF Calculations Used as the Starting Points for MR- CISD+Q Calculations . 45 4.3 Details of ABC Active Spaces . 46 4.4 Signed Errors (eV), Mean Signed Deviation (MSD), and Mean Unsigned Deviation (MUD) of MC-PDFT and MS-CAPST2 Excitation Energies with Respect to MR-CISD+Q for CH3 ........................ 47 4.5 Signed Errors (eV), Mean Signed Deviation (MSD), and Mean Unsigned Deviation (MUD) of MC-PDFT and MS-CAPST2 Excitation Energies with Respect to MR-CISD+Q for NH2 ........................ 48 4.6 Signed Errors (eV), Mean Signed Deviation (MSD), and Mean Unsigned Deviation (MUD) of MC-PDFT and MS-CAPST2 Excitation Energies with Respect to MR-CISD+Q for C2H........................ 49 4.7 Signed Errors (eV), Mean Signed Deviation (MSD), and Mean Unsigned Deviation (MUD) of MC-PDFT and MS-CAPST2 Excitation Energies with Respect to MR-CISD+Q for CN . 50 4.8 Signed Errors (eV), Mean Signed Deviation (MSD), and Mean Unsigned Deviation (MUD) of MC-PDFT and MS-CAPST2 Excitation Energies with Respect to MR-CISD+Q for BO . 51 ix 4.9 Signed Errors (eV), Mean Signed Deviation (MSD), and Mean Unsigned Deviation (MUD) of MC-PDFT and MS-CAPST2 Excitation Energies with ` Respect to MR-CISD+Q for N2 ......................... 52 4.10 Signed Errors (eV), Mean Signed Deviation (MSD), and Mean Unsigned Deviation (MUD) of MC-PDFT and MS-CAPST2 Excitation Energies with Respect to MR-CISD+Q for CO` ........................ 53 4.11 Signed Errors (eV), Mean Signed Deviation (MSD), and Mean Unsigned Deviation (MUD) of MC-PDFT and MS-CAPST2 Excitation Energies with Respect to MR-CISD+Q for C2H3 ......................
Load more

Recommended publications
  • 2018 March Meeting Program Guide
    MARCHMEETING2018 LOS ANGELES MARCH 5-9 PROGRAM GUIDE #apsmarch aps.org/meetingapp aps.org/meetings/march Senior Editor: Arup Chakraborty Robert T. Haslam Professor of Chemical Engineering; Professor of Chemistry, Physics, and Institute for Medical Engineering and Science, MIT Now welcoming submissions in the Physics of Living Systems Submit your best work at elifesci.org/physics-living-systems Image: D. Bonazzi (CC BY 2.0) Led by Senior Editor Arup Chakraborty, this dedicated new section of the open-access journal eLife welcomes studies in which experimental, theoretical, and computational approaches rooted in the physical sciences are developed and/or applied to provide deep insights into the collective properties and function of multicomponent biological systems and processes. eLife publishes groundbreaking research in the life and biomedical sciences. All decisions are made by working scientists. WELCOME t is a pleasure to welcome you to Los Angeles and to the APS March I Meeting 2018. As has become a tradition, the March Meeting is a spectacular gathering of an enthusiastic group of scientists from diverse organizations and backgrounds who have broad interests in physics. This meeting provides us an opportunity to present exciting new work as well as to learn from others, and to meet up with colleagues and make new friends. While you are here, I encourage you to take every opportunity to experience the amazing science that envelops us at the meeting, and to enjoy the many additional professional and social gatherings offered. Additionally, this is a year for Strategic Planning for APS, when the membership will consider the evolving mission of APS and where we want to go as a society.
    [Show full text]
  • Curriculum Vitae Ryan P
    Curriculum Vitae Ryan P. Steele Contact Information Department of Chemistry Phone (801) 587-3800 University of Utah Fax (801) 581-8433 315 S 1400 E Email [email protected] Salt Lake City, UT 84112 Website https://www2.chem.utah.edu/steele Professional Preparation University of California – Berkeley Berkeley, CA Ph.D., Theoretical Chemistry 2008 Iowa State University Ames, IA B.S. with distinction, Chemistry 2003 Scientific Appointments Associate Professor July 2017 – Department of Chemistry, University of Utah Assistant Professor Aug 2011 – June 2017 Department of Chemistry, University of Utah Post-Doctoral Associate Aug 2008 – Jul 2011 Department of Chemistry, Yale University Research group of Prof. John Tully Graduate Research Assistant Aug 2003 – Aug 2008 Department of Chemistry, University of CA – Berkeley Research group of Prof. Martin Head-Gordon Thesis: Dual-Basis Methods for Electronic Structure Theory Graduate Student Instructor Fall 2003, 2004, Spring 2006 Department of Chemistry, University of CA – Berkeley Undergraduate Research Associate May – Aug 2002 Georgia Institute of Technology Research group of Prof. C. David Sherrill Undergraduate Research Associate Aug 2002 – May 2003 Iowa State University Research group of Prof. William S. Jenks Teaching Assistant Aug 2002 – May 2003 Iowa State University Steele 2 Students Mentored Post-Doctoral Researchers 1. Xiaolu Cheng Fall 2013 – Fall 2017 New methods for anharmonic vibrational spectroscopy 2. Shervin Fatehi Fall 2013 – Summer 2015 Multiple-timestep ab initio molecular dynamics Currently an assistant professor at the University of Texas – Rio Grande Valley Graduate Students 1. Jonathan Herr Summer 2012 – Fall 2016 Water oxidation, Dynamics Methods 2. Nicholas Corbett Spring 2013 – Fall 2015 Nanoparticle catalysis, Sampling methods Currently employed as Quality Engineer at Ultradent 3.
    [Show full text]
  • DONALD G. TRUHLAR Personal and Contact Information Birth: Feb
    June 18, 2020 DONALD G. TRUHLAR Personal and contact information Birth: Feb. 27, 1944, Chicago, IL Phone: 1-612-624-7555 (email preferred) Email: [email protected] Postal: Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 Home page: truhlar.chem.umn.edu ORCID: 0000-0002-7742-7294; Researcher ID: G-7076-2015 Education St. Mary’s College of Minnesota, B. A., Chemistry, summa cum laude, 1965. California Institute of Technology, Ph. D., Chemistry, 1970. Graduate adviser: Aron Kuppermann (1917-2011) Appointments University of Minnesota: Department of Chemistry Member of Graduate Faculty, 1969-present Assistant Professor, 1969-72 Associate Professor, 1972-76 Professor, 1976-2006 Director of Graduate Studies, 1986-88 George Taylor Institute of Technology Professor, 1993-1998 Institute of Technology Distinguished Professor, 1998-2001 Lloyd H. Reyerson Professor, 2002-2006 Regents Professor, 2006-present Chemical Physics Program Member of Graduate Faculty, 1969-present Head and Director of Graduate Studies, 1980-84, 1992-95, 1998-99 Supercomputing Institute Fellow, 1985-present Acting Scientific Director, 1987-88 Director, 1988-2006 Graduate Program in Scientific Computation Founding Director of Graduate Studies, 1990-96, 2002 Charter Member of Graduate Faculty, 1990-2016 Graduate Minor Program in Nanoparticle Science and Engineering Charter Member of Graduate Faculty, 2002–2016 Battelle Memorial Institute: Columbus, Ohio, Visiting Fellow, 1973. Joint Institute for Laboratory Astrophysics, Boulder,
    [Show full text]
  • A N N U a L R E P O R T
    2012 a n n u a l r e p o r t Argonne Leadership Computing Facility ARGONNE LEADERSHIP COMPUTING FacILITY 2012 ANNUAL REPORT Director’s Message .............................................................................................................................1 About ALCF ......................................................................................................................................... 2 INTRODUCING MIRA Introducing Mira ..................................................................................................................................3 ALCF Contributes to Co-Design of Mira .......................................................................................4 Science on Day One ......................................................................................................................... 6 RESOURCES AND EXPERTISE ALCF Computing Resources ..........................................................................................................12 ALCF Expertise ..................................................................................................................................16 SCIENCE AT THE ALCF Allocation Programs .........................................................................................................................18 Science Director’s Message .........................................................................................................20 Science Highlights............................................................................................................................21
    [Show full text]
  • Graduate Students & Postdoctoral Researchers Lead Laboratory Safety Efforts
    DECEMBER 2012 CHEM news DEPARTMENT OF CHEMISTRY NEWSLETTER Inside this issue… Graduate students & postdoctoral researchers lead laboratory Highlights 2 safety efforts Lab experiences From safety- 6 themed posters to informative safety Current research moments before 8 meetings and seminars, creation of a safety website, and an increased 11Student honors emphasis on wearing proper safety gear in laboratories, graduate students and postdoctoral Kathryn “Kate” McGarry, a graduate student in the De- Faculty & staff awards researchers are taking the lead partment of Chemistry and chair of the Joint Safety Team 14 Administrative Committee, demonstrates how hoods and in improving and sustaining the safety culture in protective glass are important safety features that need the University of Minnesota College of Science & to be used appropriately in laboratories, as is wearing personal protective equipment. Donors Engineering’s chemistry and chemical engineering 18 laboratories. This fall, they kicked off a new safety campaign, “Safety Starts with U!” Minnesota for this safety initiative, it is sharing its best-in-class laboratory safety practices, exam- Through a unique partnership with the Dow Legacies ples, advice, and resources with U of M students 19 Chemical Company, graduate students and and postdoctorates. Last spring, Dow sponsored postdoctoral researchers from the departments of a two-day safety training for students and faculty Chemistry (CHEM) and Chemical Engineering at its facility in Michigan, and since then, it has and Materials Science (CEMS) are providing New appointment been providing ongoing advice to the graduate 20 the leadership to a first-ever pilot program to students and post doctorates. improve safety awareness and practices.
    [Show full text]
  • Chemnews Spring 2002
    • DEPARTMENT OF CHEMISTRY ChemNews www.chem.umn.edu Spring 2002 GREETINGS FROM THE CHAIR Wayne L. Gladfelter, Chair It has been too hiring campaign. At this moment we have 41 tenured many years since we have and tenure-track faculty members with 21 Full, 8 Associate assembled a newsletter and 12 Assistant Professors. With the average age of 41, for the Department of several of us bemoan the fact that we are now in the older Chemistry. One of the half (or even smaller fraction) of the faculty. It means, great outcomes of the however, that the level of energy and enthusiasm is almost alumni breakfast as hard to contain as the growing size of many research meetings we host at the groups. The growth in grant income reflects this change national ACS meetings and the number of postdoctoral associates has doubled has been the realization that you are interested in keeping over the last few years. In the Fall of 2001 our incoming in touch with us. This has provided us with the motivation class of 49 graduate students included several with major needed to prepare this letter. Even with a total of 24 fellowships. The total number of graduate students in pages, we could not hope to cover all of the changes in the department remains steady at approximately 230. The the last eight years, so this letter will include a mix of number of undergraduate chemistry majors, however, has recent (within the last year) events and trends. increased dramatically during the ‘90’s. We now graduate Throughout the 1990’s a large number of faculty an average of 80 majors every year.
    [Show full text]
  • Computational and Theoretical Chemistry 2015 PI Meeting Annapolis Westin Annapolis Maryland 26-29 April 2015
    Computational and Theoretical Chemistry 2015 PI Meeting Annapolis Westin Annapolis Maryland 26-29 April 2015 Office of Basic Energy Sciences Chemical Sciences, Geosciences , and Biosciences Division FORWARD This abstract booklet provides a record of the U.S. Department of Energy first annual PI meeting in Computational and Theoretical Chemistry (CTC). This meeting is sponsored by the Chemical Sciences, Geosciences and Biosciences Division of the Office of Basic Energy Sciences and includes invited speakers and participants from BES predictive theory and modeling centers, Energy-Frontier Research Centers, SciDAC efforts and an SBIR/STTR project. The objective of this meeting is to provide an interactive environment in which researchers with common interests will present and exchange information about their activities, will build collaborations among research groups with mutually complementary expertise, will identify needs of the research community, and will focus on opportunities for future research directions. The agenda has several invited talks and many brief oral presentations. In response to a questionnaire about meeting organization, many of the participants noted that it would be desirable to provide all CTC researchers with the opportunity for an oral presentation since this is the first annual meeting. There should be ample time during the evenings for detailed follow-up discussions and the meeting room is available during this time for informal breakout sessions. We thank Mark Gordon, Martin Head-Gordon, and Bruce Garrett for participating in pre-meeting discussions about the organization and goals of the afternoon strategic planning session and hope that everyone will be ready to actively contribute their ideas during these discussions.
    [Show full text]
  • Information Quarterly for Computer Simulation Of
    Daresbury Laboratory INFORMATION QUARTERLY FOR COMPUTER SIMULATION OF CONDENSED PHASES An informal 1\iewsletter associated with Collaborative Computational Project l\o.5 on :'vlolecular Dynamics, Monte Carlo & Lattice Simulations of Condensed Phases. :\"umber 42 October 1994 Contents • General News 3 • :vleeting and workshop announcements 7 • METHODS IN MOLECULAR SIMULATION - Spring School i' e International Symposium on Computational Molecular Dynamics 8 o The Computer Physics Communications Program Library 10 D. Fincham e How to Derive the Interatomic Potentials needed for Simulation Studies 11 R. Grimes and A. Harker o Cellular Automata and their Applications to Molecular Fluids 28 A. Masters and M. Wilson • Order in Liquids 3.5 D. Cleaver and C. Care Editor: Dr. M. Leslie DRAL Dares bury Laboratory Dares bury, Warrington WA4 4AD UK General News This issue of the newsletter contains the abstracts of three meetings with which CCP5 has been involved during the summer. First Email Copy This is the first copy of this newsletter which will not be distributed by ordinary post to all of our readers. (See Below). UK Telephone numbers All telephone numbers in the UK have changed; however the existing numbers will continue to work until Aprill995. To make the change, insert an extra digit 1 after the international code (44) but before the local area code. The Daresbury telephone number is noted in full below. FUTURE MEETINGS A summary table is given below, further details may be found inside. CCP5 has been asked to publicize the University of Minnesota Supercomputer Institute meeting but is not involved with its organisation. j TOPIC DATES LOCATION 1 International Symposium on Computational 24-26 October 1994 Minneapolis j Molecular Dynamics I METHODS IN MOLECULAR 27-31 March 1995 Southampton i SIMULATION - SPRING SCHOOL CRAY NEWS CCP5 participants are reminded that CCP5 has an annual allocation of Cray time at Rutherford Laboratory.
    [Show full text]