Advanced Theories and Computational Approaches to the Electronic Structure of Molecules PDF
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Advanced Theories and Computational Approaches to the Electronic Structure of Molecules NATO ASI Series Advanced Science Institutes Series A series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical D. Reidel Publishing Company and Physical Sciences Dordrecht, Boston and Lancaster D Behavioural and Social Sciences Martinus Nijhoff Publishers E Engineering and The Hague, Boston and Lancaster Materials Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York and Tokyo Series C: Mathematical and Physical Sciences Vol. 133 Advanced Theories and Computational Approaches to the Electronic Structure of Molecules edited by Clifford E. Dykstra School of Chemical Sciences, University of Illinois, Urbana, Illinois, U.S.A. D. Reidel Publishing Company Dordrecht / Boston / Lancaster Published in cooperation with NATO Scientific Affairs Division Proceedings of the NATO Advanced Research Workshop on Vectorization of Advanced Methods for Molecular Electronic Structure Colorado Springs, Colorado, U.S.A. September 25-29,1983 Library of Congress Cataloging in Publication Data NATO Advanced Research Workshop on Vectorization of Advanced Methods for Molecular Electronic Structure (1983: Colorado Springs, Colo.) Advanced theories and computational approaches to the electronic structure of molecules. (NATO ASI series. Series C, Mathematical and physical sciences; vol. 133) "Proceedings of the NATO Advanced Research Workshop on Vectorization of Advanced Methods for Molecular Electronic Structure, Colorado Springs, Colorado, U.S.A., September 25-29, 1983"-T.p. verso. "Published in cooperation with NATO Scientific Affairs Division." Bibliography: p. Includes index. 1. Molecular structure-Congresses. 2. Electronic structure-Congresses. I. Dykstra, Clifford E. II. North Atlantic Treaty Organization. Scientific Affairs Division. III. Title. IV. Series: NATO ASI series. Series C, Mathematical and physical sciences; vol. 133. QD461.N34 1983 541.2'2 84-15918 ISBN-13:97S-94-009-6453-2 e-ISBN-13:97S-94-009-6451-S 001: 10.1007/97S-94-009-6451-S Published by D. Reidel Publishing Company PO. Box 17, 3300 AA Dordrecht, Holland Sold and distributed in the U.S.A. and Canada by Kluwer Academic Publishers, 190 Old Derby Street, Hingham, MA 02043, U.S.A. In all other countries, sold and distributed by Kluwer Academic Publishers Group, PO. Box 322, 3300 AH Dordrecht, Holland D. Reidel Publishing Company is a member of the Kluwer Academic Publishers Group All Rights Reserved © 1984 by D. Reidel Publishing Company, Dordrecht, Holland. Softcover reprint of the hardcover 1st edition 1984 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner. CONTENTS Preface vii CHEMICAL COMPUTATIONS ON AN ATTACHED PROCESSOR: QUANTUM CHEMISTRY APPLICATIONS 1 Thom. H. Dunning, Jr. and Raymond A. Bair CONSIDERATIONS IN VECTORIZING THE CI PROCEDURE 13 Charles 11. Bauschlicher, Jr. THE METHOD OF SELF CONSISTENT ELECTRON PAIRS. A 14ATRIX 19 ORIENTED DIRECT CI Wilfried Meyer, Reinhart Ahlrichs and Clifford E. Dykstra EVALUATION AND PROCESSING OF INTEGRALS 39 Dermot Hegarty MULTI CONFIGURATION WAVEFUNCTIONS FOR MOLECULES: CURRENT 67 A?P}{OACHES Thom. H. Dunning, Jr. INTERNALLY CONTRACTED MCSCF-SCEP CALCULATIONS 79 Hans-Joachim Werner and Ernst Albrecht Reinsch COMPUTATIONAL ASPECTS OF DIRECT SCF AND MCSCF r.1ETHODS 107 Jan Almlof and Peter R. Taylor COUPLED-CLUSTER METHODS FOR MOLECULAR CALCULATIONS 127 Rodney J. Bartlett, Clifford E. Dykstra and Josef Paldus STATE-SPECIFIC THEORY OF ELECTRON CORRELATION IN 16] EXCITED STATES Cleanthes A. Nicolaides vi CONTENTS THE TREATMENT OF ELECTRON CORRELATION: WHERE DO WE 185 GO FROM THERE? Isaiah Shavitt COMPUTER TECHNOLOGY IN QUANTUM CHEMISTRY 197 Clifford E. Dykstra and Henry F. Schaefer III PROBLEM LIMITATIONS AND COST EFFECTIVENESS CONSIDERATIONS 203 IN COMPUTATIONAL QUANTUM CHEMISTRY J. S. Binkley ALGORITHMIC CONSIDERATIONS IN LARGE MAINFRAME COMPUTERS 209 J. S. Binkley BIBLIOGRAPHY 217 PARTICIPANTS 227 INDEX 231 PREFACE That there have been remarkable advances in the field of molecular electronic structure during the last decade is clear not only to those working in the field but also to anyone else who has used quantum chemical results to guide their own investiga tions. The progress in calculating the electronic structures of molecules has occurred through the truly ingenious theoretical and methodological developments that have made computationally tractable the underlying physics of electron distributions around a collection of nuclei. At the same time there has been consider able benefit from the great advances in computer technology. The growing sophistication, declining costs and increasing accessibi lity of computers have let theorists apply their methods to prob lems in virtually all areas of molecular science. Consequently, each year witnesses calculations on larger molecules than in the year before and calculations with greater accuracy and more com plete information on molecular properties. We can surely anticipate continued methodological develop ments of real consequence, and we can also see that the advance in computational capability is not about to slow down. The recent introduction of array processors, mUltiple processors and vector machines has yielded a tremendous acceleration of many types of computation, including operations typically performed in quantum chemical studies. Utilizing such new computing power to the ut most has required some new ideas and some reformulations of existing methods. For this reason, a NATO Advanced Research Work shop was organized to look at the experiences of users of these new computers in relation to electronic structure methods, parti cularly electron correlation treatments which are invariably the most computationally demanding. The workshop discussion sessions were organized around spe cific topics with the idea of assessing state-of-the-art approaches and identifying common or unifying features suited to the new generation of computers. For the most part, the papers included in this volume of proceedings follow the workshop's organization and viii PREFACE incorporate ideas and conclusions brought out in open discus sion. The workshop, officially titled "Vectorization of Advanced Methods for Molecular Electronic Structure. An Assessment of State-of-the-Art Electron Correlation Theories and Unifying Fea tures Suited to Vectorized Computation", was held under the auspices of the NATO Scientific Affairs Division. We gratefully acknowledge their generous support and their interest in this meeting. We should also like to thank Floating Point Systems, Inc. for their special grant of funds in support of advanced computa tional methods in quantum chemistry. The workshop was held during the week of September 25, 1983 in Colorado Springs, Colorado. The organizing committee consisted of Professor Reinhart Ahlrichs, Professor Wilfried Meyer and my self. The School of Chemical Sciences at the University of Illinois provided certain resources for the organization and plan ning of this workshop. The Colorado Springs Convention Bureau and the conference staff of the Antlers Plaza Hotel provided invaluable assistance for the arrangements at the meeting site. January, 1984 Clifford E. Dykstra Urbana, Illinois CHEMICAL COIPOTATIONS ON AN ATTACHED PROCESSOR: QUMmJM CHEMISTRY APPLICATIONS Thom. H. Dunning, Jr. and Raymond A. Bair Theoretical Chemistry Group, Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 The Floating Point Systems, Inc. Model 164 (FPS-164) attached processor is a high speed, pipelined, parallel proc essor designed for large-scale scientific computations. Bench mark studies indicate that the FPS-164 is more than an order of magnitude faster than a DEC VAX 11/780 and comparable in speed to an IBM 3033 or CDC Cyber 175 mainframe computer. Vectoriza tion and optimization techniques applied to electronic struc ture codes for the FPS-164 can lead to further improvements, e.g, GVB164, a generalized valence bond program, runs 30 to 40 times faster on the FPS-164 than on the VAX 11/780. I. INTRODUCTION In the 1960s and early 1970s most theoretical chemists used the large mainframe computers available in their institu tion's central computing facility for all calculations. While this offered the opportunity of carrying out large-scale calcu lations, in fact, the large operating cost associated with the general purpose computing facility discouraged most large-scale applications unless they were heavily subsidized. In 1972, Schaefer & Miller implemented a number of codes for chemistry computations on a Harris/4 minicomputer from Harris Corpora tion. They found that such a special purpose computer was a cost-effective alternative to the large mainframe computers in the central facility (1). Use of minicomputers in large-scale chemical computations was given further impetus in 1976 with the introduction of the VAX 11/780 super-minicomputer by Digital Equipment Corporation. C H. Dykstra (ed.), Advanced Theories and Computational Approaches to the Hlectronic Structure of Molecules, 1-12. e 1984 by D. Reidel Publishing Company. 2 T. H. DUNNING, Jr. AND R. A. BAIR The VAX 11/780 was not only substantially faster than the Harris/4 but in addition many of the architectural limitations that restricted the applications of the latter machine were eliminated in the VAX 11/780. Since 1976 use of VAX 11/780 super-minicomputers or its equivalents (the Harris 800 from Harris Corporation, the PE 3240 and 3250 from Perkin-Elmer Corporation, and the 4331 and 4341 from IBM Corporation) in chemical computations has proliferated; today most major theo retical chemistry groups as well as many chemistry departments possess super-minicomputers for scientific computations, data analysis, etc. Today, however, even the VAX 11/780 super-minicomputer is inadequate for more than routine applications. A typical large-scale calculation at the forefront of research in theo retical chemistry may require several days to complete on such a machine - a research program simply cannot be effectively pursued in this manner. Within the last year a new generation of super-minicomputers has been introduced - by Data General (the MV 10000), Gould/ SEL (the Concept 32/87), Prime (Prime 9950), Harris (Harris 1000), IBM (IBM 4361 and 4381) and Perkin Elmer (3250XP); see reference 2. These machines all promise speeds several times that of the VAX 11/780 at comparable costs. While the introduction of these new computers will help alleviate the shortfall of computing power in theoretical chem istry research, it should be noted that they are still several times slower than common mainframe computers, such as the IBM 3033 or the CDC Cyber 175, and as much as two orders of magni tude slower than the supercomputers in widespread use, the Cray-IS and the CDC Cyber 205. In mid-1982 the Theoretical Chemistry Group at Argonne National Laboratory acquired a Floating Point Systems, Inc. Model 164 (FPS'-164) Attached Scientific Processor. The FPS-164 is a high speed, vector (parallel, pipelined) processor designed for large-scale scientific computations - in effect, a mini-supercomputer. For large-scale scientific computations the FPS-164 provides performance comparable to that of modern mainframe computers at a cost comparable to that of a super minicomputer system. However, like all vector processors, e.g., the Cray-IS and CDC Cyber 205 supercomputers, to achieve this performance care must be exercised in developing and implementing codes on the FPS-164. The FPS-164 has been discussed in some detail in earlier papers by Bair & coworkers (3). In this paper we briefly re view the hardware and software features of the FPS-164, present the results of selected benchmark calculations including that of a production benchmark, and briefly discuss the general principles which are important in coding applications for the
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