Ideas of Quantum Chemistry PDF
Preview Ideas of Quantum Chemistry
F Compose your own book according to your needs Choose your own path through the TREE (all paths begin at the basis of the TREE). You may also consider the author’s recommendations with two basic paths: • minimum minimorum (a few dozen of pages) with the sign for those who want to proceed as quickly as possible to get idea what quantum chemistry is all about, • minimum with the signs and for those who seek basic information about quantum 4 chemistry, as well as other paths, that consist of the minimum path, i.e. and , and (following the 4 corresponding flags) special excursions into the subjects of • large molecules ( ) • molecular mechanics and molecular dynamics ( ) Ä • solid state chemistry/physics ( ) • chemical reactions (ʊ) • spectroscopy () • exact calculations on atoms or small molecules () • relativistic and quantum electrodynamics effects () • most important computational methods of quantum chemistry (♦) • future of quantum chemistry (F ) • “magical” aspects of quantum physics () IDEAS OF QUANTUM CHEMISTRY Second edition “Things appear, ideas persist” Plato IDEAS OF QUANTUM CHEMISTRY Second edition by LUCJAN PIELA Department of Chemistry, University of Warsaw, Warsaw, Poland AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Elsevier 225 Wyman Street, Waltham, MA 02451, USA 525 B Street, Suite 1800, San Diego, CA 92101-4495, USA Second edition 2014 © 2014 Elsevier B.V. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher. Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone ( 44) (0) 1865 843830; fax ( 44) (0) 1865 853333; + + email: [email protected]. Alternatively you can submit your request online by visit- ing the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material. Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library For information on all Elsevier publications visit our web site at store.elsevier.com Printed and bound in United Kingdom 14 15 16 17 18 10 9 8 7 6 5 4 3 2 1 ISBN: 978-0-444-59436-5 To all on the quest for the Truth Sources of Photographs and Figures ✶ The Figures in this book, except those listed below or acknowledged in situ, are manufactured by the author and reproduced thanks to the courtesy of Wydawnictwo Naukowe PWN, Poland from “ Idee chemii kwantowej”, © 2012 PWN, ✶ the postal stamps of several countries have been used (Austria pp. 30, 77, 106, 615, Canada 591, 886, Denmark 7, France 979, e17, e121, 371, Gabon 354, Gambia 4, 927, Germany 302, Great Britain 1003, Greece 795, Guiné-Bissau 111, 874, Guinée 12, 74, 155, 764, 270, 764, Guyana 512, Holland 11, 796, Hungary 250, 524, Ireland 1004, Komi 328, Mali 1, 4, 26, 124, Marshall Islands 446, Micronesia 36, Nevis 340, Sweden 952, Uganda 9, Uruguay 110, USA 107, 260, 594, 612, 723, Vatican 796) ✶ courtesy of The Nobel Foundation (John Rayleigh 5, Niels Bohr 7, Albert Einstein 107, Carl Anderson 126, James Watson 345, Francis Crick 345, Tjalling Koopmans 466, John Pople 501, Walter Kohn 676, John Van Vleck 721, Norman Ramsey 771, Edwards Purcell 771, Yuan Lee 886, Dudley Herschbach 886, Rudolph Marcus 950, Ilya Prigogine 982) ✶ Wikipedia - the web ency- clopedia, public domain (7, 27, 62, 64, 110, 111, 172, 286, 347, 363, 505, 507, 516, 585, 771, 975, 991, 745, e10) ✶ photo of Aleksander Jabłoński p.460, courtesy of Physics Department, Nicolaus Copernicus University, Toruń, Poland ✶ courtesy of Professor Roald Hoffmann (Cornell University, USA) 533, 536, 542, 546, 547 ✶ courtesy of Professor Jean-Marie André (Université de Namur, Belgium) 543, 544 ✶ courtesy of Professor Hiroshi Nakatsuji, Japan 658 ✶ courtesy of Professor Sadlej’s family, Poland p.749 ✶ photo of Charles Galton Darwin p.124 - courtesy of Dr.R.C.McGuiness, UK ✶ photo of Christopher Longuet-Higgins, p.261- courtesy of Professor J.D.Roberts, California Institute of Technology, USA ✶ photo of Friedrich Hund p.461- courtesy of Mr Gerhard Hund, Germany ✶ photo of Richard Bader 672 - courtesy of Professor Richard Bader, Canada ✶ portrait of Hans Hellmann p.722 reproduced from a painting by Ms Tatiana Livschitz, courtesy of Professor W.H. Eugen Schwartz, Germany ✶ photo, cour- tesy of Jean-Marie Lehn, France 976 ✶ photo of Gregory Breit - courtesy of Alburtus Yale News Bureau (through Wikipedia) - 146 ✶ Figs. 11.10-11.12 reused from S. Kais, D.R. Herschbach, N.C. Handy, C.W. Murray, G.J. Laming, J. Chem. Phys., 99 (1993) 417. ✶ Tables 14.1-14.5, courtesy of Professor Sason Shaik, Israel ✶ Fig. 8.33 - courtesy of Dr.Witold Mizerski, Poland 493, photographs by the author (Per- Olov Löwdin 445, Rudolph Peierls 535, Włodzimierz Kołos 591, Lutosław Wolniewicz 591, Szkocka Café in Lwów 372, Roald Hoffmann 925). Despite reasonable attempts made, we were unable to contact the owners of the copyright of the fol- lowing images: ✶ photo of Boris Belousov p.995 from “ Geroi i zladiei rossiyskoi nauki”, Kronpress, Moscow, 1997, Figs on p.874 and 875 reproduced from “ Biology Today”, CRM Books, Del Mar, USA, © 1972 Communications Research Machines, MPn method 653 ✶ in the website of St Andrews University, United Kingdom http://www-gap.dcs.st-and.ac.uk/~history (Sommerfeld 8, Bose 26, Bell 48, Weyl 80, Minkowski 119, Klein 123, Hartree 393, Riemann 560, Friedmann 593, Thom 671, Feigenbaum 978, 873 (Tomaglia), Shannon 876, Adleman 1002, Turing 879, Lagrange 997 ✶ in the website of Physics Department, Moscow University http://nuclphys.sinp.msu.ru (Edward Condon 302) ✶ in the website of Duke University (USA) www.phy.duke.edu, photo Lotte Meitner-Graf: Fritz London 611 ✶ in the website of www.volny.cz Gilbert Lewis 7 ✶ in the website met www.epfl.ch: Brillouin 438 ✶ in the website http://osulibrary.orst.edu Slater 397 ✶ in the website http://www.mathsoc.spb.ru: Fock 394 ✶ xxi Sources of Photographs and Figures in the website www.stetson.edu Ulam 372 ✶ in the website http://www.quantum-chemistry-history.com (Hückel 427, Roothaan 432, Hall 432). If you are the copyright owner to any of the images we have used without your explicit permission (because we were unable to reach you during our search), please contact prof.Lucjan Piela, Chemistry Department, Warsaw University, 02093 Warsaw, Poland e-mail: [email protected], phone (48)-22- 7226692. We will be pleased to place the appropriate information on our website at booksite.elsevier. com/978-0-444-59436-5 which supports the present book and represents its integral part. xxii Introduction Quantumscimus–guttaest,ignoramusmare. Whatweknowisadrop,whatwedonotknowisasea. (Latinsentence) : We and the Universe A Potent Interaction Hereareafewwaysthatphotonsplayapartinmylife:Crocusesfirstappearafterwinterand look breathtaking on the snow, then ultramarine of the violets. Later, magnolia flowers seem like proud queens–a bright white with a subtle rosy tint. A week later, the lilacs, the ecru of acacia,andfinallytherich,extraordinarykingdomofrosesallmaketheirdebuts.Thebudsof thehydrangea(thebelovedflowersofthisauthor)arewhite,butwhentheyfirstopen,thewhite reacts with light quanta, and the flowers acquire vibrant, clean colors, ranging from light to darkblue.Whydoesallthishappen?Notonlydocolorscreateasenseofwonder,butunusual shapes,textures,andhuesdoaswell.Whatisinourbrainthatcanusephotonstotranslateour interactionswiththeUniverseintoanunimaginablevarietyofcomplexphenomena,alreadyin ourbody,thatcanaffectourdecisionsandactions?Sightrepresentsthemostpowerful(highly directional and long-range) and, at the same time, the most subtle information channel to our brain. Hearing. What could compete with the fantasy of the thrush, which sings different master- pieceseveryspringinmythreepinetrees?Whydoesafinchsingcompletelydifferentlyfrom thethrush,andwhydoesitrepeatitsmelodywithamazingregularity?Whydoallfinchessing similarsongs?Whatkindofinternalprogrammingcompelsthemtodoso?Theprogrammust bequiterobust,beinginsensitivetothousandsofdetailsoftheneighborhood,butnottosome particularsignalsofdanger.Birdsongisstilllessinterestingthanhumanverbalcommunication, though.Apersonpronouncesaparticularword,whichmayhavethestrengthofatornadofor others. How is it possible that a local sequence of tiny air pressure amplitudes (sound) can changeourworldintheglobalscale? Springalsoprovidesfantasticfragrances:Justafterwinter,onecansmelltheheavenlyaroma ofvioletsandhyacinths,sometimesthesubtlescentofbirdcherryisbroughtbythewindfromfar xxiii xxiv Introduction away,thenavarietyofotherexcitingfragrancesfollow.Whatisthemechanismofrecognizing andrememberingsmells,admiringsomeofthemandbeingrepelledbyothers? The taste of fresh bread is unforgettable and is linked to a feeling of happiness, not only for me, but for many people. There must be a program imprinted in us with some chemical hardwarethatletsusappreciatethewaythingstaste.Whatdoesthishardwarelooklike? Touching, which is based on the Pauli exclusion principle, has changed the history of the world many times (just think about kissing etc.). Such giant consequences from such a small cause? What Do We Know? Our senses connect us to what we think of as the Universe. Using them, we are aware of its presence,whileatthesametimewebecomeapartofit.Sensoryoperationsarethedirectresult ofinteractionsbetweenmolecules,aswellasbetweenlightandmatter.Allofthesephenomena deal first with information processing, but at the same time with chemistry, physics, biology, and even psychology. In these complex events, it is impossible to discern precisely where the disciplines of chemistry, physics, biology, and psychology begin and end. Any separation of thesedomainsisartificial.Theonlyreasonformakingsuchseparationsistofocusourattention on some aspects of one indivisible phenomenon. Touch, taste, smell, sight, and hearing–are these our only links and information channels to the Universe? How little we know about it! Torealizethat,justlookupatthesky.Amyriadofstarsarounduspointtonewworlds,which willremainunknownforever.Ontheotherhand,imaginehowincrediblycomplicatedmustbe thechemistryoffriendship.Sciencecannotansweralllegitimatequestionsthatahumanbeing mayask.Scienceisabletodiscoverlawsofnature,butisunabletoansweraquestionlike“Why doesourworldconformtoanylawsatall1?”Thisgoesbeyondscience. Wetrytounderstandwhatisaroundusbyconstructinginourmindspicturesrepresentinga “reality,”whichwecallmodels.Anymodelreliesontheperceptionofreality(ontheappropriate scaleofmassandtime)emanatingfromourexperience,and,ontheotherhand,onourability toabstractbycreatingidealbeings.Manysuchmodelswillbedescribedinthisbook. Itisfascinatingthathumansareabletomagnifytherealmofthesensesbyusingsophisticated tools (e.g., to see quarks sitting in a proton2), to discover an amazingly simple equation of motion3 that describes cosmic catastrophes, with intensity beyond our imagination, and the delicateflightofabutterflyequallywell.Awatermoleculehasexactlythesamepropertiesin thePacificOceanasitdoesonMars,orinanothergalaxy.Theconditionsinthoseenvironments 1 “Themostincomprehensiblethingabouttheworldisthatitisatallcomprehensible.”(AlbertEinstein). 2 Aprotonis1015timessmallerthanahumanbeing. 3 Accelerationisdirectlyproportionaltoforce.Higherderivativesofthetrajectorywithrespecttotimedonotenter thisequation,andneitherdoesthenatureorcauseoftheforce.Theequationisalsoinvariantwithrespecttoany possiblestartingpoint(position,velocity,andmass).Whatremarkablesimplicityandgeneralitythereis(within limits,seeChapter3).
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