Advances in the theory of quantum systems in chemistry and physics

652 389 0
  • Loading ...
1/652 trang
Tải xuống

Thông tin tài liệu

Ngày đăng: 14/03/2018, 15:22

ADVANCES IN THE THEORY OF QUANTUM SYSTEMS IN CHEMISTRY AND PHYSICS Progress in Theoretical Chemistry and Physics VOLUME 22 Honorary Editors: Sir Harold W Kroto (Florida State University, Tallahassee, FL, U.S.A.) Pr Yves Chauvin (Institut Franc¸ais du P´etrole, Tours, France) Editors-in-Chief: J Maruani (formerly Laboratoire de Chimie Physique, Paris, France) S Wilson (formerly Rutherford Appleton Laboratory, Oxfordshire, U.K.) Editorial Board: V Aquilanti (Universit`a di Perugia, Italy) E Brăandas (University of Uppsala, Sweden) L Cederbaum (Physikalisch-Chemisches Institut, Heidelberg, Germany) G Delgado-Barrio (Instituto de Matem´aticas y F´ısica Fundamental, Madrid, Spain) E.K.U Gross (Freie Universităat, Berlin, Germany) K Hirao (University of Tokyo, Japan) E Kryachko (Bogolyubov Institute for Theoretical Physics, Kiev, Ukraine) R Lefebvre (Universit´e Pierre-et-Marie-Curie, Paris, France) R Levine (Hebrew University of Jerusalem, Israel) K Lindenberg (University of California at San Diego, CA, U.S.A.) R McWeeny (Universit`a di Pisa, Italy) M.A.C Nascimento (Instituto de Qu´ımica, Rio de Janeiro, Brazil) P Piecuch (Michigan State University, East Lansing, MI, U.S.A.) M Quack (ETH Zăurich, Switzerland) S.D Schwartz (Yeshiva University, Bronx, NY, U.S.A.) A Wang (University of British Columbia, Vancouver, BC, Canada) Former Editors and Editorial Board Members: I Prigogine (†) J Rychlewski (†) Y.G Smeyers (†) R Daudel (†) M Mateev (†) W.N Lipscomb (†) ˚ H Agren (*) D Avnir (*) J Cioslowski (*) W.F van Gunsteren (*) † deceased, * end of term For further volumes: http://www.springer.com/series/6464 H Hubaˇc (*) M.P Levy (*) G.L Malli (*) P.G Mezey (*) N Rahman (*) S Suhai (*) O Tapia (*) P.R Taylor (*) R.G Woolley (*) Advances in the Theory of Quantum Systems in Chemistry and Physics Edited by PHILIP E HOGGAN Universit´e Blaise-Pascal, Clermont-Ferrand, France ă ERKKI J BRANDAS Department of Quantum Chemistry, University of Uppsala, Sweden JEAN MARUANI Laboratoire de Chimie Physique, CNRS and UPMC, Paris, France PIOTR PIECUCH Michigan State University, East Lansing, Michigan, USA and GERARDO DELGADO-BARRIO Instituto de F´ısica Fundamental, CSIC, Madrid, Spain 123 Editors Philip E Hoggan Pascal Institute Labex IMOBS3, BP 80026 F-63171 Aubi`ere Cedex France pehoggan@yahoo.com Erkki J Brăandas Department of Quantum Chemistry University of Uppsala S-751 20 Uppsala Sweden erkki@kvac.uu.se Jean Maruani Laboratoire de Chimie Physique CNRS & UPMC 11 Rue Pierre et Marie Curie F-75005 Paris France marjema@wanadoo.fr Piotr Piecuch Department of Chemistry Michigan State University East Lansing, Michigan 48824 USA piecuch@chemistry.msu.edu Gerardo Delgado-Barrio Instituto de F´ısica Fundamental CSIC Serrano 123 E-28006 Madrid Spain gerardo@imaff.cfmac.csic.es ISSN 1567-7354 ISBN 978-94-007-2075-6 e-ISBN 978-94-007-2076-3 DOI 10.1007/978-94-007-2076-3 Springer Dordrecht Heidelberg London New York Library of Congress Control Number: 2011942474 © Springer Science+Business Media B.V 2012 No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission from the Publisher, with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com) PTCP Aim and Scope Progress in Theoretical Chemistry and Physics A series reporting advances in theoretical molecular and material sciences, including theoretical, mathematical and computational chemistry, physical chemistry and chemical physics and biophysics Aim and Scope Science progresses by a symbiotic interaction between theory and experiment: theory is used to interpret experimental results and may suggest new experiments; experiment helps to test theoretical predictions and may lead to improved theories Theoretical Chemistry (including Physical Chemistry and Chemical Physics) provides the conceptual and technical background and apparatus for the rationalisation of phenomena in the chemical sciences It is, therefore, a wide ranging subject, reflecting the diversity of molecular and related species and processes arising in chemical systems The book series Progress in Theoretical Chemistry and Physics aims to report advances in methods and applications in this extended domain It will comprise monographs as well as collections of papers on particular themes, which may arise from proceedings of symposia or invited papers on specific topics as well as from authors’ initiatives or translations The basic theories of physics – classical mechanics and electromagnetism, relativity theory, quantum mechanics, statistical mechanics, quantum electrodynamics – support the theoretical apparatus which is used in molecular sciences Quantum mechanics plays a particular role in theoretical chemistry, providing the basis for the valence theories, which allow to interpret the structure of molecules, and for the spectroscopic models employed in the determination of structural information from spectral patterns Indeed, Quantum Chemistry often appears synonymous with Theoretical Chemistry: it will, therefore, constitute a major part of this book series However, the scope of the series will also include other areas of theoretical v vi PTCP Aim and Scope chemistry, such as mathematical chemistry (which involves the use of algebra and topology in the analysis of molecular structures and reactions); molecular mechanics, molecular dynamics and chemical thermodynamics, which play an important role in rationalizing the geometric and electronic structures of molecular assemblies and polymers, clusters and crystals; surface, interface, solvent and solidstate effects; excited-state dynamics, reactive collisions, and chemical reactions Recent decades have seen the emergence of a novel approach to scientific research, based on the exploitation of fast electronic digital computers Computation provides a method of investigation which transcends the traditional division between theory and experiment Computer-assisted simulation and design may afford a solution to complex problems which would otherwise be intractable to theoretical analysis, and may also provide a viable alternative to difficult or costly laboratory experiments Though stemming from Theoretical Chemistry, Computational Chemistry is a field of research in its own right, which can help to test theoretical predictions and may also suggest improved theories The field of theoretical molecular sciences ranges from fundamental physical questions relevant to the molecular concept, through the statics and dynamics of isolated molecules, aggregates and materials, molecular properties and interactions, and to the role of molecules in the biological sciences Therefore, it involves the physical basis for geometric and electronic structure, stales of aggregation, physical and chemical transformations, thermodynamic and kinetic properties, as well as unusual properties such as extreme flexibility or strong relativistic or quantum-field effects, extreme conditions such as intense radiation fields or interaction with the continuum, and the specificity of biochemical reactions Theoretical Chemistry has an applied branch – a part of molecular engineering, which involves the investigation of structure–property relationships aiming at the design, synthesis and application of molecules and materials endowed with specific functions, now in demand in such areas as molecular electronics, drug design and genetic engineering Relevant properties include conductivity (normal, semi- and supra-), magnetism (ferro- and ferri-), optoelectronic effects (involving nonlinear response), photochromism and photoreactivity, radiation and thermal resistance, molecular recognition and information processing, biological and pharmaceutical activities, as well as properties favouring self-assembling mechanisms and combination properties needed in multifunctional systems Progress in Theoretical Chemistry and Physics is made at different rates in these various research fields The aim of this book series is to provide timely and in-depth coverage of selected topics and broad-ranging yet detailed analysis of contemporary theories and their applications The series will be of primary interest to those whose research is directly concerned with the development and application of theoretical approaches in the chemical sciences It will provide up-to-date reports on theoretical methods for the chemist, thermodynamician or spectroscopist, the atomic, molecular or cluster physicist, and the biochemist or molecular biologist who wish to employ techniques developed in theoretical, mathematical and computational chemistry in their research programmes It is also intended to provide the graduate student with a readily accessible documentation on various branches of theoretical chemistry, physical chemistry and chemical physics Obituary – W.N Lipscomb (1919–2011) On 14 April, 2011, Nobel Laureate William Nunn Lipscomb Jr passed away at Mount Auburn Hospital in Cambridge, Massachusetts He died from pneumonia and complications from a fall he suffered several weeks earlier Lipscomb was Abbott and James Lawrence Professor of Chemistry at Harvard University, Emeritus since 1990 Lipscomb was born on December, 1919 in Cleveland, Ohio, but his family moved to Lexington, Kentucky, when he was one year old His mother taught music and his father practiced medicine They “stressed personal responsibility and self reliance”1 and created a home in which independence was encouraged A chemistry kit that was offered him when he was 11 years old kindled Lipscomb’s interest in science He “recalled creating ‘evil smells’ using hydrogen sulfide to drive his two sisters out of his room”2 But it was through a music scholarship (he was a classical clarinetist) that he entered the University of Kentucky, where he eventually earned a bachelor of science degree in chemistry in 1941 As a graduate student at the California Institute of Technology, Lipscomb was a prot´eg´e of Nobel Laureate Linus C Pauling, whose famous book The Nature of the Chemical Bond was to revolutionize our understanding of chemistry Lipscomb records1 that Pauling’s course in The Nature of the Chemical Bond was worth attending every year, because each lecture was new In 1946, Lipscomb gained a Ph.D degree in chemistry from Caltech with a dissertation in four parts The first two were entitled: Electron Diffraction Investigations of Vanadium Tetrachloride, Dimethylketene Dimer, Tetrachloroethylene, and Trichloroethylene, and: The Crystal Structure of Methylammonium Chloride Parts Process of Discovery (1977): an Autobiographical Sketch, in: Structures and Mechanisms: from Ashes to Enzymes, G.R Eaton, D.C Wiley and O Jardetzky, ACS Symposium Series, American Chemical Society, Washington, DC (2002) The New York Times, 15 April, 2011 vii viii Obituary – W.N Lipscomb (1919–2011) and were classified work for W.W.II His thesis ends with a set of propositions, the last of which display his sense of humor: (a) Research and study at the Institute have been unnecessarily hampered by the present policy of not heating the buildings on weekends (b) Manure should not be used as a fertilizer on ground adjacent to the Campus Coffee Shop Before eventually arriving at Harvard, Lipscomb taught at the University of Minnesota from 1946 to 1959 By 1948, he had initiated a series of low temperature X-ray diffraction studies, first of small hydrogen bonded systems, residual entropy problems and small organic molecules [and] later [of] the boron hydrides B5 H9 , B4 H10 , B5 H11 , B6 H10 , B9 H15 , and many more related compounds in later years (50 structures of boron compounds by 1976) Lipscomb authored two books, both published by W.A Benjamin Inc (New York) The first (1963) was entitled Boron Hydrides The second (1969), co-authored with G Eaton, was on NMR Studies of Boron Hydrides and Related Compounds He published over 650 scientific papers between 1942 and 2009 His citation for the Nobel Prize in chemistry in 1976, “for his studies on the structure of boranes illuminating problems of chemical bonding”, echoes that of his mentor Linus Pauling in 1954, “for his research into the nature of the chemical bond and its application to the elucidation of the structure of complex substances” It is for his work on the structure of boron hydrides that Lipscomb is most widely known The field of borane chemistry was established by Alfred Stock, who summarized his work in his Baker Lectures3 at Cornell in 1932 As early as 1927, it had been recognized that there exist relatively simple compounds which defy classification within the Lewis-Langmuir-Sidgwick theory of chemical bonding4 A particularly outstanding anomaly is the simplest hydride of boron, which Stock’s pioneering work4 established to be the dimer B2 H6 : The electronic formulation of the structure of the boron hydrides encounters a number of difficulties The ordinary concepts of valence will not suffice to explain their structure; this is shown by the fact that in the simplest hydride, diborane B2 H6 , which has × + = 12 electrons, as many bonds must be explained as are required for C2 H6 which has two more (2×4+6 = 14) electrons available Thus it is that any structural theory for these compounds requires new hypotheses Diborane is said to be electron deficient, since it has only 12 valence electrons and appears to require 14 to form a stable species After some years of uncertainty, the structure of diborane was definitively settled by the infrared studies of Price5 (in 1940–41, Stitt had produced infrared and A Stock, Hydrides of Boron and Silicon, Cornell University Press (1933) Lewis, J Am Chem Soc 38, 762 (1916); I Langmuir, J Am Chem Soc 41, 868, 1543 (1918); N.V Sidgwick, The Electronic Theory of Valency, Oxford University Press (1927); L Pauling, The Nature of the Chemical Bond, Cornell University Press (1939) W.C Price, J Chem Phys 15, 614 (1947); ibid 16, 894 (1948) G.N Obituary – W.N Lipscomb (1919–2011) ix thermodynamic evidence for the bridge structure of diborane6) and the electrondiffraction study of Hedberg and Schomaker7 The bridging structure of the diborane bonding was confirmed by Shoolery8 from the 11 B NMR spectrum The invariance of the single-determinant closed-shell molecular orbital wave function under a unitary transformation of the occupied orbitals was exploited by Longuet-Higgins9 to show that for a minimal basis set the molecular orbitals involved in the B-H-B bridge could be localized to form two three-centre twoelectron bonds Lipscomb, W H Eberhardt and B L Crawford10 demonstrated how this simple procedure could be extended to higher boron hydrides Noticing the similarity of bonding in B2 H6 and in the bridge regions of B4 H10 , B5 H9 , B5 H11 , and B10 H14 led Lipscomb to write11 : These ideas suggest that the hybridization about boron in many of these higher hydrides is not greatly different from the hybridization in diborane In addition, the probable reason for the predominance of boron triangles is the concentration of bonding electron density more or less towards the center of the triangle, so that the bridge orbitals (π -orbitals in B2 H6 ) of the three boron atoms overlap It does seem very likely that the outer orbitals of an atom are not always directed toward the atom to which it is bonded This property is to be expected for atoms which are just starting to fill new levels and therefore may be a general property of metals and intermetallic compounds In the early 1960s, Edmiston and Ruedenberg12 placed the localization of molecular orbitals on a somewhat more objective foundation by transforming to that basis in which interorbital exchange is a minimum Lipscomb and coworkers13 found that when applied to diborane this approach indeed leads to localized threecentre bonds for the B-H-B bridge Lipscomb recalls1 how the localization of molecular orbitals produced a vivid connection between the highly delocalized symmetry molecular orbitals and the localized bonds in which chemists believe so strongly He also records1 : One disappointment was that the National Science Foundation refused to support the work started by J Gerratt and me on spin-coupled wave functions Gerratt and Lipscomb introduced spin-coupled wave functions in 196814 The energy expression for spin-coupled wave functions F Stitt, J Chem Phys 8, 981 (1940); ibid 9, 780 (1941) Hedberg and V Schomaker, J Am Chem Soc 73, 1482 (1951) J Shoolery, Discuss Faraday Soc 19, 215 (1955) H.C Longuet-Higgins and R.P Bell, J Chem Soc 250 (1943); H.C Longuet-Higgins, J Chim Phys 46, 275 (1949); Rev Chem Soc 11, 121 (1957) 10 W.H Eberhardt, B Crawford and W.N Lipscomb, J Chem Phys 22, 989 (1954) 11 W.N Lipscomb, J Chem Phys 22, 985 (1954) 12 C Edmiston and K Ruedenberg, Rev Mod Phys 35, 457 (1963); J Chem Phys 43, 597 (1965) 13 E Switkes, R.M Stevens, W.N Lipscomb and M.D Newton, J Chem Phys 51, 2085 (1969) 14 J Gerratt and W.N Lipscomb, Proc Natl Acad Sci U.S 59, 332 (1968) K 32 A Review of Bonding in Dendrimers and Nano-Tubes 615 The association between SMI polymers was modelled using SMI hexamers Linear associations between SMI polymers were previously studied New additional calculations on bent associations were found and compared to previous results Semi-empirical PM3 calculations were used as above The stabilization energy and stacking geometry of the styrenes agree with results for similar systems All calculations were performed using the Gaussian 03 program 32.3 Results and Discussion The Bond Lengths and Angles of one of the dendrons on each of the structures was measured, Tables 32.1–32.3 Because the arms are degenerate only the bond lengths and angles of one dendron on each structure need be measured In the siloxane dendrimer even though there is an extra CH2 group on one of the dendrons because a different core molecule is used, the arms still remain effectively degenerate [12] The numbers assigned to the atoms of each dendron are shown below in Fig 32.2 From the Bond Angles and Lengths in Tables 32.2 and 32.3 it is clear that the DFT calculations not significantly alter the overall structure of the Tin or siloxane dendrimers This data supports our assumption that the DFT optimized structure of the Platinum dendrimer correlates with what would have been obtained if it had been possible to perform PM3 calculations The subsequent PM6 calculations proved this assumption correct Table 32.1 Bond lengths and angles for platinum dendrimer Bond lengths Bond angles Atoms 0-1 1-2 2-3 3-4 3-5 3-6 6-7 7-8 8-9 9-10 10-11 11-12 12-13 13-8 10-14 14-15 12-16 16-17 Bond C–C C≡C C–Pt Pt–P Pt–P Pt–C C≡C C–C(aromatic) C–C(aromatic) C–C(aromatic) C–C(aromatic) C–C(aromatic) C–C(aromatic) C–C(aromatic) C–C C≡C C–C C≡C Length (A) 1.439 1.240 2.019 2.367 2.367 2.014 1.240 1.436 1.417 1.413 1.413 1.413 1.413 1.417 1.438 1.224 1.438 1.224 Bond 0-1-2 1-2-3 2-3-4 2-3-5 2-3-6 3-6-7 6-7-8 7-8-9 8-9-10 9-10-11 10-11-12 11-12-13 12-13-8 10-14-15 9-10-14 11-12-16 12-16-17 Angle (◦ ) 179.9 179.9 88.1 89.8 179.8 180.0 180.0 120.7 121.0 119.7 120.1 119.7 121.0 180.0 120.2 120.1 180.0 616 M.A Whitehead et al Table 32.2 Bond lengths and angles for tin dendrimer Bond lengths PM3 Atoms 0-1 1-2 2-3 3-4 3-5 3-6 6-7 7-8 8-9 9-10 10-11 11-12 12-13 13-8 10-14 14-15 12-16 16-17 Bond C–C C≡C C–Sn C–Sn C–Sn C–Sn C≡ C–C (aromatic) C–C (aromatic) C–C (aromatic) C–C (aromatic) C–C (aromatic) C–C (aromatic) C–C (aromatic) C–C C≡C C–C C≡C Bond angles DFT Length (A) 1.418 1.199 2.007 2.092 2.093 2.007 1.199 1.418 1.398 1.398 1.398 1.398 1.398 1.398 1.418 1.192 1.418 1.192 1.437 1.234 2.081 2.129 2.129 2.084 1.234 1.437 1.414 1.413 1.413 1.413 1.413 1.414 1.437 1.224 1.437 1.223 Bond 0-1-2 1-2-3 2-3-4 2-3-5 2-3-6 3-6-7 6-7-8 7-8-9 7-8-13 8-9-10 9-10-11 10-11-12 11-12-13 9-10-14 10-14-15 11-12-16 12-16-17 PM3 DFT Angle (◦ ) 180.0 179.8 109.3 109.3 107.7 179.7 180.0 119.8 119.7 119.5 120.5 119.5 120.5 119.7 180.0 119.7 180.0 179.8 179.4 109.1 109.3 106.6 179.5 179.7 120.4 120.2 120.6 119.5 120.4 119.6 120.2 180.0 120.2 180.0 Table 32.3 Bond lengths and angles for siloxane dendrimer Bond lengths Bond angles Angle (◦ ) Length (A) Atoms 0-1 1-2 2-3 2-4 2-5 5-6 6-7 7-8 8-9 9-10 10-11 11-12 12-7 9-13 11-14 Bond type C–O O–Si Si–C Si–C O–Si C–O C–C C–C (aromatic) C–C (aromatic) C–C (aromatic) C–C (aromatic) C–C (aromatic) C–C (aromatic) C–O C–O PM3 1.353 1.709 1.891 1.895 1.706 1.392 1.511 1.392 1.402 1.399 1.400 1.400 1.396 1.368 1.368 DFT 1.383 1.720 1.873 1.881 1.700 1.451 1.523 1.411 1.408 1.404 1.406 1.406 1.405 1.402 1.400 Bond 0-1-2 1-2-3 1-2-4 1-2-5 2-5-6 5-6-7 6-7-8 6-7-12 7-8-9 8-9-10 9-10-11 10-11-12 8-9-13 10-9-13 12-11-14 10-11-14 PM3 123.9 115.0 102.3 109.1 119.6 112.7 120.0 119.5 119.3 121.5 117.9 121.4 116.0 122.5 122.8 115.8 DFT 137.4 111.5 109.0 103.2 128.9 113.0 119.3 120.3 119.4 121.2 118.4 121.5 122.5 116.3 116.7 121.8 32 A Review of Bonding in Dendrimers and Nano-Tubes Table 32.4 Diameters Dendrimer Tin Silicon Platinum Optimization model PM3 DFT PM3 DFT DFT 617 ˚ Diameter range (A) 21.9–22.0 22.0–22.4 16.1–19.2 13.7–17.4 26.7–30.0 Fig 32.3 Numbers assigned to the atoms of each non-degenerate dendron to facilitate the report of bond lengths and angles, shown in Table 32.1 for dendrimers with (a) Si (b) Sn and (c) Pt linking units The diameters of each of the dendrimers was also measured, this data is in Table 32.4 Because these structures are not perfectly spherical, multiple diameters were measured for each structure and a range of values is presented The values presented for the PM3 optimized siloxane [12] Si and Tin [7] Sn dendrimers have previously been reported The relatively narrow range of diameters of the Tin dendrimer is caused by its more regular, globular shape compared to the other two structures This is caused by both the tetrahedral geometry enforced by the Tin centre, as well as the rigidity of the TEB backbone The tetrahedral shape enforced by the Tin, moiety causes it to be more globular than the Platinum dendrimer as the arms fold back on themselves in a Turbine Shape, where the Square Planar arrangement caused by the Platinum centre leads to a more spread out planar conformation, shown by the side views of the dendrimers, Fig 32.3 The rigidity of the TEB backbone gives the Tin, and Platinum dendrimers a more rigid and regular shape unlike Silicon dendrimer Also, the third arm in the Silicon dendrimer which contains an extra CH2 group further decreases the regularity Although all three structures should be about the same size the Platinum dendrimer is clearly the most elongated, as evidenced by its larger diameter, Table 32.4 This is caused by both the rigid square planar geometry caused by the Platinum centre, as well as the rigidity of the TEB backbone, both of which prevent the arms of this dendrimer from folding back The PM3 method gave the Delocalized Molecular Orbitals (DLMO) of the Tin and siloxane dendrimers Those for the siloxane dendrimer have previously been reported [12] and will not be discussed here The three Degenerate Highest 618 M.A Whitehead et al Fig 32.4 Side views of dendrimers with (a) Si (b) Sn and (c) Pt linking units Fig 32.5 The Highest Occupied Molecular Orbitals (HOMO) of the tin dendrimer along with their numbers and energies Occupied Molecular Orbitals (HOMO) of the Sn structure are shown in Fig 32.4 The Degeneracy of these three Valence Orbitals shows the equal reactivity of each arm of the dendrimer 32.4 Interactions Between SMI Polymers Ithas been shown [18–24], that the methods used predict π bonding correctly for many different molecular structures, in the gas phase and when hydrated The theoretical predictions were proved by experiment π-Stacking interactions between styrenes and the van der Waals forces between maleimide chains cause SMI polymer aggregation Racemo-di-isotactic SMI polymers have an ordered distribution of styrenes along a main axis, with maleimide chains at 70◦ to the styrenes In contrast, atactic polymers structures are not periodic, preventing ordered association [25] Two possible association conformations occur: head-to-tail in which the polymers are in identical orientation and head-to-head where they are in opposite orientation [25] SMI polymers can join with different association angles, and three limiting geometries exist: when there is no rotation between polymers (linear association) and two limiting cases if the rotation is ±60◦ (bent associations) Association distances and stabilizaion energies have been previously calculated for the linear associations and using a series of constrained optimizations, followed by relaxing the system [25] Here, the associations 1, 3, and = are calculated using the methods for (Fig 32.6) 32 A Review of Bonding in Dendrimers and Nano-Tubes 619 Fig 32.6 (a) Lateral and cross-section view of a racemo-di-isotactic SMI polymer [25] (hydrogens removed for clarity) (b) The six associations studied: 2, are linear and 1, 3, 4, are bent associations Associations and are equivalent, and associations and have been studied previously [25] Evaluating the energy as a function of inter-phenyl distance (r ) allows compar˚ and 5.5 A ˚ ison of the six associations (Fig 32.7) The average r is between 4.2 A The bent associations 1, 3, 4, and are the most stable, with 20 kJ/mol of stabilization energy for each π-stacking monomer pair (for two hexamers, there are three π-stacking pairs) Figure 32.6 summarizes the PM3 results obtained when the constraints are released The stabilization energy from π-stacking was previously determined by the same type of calculation on the linear association complexes and [25] Chain-chain interactions are negligible for linear associations, and the stabilization energy represents only π-stacking: 13 kJ/mol per π-stack The increased stabilization energy for bent associations compare to linear ones comes from chainchain stabilizing van der Waals interactions between the maleimide chains, and this contributes about kJ/mol per monomer pair Both π-stacking and van der Waals interactions are present in bent associations and produce more stable complexes than linear ones If maleimide chains are shorter, the stabilization energy for bent associations does not change much compared to linear ones Complexes with no chain-chain interactions would become insensitive to changes in association angles 32.5 Nanotubes from Self-assembled SMI Polymers Associating more than two hexamers (500 atoms) was built up from smaller units The optimal inter-phenyl distances and association angles for the most stable bent associations were used to build larger complexes The inter-phenyl distance 620 M.A Whitehead et al Fig 32.7 Stabilization energy as a function of r for the different associations The stabilization energies are given for two hexamers and therefore for three π-stacking SMI styrene pairs ˚ with association angles of 60◦ The bent association (1, 3, = 6) have is about A equivalent energies, are equally probable, and give polymer sheets, from combining bent associations and grown by addition of racemo-di-isotactic polymers When the sheets grow, non-associated peripheral styrenes remain The system is more stable when additional π-stacks form between peripheral styrenes The curvature forms a closed tube because the bent associations already form a 60◦ angle In a closed loop, the hydrophobic styrenes and half of the maleimide chains are no longer in contact with the hydrophilic solvent, but interact with a more hydrophobic environment inside the nanotube walls A closed octagonal structure consisting of eight SMI polymers forms a short polymer nano-tube segment Figure 32.8 shows an SMI nano-tube from eight polymers in the head-to-head conformation The inter-phenyl distances and association angles of the optimized values were used to build the 3dimensional nano-tube Using different periphery atoms as reference points gave an outer diameter of 4.8 ± 0.2 nm and an inner diameter of 1.7 ± 0.2 nm An equivalent structure is also possible for SMI polymers associating in a head-to-tail conformation and a mixture of the two conformations Stabilization energies, inter-phenyl distances, and association angles are comparable between head-to-head and headto-tail conformations The nano-tube forms with racemo-di-isotactic polymers Polymers are polydisperse, and π-stacking is rarely perfect between associated polymers, the short closed segment can have protruding polymers These ends offer nucleation points where addition of further racemo-di-isotactic polymers can occur The nanotube linear growth is illustrated in Fig 32.9 SMI nanotubes are not expected to associate in bundles, as was the case for SMA nanotubes, but to give individual rods The styrenes π-stack inside the walls of the nanotubes and are unavailable for further interaction between nanotubes Unfavorable solvent-styrene interactions are decreased, and favorable hydrophobic styrene-styrene and chainchain interactions are increased in polar solvents such as water unlike SMA [26] 32 A Review of Bonding in Dendrimers and Nano-Tubes 60° row of π-stacking styrene monomers 621 van der Waals radii (1.7±0.2) nm (4.8±0.2) nm Fig 32.8 SMI nanotube (cross section, perpendicular to association plane): (top) the nanotube has an octagonal shape, made from eight racemo-di-isotactic SMI polymers in the head-to-head conformation; (bottom) SMI nanotube shown with van der Waals radii Fig 32.9 Proposed linear growth mechanism for SMI nanotubes SMI polymers self-assemble at the edges of an initially closed structure, and the addition makes the nanotube grow in length (arrows) (lighter shade atoms are further behind the plane of view) 622 M.A Whitehead et al 32.6 Conclusions Theoretical calculations using the Semi-Empirical Parameterization Model (PM3 and PM6) Molecular Orbital Theory and the Density Functional Theory (DFT) proved useful to compare dendrimers with different metal linking centres and organic building blocks The structure optimizations showed how the overall shape of the dendrimers change when the backbone is varied The dendrimer which employed a Platinum linking unit was shown to be a rigid planar structure, while that containing Tin was more turbine shaped However both of these structures have much more inflexible conformations than the Silicon dendrimer, because of the increased rigidity of the TEB backbone compared to DHBA This is caused by the triple bonds in the TEB structure The optimized structures also gave insight about ˚ to 22.4 A ˚ for the Tin dendrimer, the size of the dendrimers which ranged from 21.9 A ˚ for silicon dendrimer and 26.7–30.0 A ˚ for the Platinum structure The 13.7–19.2 A increasing rigidity of the backbone in going from the DHBA Silicon structure to the TEB Tin structure and finally to the TEB Platinum dendrimer decreases the number of permutations in the angle at which the arms attach to the core and restricts the possible conformations to more spread out structures It is clear that as the rigidity of the backbone is increased, the dendrimer structure becomes less globular and more planar and elongated Association between racemo-di-isotactic SMI polymers was investigated theoretically and gave rod-shaped aggregates The bent associations are more stable because of van der Waals interactions between maleimide chains Multiple bent associations form a minimum-energy nanotube structure Although only the selfassembly of relatively long maleimide chains has been studied here, the conclusions apply to other styrene and maleimide copolymers because removing the maleimide chains does not affect the overall geometry of the polymer [25] Additionally, the chemical structure of maleimide chains can modify the van der Waals interaction This study shows that by functionalizing SMA the size of the styrene-based alternating copolymer nanotubes can be changed The shape of SMI nanotubes remains octagonal, the outer diameter increases from 4.4 to 4.8 nm, the inner diameter decreases from 2.0 to 1.7 nm, and aggregation between SMI nanotubes is not possible In the sample studied, a very small fraction of the SMI actually self-assembled in nanotubes because polymer chirality occurs randomly, and only a low percentage is actually racemo-di-isotactic Synthesis of racemo-di- isotactic SMI and their derivatives would be very interesting, if achievable [27] References Vassilieff, T.; Sutton, A; Kakkar, A J Mater Chem 2008, 18, 4031 R van Heerbeek, P C J Kamer, P W N M van Leeuwen and J N H Reek, Chem Rev., 2002, 102, 3717 A Andronov and J M J Frechet, Chem Commun., 2000, 1701 32 A Review of Bonding in Dendrimers and Nano-Tubes 623 D Astruc and F Chardac, Chem Rev., 2001, 101, 2991 J M Lupton, I D W Samuel, P L Burn and S Mukamel, J Chem Phys., 2002, 116, 2, 455 Zeng, F and Zimmerman, S C.; Chem Rev 1997, 97, 1681 Hourani, R.; Whitehead, M A.; Kakkar, A.; Macromolecules, 2008, 41, 508 Bourrier, O.; Kakkar, A.; J Mater Chem, 2003, 13, 1306 Koch, W.; Holthausen, M.C.; A Chemists Guide to Density Functional Theory, 2000, Wiley-VCH 10 (a) J.J.P Stewart, J Comput Chem., 1989, 10, 2, 209 (b) J.J.P Stewart, J Comput Chem., 1989,10, 2, 221 11 M.J Frisch, G.W Trucks, H.B Schlegel, G.E Scuseria, M.A Robb, J.R Cheeseman, V.G Zakrzewski, J.A Montgomery, R.E Stratmann, J.C Burant, S Dapprich, J.M Millam, A.D Daniels, K.N Kudin, M.C Strain, O Farkas, J Tomasi, V Barone, M Cossi, R Cammi, B Mennucci, C Pomelli, C Adamo, S Clifford, J Ochterski, G.A Petersson, P.Y Ayala, Q Cui, K Morokuma, D.K Malick, A.D Rabuck, K Raghavachari, J.B Foresman, J Cioslowski, J.V Ortiz, B.B Stefanov, G Liu, A Liashenko, P Piskorz, I Komaromi, R Gomperts, R.L Martin, D.J Fox, T Keith, M.A Al-Laham, C.Y Peng, A Nanayakkara, C Gonzalez, M Challacombe, P.M.W Gill, B.G Johnson, W Chen, M.W Wong, J.L Andres, M Head-Gordon, E.S Replogle and J.A Pople, Gaussian 98W (revision A.5), Gaussian Inc., Pittsburgh, PA, 2003 12 Hourani, R.; Kakkar, A.; Whitehead, M A.; J Mater Chem, 2005, 15, 2106 13 Hourani, R.; Kakkar, A.; Whitehead, M A.; Theochem, 2007, 807, 101 14 a) Becke, A.D J Chem Phys 1993, 98, 5648 b) Lee, C.; Yang, W.; Parr, R G.; Phys Rev B, 1988, 37, 785 15 Hay, P J.; Wadt, W R J Chem Phys 1985, 82, 270 16 HyperChem release 5.11 For Windows molecular modelling system, Hypercube Inc., 419 Philip Street, Waterloo, Ont., Canada, N2L 3X2, 1999 17 Villamagna, F.; Whitehead, M.A.; J Chem Soc., Faraday Trans., 1994, 90, 1, 47 18 M.A Whitehead, Theo van de Ven and Cecile Malardier-Jugroot, Journal of Molecular Structure: THEOCHEM (2004), 679, 171–177 19 C´ecile Malardier-Jugroot, T.G.M van de Ven and M.A Whitehead, Proceedings of the First Applied Pulp & Paper Molecular Modelling Symposium, Cascades Ltd (2006), 257–270 20 C Malardier-Jugroot, M.A Whitehead and Theo van de Ven, Proceedings of the First Applied Pulp & Paper Molecular Modelling Symposium, Cascades Ltd (2006), Poster 21 Thomas D Lazzara, Theo G.M van de Ven, M.A (Tony) Whitehead, IPCG NewsletterFebruary 2008 22 Theo G.M van de Ven, Thomas Dominic Lazzara and M.A (Tony) Whitehead, The Proceedings ot the Fundamental and Applied Pulp & Paper Modelling Symposium, 2008 Cascades Inc 2009, 63–75 23 M.A (Tony) Whitehead, Ye Tien, Rami Hourani, Ashok Kakkar, Thomas D Lazzara, Theo G.M van de Ven, Joseph Kinghorn Taenzer and Intakhab Alam Zeeshan, The Proceedings ot the Fundamental and Applied Pulp & Paper Modelling Symposium, 2008 Cascades Inc 2009, 23–48 24 Thomas D Lazzara, Michael A Whitehead and Theo G M van de Ven, European Polymer Journal, 45, 1883–1890, 2009 25 Lazzara, T D.; Whitehead, M A.; van de Ven, T G M J Phys Chem B 2008, 112, 16, 4892 26 M.A Whitehead, Cecile Malardier-Jugroot and Theo T.G.M van de Ven, J Phys Chem B (2005), 109(15), 7022–7032 27 Thomas D Lazzara , Theo G.M van de Ven, M A (Tony) Whitehead Macromolecules, 2008, 41, 674 Index A Ab-initio calculations (electronic structure of atoms and molecules), 373, 397, 407, 443, 464 Ab-initio molecular calculations, 370 Ab-initio real-space calculations, 200 Absorption spectra, 244, 609, 610 Accuracy, 5, 72, 74, 76, 78, 90, 92, 93, 100, 103, 105, 107, 110, 176, 181, 211, 212, 222, 224, 242, 245, 286, 287, 292, 304, 309, 336, 359, 370, 379, 440, 469, 478, 490, 526 Activation barrier, 92, 396, 397, 401, 402 Adiabatic correction, 405–428, 486, 513, 515, 516, 518 Adiabatic energy, 426 Anisotropy, 356, 357, 359, 360 Anti-adiabatic state, 481–508 Aromaticity, 555–556, 558–566 Artificial and natural DNAs, 435, 452, 460 Atoms, 49–52, 57, 63, 64, 86, 88, 93, 94, 103, 106, 110, 111, 139, 140, 142, 156–162, 166, 168, 175, 183, 184, 187, 195, 234, 235, 327, 338, 339, 344, 370, 382, 383, 386, 387, 389–393, 397, 406, 435, 441, 442, 445–448, 451–453, 463, 474, 475, 490–492, 500–505, 512, 513, 554, 572–575, 577, 582–585, 587, 588, 592, 594, 596, 605, 606, 615–617, 621–623 Auger capture cross-section, 56, 57 Avoided crossings, 129–135, 357, 358, 360, 365, 370, 372, 373, 376, 407, 411, 413, 415, 416, 419, 420, 426 B Bath modes, 271, 274–276, 279, 280, 289, 290 Bipolar spherical harmonics, 73 Born-Handy ansatz, 513, 515, 516, 519, 521, 523, 526–529 Boron, 103–115 Breakdown of Born-Oppenheimer approximation, 300, 406, 426 C Calculations, 53, 55–57, 59, 61–65, 68, 76, 80, 85, 87, 89, 90, 92, 96, 98, 105, 106, 109, 111–113, 115, 145, 150, 156, 157, 159, 167, 178, 203, 206–208, 212, 240, 292, 293, 304, 305, 328, 333, 339, 344, 349, 357, 373, 374, 376, 396–399, 401, 407–409, 414, 417, 420, 426, 435, 437–439, 441, 443, 445, 452, 453, 458, 484, 485,490, 498, 499, 505–507, 514, 530, 532, 602, 614, 619 Chalcogen substitution effect, 458 Charge transfer process, 357, 359–362, 364, 365, 369, 370, 374 Charge transfer transitions, 302, 608, 609 Complete active space, 344, 347, 349, 357 Complexation energies, 606, 609 Complexity measures, 130 Complex symmetry, 12, 16, 17, 19, 21, 23, 24, 27 Conductance of model base pairs, 451, 459 Conductivity, 434, 435, 451–452, 455, 458, 459, 485, 532–534, 546 P.E Hoggan et al (eds.), Advances in the Theory of Quantum Systems in Chemistry and Physics, Progress in Theoretical Chemistry and Physics 22, DOI 10.1007/978-94-007-2076-3, © Springer Science+Business Media B.V 2012 625 626 Configuration interaction, 104, 106, 113, 141, 225, 301, 304, 347, 357 Conical intersection, 17, 273, 279, 285–296, 300, 302, 306, 407 Continued fractions, 272, 276, 281 Cooperative e-, μ -, γ -nuclear processes, 65 Core-electron, 199 Correlation energy, 97, 98, 111, 141, 150, 187, 191, 193, 195, 236, 397, 487, 488, 494, 508, 533, 545 Correlation function, 56, 93, 264, 265, 271, 278, 282, 337, 340 Coulomb systems, 186, 187 Cross-section of muon capture, 53, 57, 58 D Degenerate states, 16, 53, 529–531 Delocalized bonding, 553, 558–561 Dendrimers, 611–622 Density-functional theory, 64, 87–89, 95, 142, 185–187, 199–216, 219–245, 301, 336, 337, 435, 436, 458, 557, 577, 600, 608, 614 Density matrix, 17, 18, 27, 28, 31, 97, 143, 144, 169, 225, 250, 261–262, 280, 300, 303, 313, 314 Determinant, 22, 26, 88, 95, 97, 114, 145, 174–176, 179, 227, 229, 230, 250, 257, 258, 261, 264, 265, 304, 305, 336, 337, 344, 345, 347–350, 356, 369, 370, 373, 375, 376, 516, 518 DFT calculations, 89, 93, 94, 99, 557, 558, 615 Diabatic energy, 411, 413, 423 Diabatic population, 280, 292, 294, 295 Dibenzo-18-crown-6 ether, 600–602, 605, 606, 608, 609 Diffusion Monte Carlo (DMC), 89–92, 94–96, 106, 114, 327–329, 331, 336, 340, 344, 346–350 Diphenylammonium cation, 600–605, 608 Dirac-Kohn-Sham relativistic wave functions, 55–57 Dirac-Woods-Saxon model, 53, 62, 64 Discharge of a metastable nucleus, 53 Dispersion force, 435, 436, 441, 601 E Edge states, 554 Effective mass, 512, 519 Effective modes, 269–282, 286–296 Effective vibronic modes, 279 Index Eigenfunctions, 39, 41–49, 55, 83–89, 106, 107, 110, 115, 131, 135, 141, 152, 192 Electromagnetic and gravitational fields, 8, 31, 61 Electronic band structure, 123, 190 Electronic cusp, 104 Electronic structure density-functional theory, 199–216 Electronic structure of artificial DNAs, 435 Electron localization function (ELF), 174–177 Electron pairs, 88, 90, 173, 539, 540 Enthalpy, 124, 125, 467 Enthalpy of solvation, 465, 475, 478 Enthalpy of vaporization, 465, 475, 477 Environment, 18–20, 28, 31, 200, 206–207, 211, 215, 221–227, 234–245, 270, 271, 286–290, 301, 314, 317, 356, 398, 467, 471, 474, 620 Environmnet-reflecting pseudopotential, 200, 206–207, 211, 214 Exact solutions, 104, 105, 176, 529 Excitation energy, 61, 186, 220, 221, 223, 227, 231–233, 236, 239–45, 270, 273, 346–349, 450 Excitation energy transfer, 270, 273 Exponential type orbitals, 71, 72, 76, 78, 84–87, 99, 100 π -extended tetrathiafulvalene (π -exTTF), 600, 601, 604 F Factorization method, 37 Fermion, 18, 28, 53, 176, 181, 183, 249, 252, 266, 285, 340, 487, 488, 495, 522–527, 530, 538, 539, 550, 551 Finite-element method, 200, 216 First derivative, 123, 207, 407–408, 412–416, 517 Fullero-N-methylpyrrolidine, 600, 601 G Gauge-dependent contribution to radiation width, 56 Gegenbauer addition theorem, 73 Gill, P.M.W., 85 Graphene edge, 554 Ground state, 15, 32, 33, 52, 60, 89, 95, 97, 106, 107, 112–114, 150, 151, 157–159, 175, 181, 185–187, 190, 192, 193, 226–229, 231, 232, 235, 236, 250, 252, 265, 278, 279, 285, 287, 291, 302, 308–313, 320, 335, 336, 339, 344, 346, Index 627 348, 349, 357, 359, 371, 372, 374, 375, 399, 406, 418, 420, 423, 486–487, 494–499, 501–503, 508, 515, 527, 529, 531–533, 535, 537–543, 554, 573, 575, 577, 583–92, 594, 613 H Hydrogen, 52, 53, 58, 84, 86–88, 91, 94, 96–99, 130–132, 134, 173, 175, 219–245, 335, 337, 338, 357, 364, 365, 370, 371, 395, 396, 399, 434–436, 440–443, 454, 455, 459, 463, 467, 475, 514, 515, 573, 601, 605, 606, 608 Hydrogen bonds, 100, 220, 434, 443, 601, 605, 606, 608 Hydrostatics, 120 Hylleraas-CI, 103–115 Hyperphonon, 519, 521, 523, 528, 533, 534, 536, 537, 543, 544, 546 Hypervibration, 519, 521, 522, 526, 544 Linear vibronic coupling (LVC) model, 271–273, 279, 281, 287, 288, 291–295 LiRb, 405–429 LMC shape complexity, 130 Local-density approximation, 55, 93, 120–122, 126, 337, 505 Loges, 175, 176, 182 Long-range corrected exchange-correlation functional, 436 Lorentz friction, 86 LVC See Linear vibronic coupling (LVC) K Kato’s theorem, 186, 187 Kohn-Sham equations, 190, 194, 236 Kohn-Sham-like equations, 56, 186, 188–189, 226 Krieger-Li-Iafrate (KLI) method, 186, 189, 192–195 M Magnetic confinement exchange between quantum states, 134 Many-body distribution, 249 Mass density, 464, 475, 476 MCSCF See Multiconfiguration self-consistent field (MCSCF) Metropolis-Hastings sampling bounce algorithm, 337 CO doped clusters, 339 continuous-time lattice diffusion Monte Carlo, 340 coupled electron-ion Monte Carlo, 337 graphics processing units, 340 Langevin diffusion, 329, 331 solvated He clusters, 337, 338 transition metal oxides, 336 variants of reptation quantum Monte Carlo, 333–340 Missing information function, 175, 182, 183 Molecular dynamics (MD) simulations, 200, 271, 278, 395–402, 436, 462–465, 475, 476 Molecular volume, 465, 475–476 Møller-Plesset perturbation theory (MP2), 233, 243, 397, 399, 402, 436–439, 445, 463–465, 467–476, 478, 479, 559, 560 Mori theory, 276 Morse potential, 38–49 Multiconfiguration self-consistent field (MCSCF), 344–346, 348, 349, 370 Muon conversion, 62, 65 Muonic chemistry, 65 Muon-γ -nuclear interaction effects, 51–66 Muon spectroscopy, 52 L Laplace expansion, 72, 74 Lewis structure, 182 N Nano-rods, 612 Nano-tubes, 611–624 I Ideal gas, 477 Information theory, 140, 155, 159, 161–163, 165–169 Interelectronic distances, 107, 110, 115 Ion-atom collisions, 356 Ion-molecule collisions, 356–366 Isomers, 381, 382, 389–391, 465–467, 469, 564, 565, 575, 601, 607, 608 Isospectral potentials, 37–50 J Jahn-Teller effect, 516, 519, 529–532 Jastrow factor, 88–90, 95, 336, 344–347, 349 Jordan blocks, 14–20 628 Non-adiabatic, 356, 357, 359, 360, 362, 363, 365, 366, 370, 484–486, 500, 513, 514, 528, 531, 539, 544, 546 Non-adiabatic interactions, 356, 357, 359, 360, 362, 364, 365, 370 Non-equilibrium Green’s function, 433 Non-interacting kinetic energy, 189, 190 Non-interacting system, 188–190 Non-periodic structures, 215 Nuclear quantum optics, 52, 66 Nuclear shielding tensor, 87, 88, 96–99 O One-particle density, 175, 225 OPM See Optimized potential method (OPM) Optimized potential method (OPM), 185, 186, 189, 192–195 Overlap integrals, 76–80, 305 P Parallel electric and magnetic fields, 131, 132, 134, 135 Particles in a box, 182 Partition of space, 180–182 Pauli principle, 176 PBE, 89, 91, 93, 98, 99, 464–72, 475–479 PEG See Poly-ethylene glycol (PEG) PEO See Poly-ethylene oxide (PEO) Phase transitions solid-solid, 124 Platinum, 435, 446, 448, 613–615, 617, 624 Point canonical transformations, 37, 38, 50 Poisson equation, 80, 85, 201 Polyaromatic hydrocarbons, 554 Poly-ethylene glycol (PEG), 460, 461 Poly-ethylene oxide (PEO), 461 Polymer, 270, 463, 612, 618–620, 622 Poly-phenylene vinylene (PPV), 271, 276–277 PPV See Poly-phenylene vinylene (PPV) Pressure effects on crystal structure, 120–121 Probability, 3, 4, 7, 21, 22, 53, 60, 61, 65, 130, 131, 146, 155, 161–166, 173–184, 292, 303, 304, 311, 314, 329, 330, 332–335, 337, 398, 476, 477, 538 pyrazine, 286, 287, 291–296 Q Quadratic vibronic coupling, 287 Index R Random matrix, 264, 265 Rate constants, 371, 375, 377, 378, 402 Reactivity, 155, 156, 161, 162, 397, 446, 571–595, 618 Relativistic energy approach, 53–59, 61 Relativistic many-body perturbation, 53, 65 Relativity, 5, 21–27, 159, 169 RESP charges, 464, 474, 478, 479 Riccati equation, 39 Riemann hypothesis, 264, 265 Roton, 528, 529, 541, 544 Rubin chain, 279 S Scaled density, 190193 Schrăodinger equation, 5, 7, 10, 11, 17, 3139, 84, 86, 89, 95, 141, 144, 146, 186, 209, 221, 227, 303, 314, 317, 512, 514 Schwarzschild radius, 25, 26, 28 Second derivative, 207, 408–409, 412–417, 423, 426 Self-assembly, 462 Semi-classical cross sections, 359, 371 Semi-empirical, 279, 561, 565, 615–617, 626 Shibuya-Wulfman integral, 80 Singlet-triplet energy gap, 444–445 Slater basis set, 346, 348, 350 Slater orbitals, 105, 107, 111, 112 Slater-type orbitals (STOs), 72, 73, 76, 80, 85, 87, 92, 105, 110, 114 Solid spherical harmonics, 71, 74 Space chemistry, 11, 12, 30, 175 Special and general relativity, 5, 24, 27 Spectral density, 271, 276–281 Spectroscopic constants, 406, 407, 420–423, 426 Spherical modified Bessel functions, 75, 77 Spin-boson model, 269, 271–273 Spin-orbit coupling in condensed matter, 132, 357 π -stacking, 439, 455, 458, 459, 608, 611, 620, 622, 623 State-average, 344–350, 357 State-specific, 229, 344–350 STOs See Slater-type orbitals (STOs) Strong fields, 129–135 Structure of crystalline solids, 61, 66 Sturm-Liouville theory, 85 Superconductivity, 28, 482–488, 507, 513–515, 519, 530, 535, 536, 539–543, 545–547 Supersymmetry, 37 Index T Theory for a single excited state, 186–188 Theory of superconductivity, 482–488, 514 Tin, 121, 541, 613–618, 621 Total energy, 19, 53, 88, 96, 99, 120–122, 141, 150, 151, 189, 191, 193, 200, 232, 346, 439, 465, 473, 478, 495, 503, 531, 533, 536, 540, 544, 586 Translon, 528, 529, 541, 544 U Ultrafast dynamics, 300, 312, 316 UV spectra of artificial DNAs, 449–451, 459 V van der Waals (vdW), 88, 336, 337, 434, 436–440, 443, 444, 451, 458, 465, 470, 572, 601, 602, 604–606, 619, 621, 622 van der Waals correction, 441, 443–445 629 Variational Monte Carlo (VMC), 90, 95, 114, 329, 331, 344, 346, 348, 349 vdW See van der Waals (vdW) Vibrational analysis, 423 Vibronic coupling, 270, 271, 279, 287, 293–295, 530–532, 537, 544–546 Vibronic shift, 406, 407 VMC See Variational Monte Carlo (VMC) W Wave function optimization, 56, 95, 347 Y Yukawa potential, 75 Z Zeta function, 250, 263–267 ... continents The lectures presented at QSCP-XV were grouped into the following seven areas in the field of Quantum Systems in Chemistry and Physics: Concepts and Methods in Quantum Chemistry and Physics; ... (www.springer.com) PTCP Aim and Scope Progress in Theoretical Chemistry and Physics A series reporting advances in theoretical molecular and material sciences, including theoretical, mathematical and. .. an associate professor and, starting 1984, a full professor at the Faculty of Physics of Sofia University In 1996 he was appointed Head of the Department of Theoretical Physics During his career
- Xem thêm -

Xem thêm: Advances in the theory of quantum systems in chemistry and physics , Advances in the theory of quantum systems in chemistry and physics , 2 Time Evolution, Partitioning Techniqueand Associated Dynamics, 6 Analyzing Atomic Densities: Concepts from Quantum Chemistry, 8 Analyzing Atomic Densities: Concepts from Information Theory, 5 Appendix: Detailed Description of the Models, 5 The ζOPM and ζ KLI Methods for a Single Excited State, 2 Nonadiabatic Dynamics ``on the Fly'' in the Framework of Time-Dependent Density Functional Theory (TDDFT), 4 Application of the Nonadiabatic Dynamics ``on the fly'' for the Simulation of Ultrafast Observables of Furan: Comparison with Experiment, 5 Field-Induced Surface-Hopping Method (FISH) for Simulation and Control of Ultrafast Photodynamics, 3 The Si2++H and Si3++He Collision Systems, 2 Electronic Structure Instability – Transition to the Antiadiabatic State, 8 Fröhlich Hamiltonian and the BCS Theory, 4 Void Reactivity of 20-Nanogold Cages: Few Approaches for Measuring

Mục lục

Xem thêm

Gợi ý tài liệu liên quan cho bạn

Nhận lời giải ngay chưa đến 10 phút Đăng bài tập ngay