1st Edition

Accurate Condensed-Phase Quantum Chemistry

Edited By Fred Manby Copyright 2011
    220 Pages 43 B/W Illustrations
    by CRC Press

    220 Pages 43 B/W Illustrations
    by CRC Press

    The theoretical methods of quantum chemistry have matured to the point that accurate predictions can be made and experiments can be understood for a wide range of important gas-phase phenomena. A large part of this success can be attributed to the maturation of hierarchies of approximation, which allow one to approach very high accuracy, provided that sufficient computational resources are available. Until recently, these hierarchies have not been available in condensed-phase chemistry, but recent advances in the field have now led to a group of methods that are capable of reaching this goal.

    Accurate Condensed-Phase Quantum Chemistry addresses these new methods and the problems to which they can be applied. The book begins with an overview of periodic treatments of electron correlation, with an emphasis on the algorithmic features responsible for their computational efficiency. The first section of the book:

    • Describes the Laplace-transform approach to periodic second-order perturbation theory (MP2)
    • Examines local and density fitted schemes for MP2 in crystalline systems
    • Presents test calculations for a variety of systems with small and medium-sized unit cells

    The next section focuses on methods based on treatment of the periodic solid in terms of fragments. This part of the book:

    • Explores the incremental many-body scheme for electron correlation in solids, and describes progress towards metals and molecules on surfaces
    • Describes the hierarchical method as an alternative fragment-based approach to electron correlation in crystalline solids, using conventional molecular electronic structure methods
    • Examines electrostatically embedded many-body expansion for large systems, with an emphasis on molecular clusters and molecular liquids
    • Explores delocalized and localized orbital approaches to the electronic structures of periodic and non-periodic solids

    Lastly, the book describes a practical method by which conventional molecular electronic structure theory can be applied to molecular liquids and solids. Along with the methodology, it presents results on small to medium water clusters as well as on liquid water.

    Laplace transform second-order Møller-Plesset methods in the atomic orbital basis for periodic systems
    Artur F. Izmaylov and Gustavo E. Scuseria

    Implementation details
    RI basis extension
    Basis pair screening
    Distance screening
    Laplace quadratures
    Relation between quadrature points
    Transformation and contraction algorithms
    Lattice summations
    Benchmark calculations
    RI approximation
    AO-LT-MP2 applications

    Density fitting for correlated calculations in periodic systems
    Martin Schütz, Denis Usvyat, Marco Lorenz, Cesare Pisani, Lorenzo Maschio, Silvia Casassa and Migen Halo

    DF in molecular LMP2 calculations
    DF in periodic LMP2 calculations
    Local direct-space fitting in periodic systems
    Multipole-corrected-reciprocal fitting
    Direct-reciprocal-decoupled fitting
    Test calculations
    Fitting basis sets
    General computational parameters
    DF accuracy criteria
    Adjustment of DF parameters
    Performance of the Three DF Schemes
    Sodalite: a benchmark calculation

    The method of increments—a wavefunction-based correlation method for extended systems
    Beate Paulus and Hermann Stoll

    The method of increments
    General ideas
    Extension to metals
    Extension to surface adsorption
    Application to systems with a band gap
    Application to group 2 and 12 metals
    Application to adsorption on CeO2 and graphene

    The hierarchical scheme for electron correlation in crystalline solids
    Stephen Nola, Peter Bygrave, Neil L. Allan, Michael J. Gillan, Simon Binnie, and Frederick R. Manby

    Overview of results
    Properties of crystalline lithium hydride
    Surface (001) energy of LiH
    Lithium fluoride
    Calibration of other methods

    Electrostatically embedded many-body expansion for large systems
    Erin Dahlke Speetzen, Hannah R. Leverentz, Hai Lin, and Donald G. Truhlar

    Many-body methods
    Electrostatically embedded many-body methods

    Use in simulations
    Routes for extending EE-MB to the bulk
    Monte carlo simulations
    Molecular dynamics

    Electron correlation in solids: delocalized and localized orbital approaches
    So Hirata, Olaseni Sode, Murat Keçeli, and Tomomi Shimazaki

    Delocalized orbital approach

    Localized orbital approach

    Ab-initio Monte-Carlo simulations of liquid water
    Darragh P. O’Neill, Neil L. Allan and Frederick R. Manby

    Many-body expansion
    Spatial partitioning of interactions
    Quantum-mechanical description of interactions
    Classical description of interactions
    Self-consistent induction calculations
    Periodic-boundary conditions
    Two-body interactions
    Three-body interactions
    Water clusters
    Liquid water


    Frederick R. Manby is a Reader in the Centre for Computational Chemistry in the School of Chemistry at the University of Bristol, and was previously a Royal Society University Research Fellow. His research has focused on two main areas: first, on the development of efficient and accurate electronic structure methods for large molecules. Second, he has worked on the accurate treatment of condensed-phase systems, including electron correlation in crystalline solids, and on the application of wavefunction-based electronic structure theories to molecular liquids, particularly water. Dr. Manby was awarded the Annual Medal of the International Academy of Quantum Molecular Sciences (2007) and the Marlow Medal of the Royal Society of Chemistry (2006) in recognition of his research on molecular electronic structure theory.