Geometrical Derivatives of Energy Surfaces and Molecular Properties

ISBN-13: 9789401085373 / Angielski / Miękka / 2012 / 342 str.

Poul Jorgensen; Jack Simons

Opis

The development and computational implementation of analytical expres sions for the low-order derivatives of electronic energy surfaces and other molecular properties has undergone rapid growth in recent years. It is now fairly routine for chemists to make use of energy gradient information in locating and identifying stable geometries and transition states. The use of second analytical derivative (Hessian or curvature) expressions is not yet routine, and third and higher energy derivatives as well as property (e.g., dipole moment, polarizability) derivatives are just beginning to be applied to chemical problems. This NATO Advanced Research Workshop focused on analyzing the re lative merits of various strategies for deriving the requisite analyti cal expressions, for computing necessary integral derivatives and wave function parameter derivatives, and for efficiently coding these expres sions on conventional scalar machines and vector-oriented computers. The participant list contained many scientists who have been instrumen tal in bringing this field to fruition as well as eminent scientists who have broad knowledge and experience in quantum chemistry in general."

Spis treści

Hamiltonian Expansion in Geometrical Distortions.- MCSCF Analytical Energy Derivatives Using a Response Function Approach.- Configuration Interaction Energy Derivatives.- Analytical Evaluation of Gradients in Coupled-Cluster and Many-Body Perturbation Theory.- MCSCF Energy Derivatives Using Fock Operator Methods.- Third and Fourth Derivatives of the Hartree-Fock Energy: Formalism and Applications.- Strategies of Gradient Evaluation for Dynamical Electron Correlation.- MBPT Evaluation of Energy Derivatives Using Fock-Operator Methods.- Calculation of Dipole Moments, Polarizabilities and Their Geometrical Derivatives.- The Calculation of Dipole Moment and Polarizability Derivatives with SCF Wavefunctions.- A Unified Treatment of Energy Derivatives and Non-Adiabatic Coupling Matrix Elements.- Geometrical Derivatives of Frequency-Dependent Properties.- Energy Derivatives and Symmetry.- Techniques Used in Evaluating Orbital and Wavefunction Coefficients and Property Derivatives — eg The Evaluation of M(B)P(T)-2 Second Derivatives.- The Evaluation of the Wave Function Response Contributions to the Geometrical Derivatives of the Electronic Energy.- Single Configuration SCF Second Derivatives on a Cray.- Direct Methods in the Calculation of Analytical Derivatives of Energy Surfaces and Molecular Properties.- Walking on MCSCF Potential Energy Surfaces: Application to H2O2 and NH3.- The Location and Characterization of Stationary Points on Molecular Potential Energy Surfaces.- Newton Based Optimization Procedures for Searching Potential Energy Surfaces.- Electric Dipole and Electronic Transition Moment Functions in Molecular Spectroscopy.- Relationship Between Raman Intensities and Derivatives of the Dipole Polarizability.- Chemical Applications of Energy Derivatives: Frequency Shifts as a Probe of Molecular Structure in Weak Complexes.- Chemical Applications of Energy Derivatives: Are Second Derivatives Enough?.- On the Graphical Display of Molecular Electrostatic Force-Fields and Gradients of the Electron Density.- Participants.