Computational_Chemistry.pptVIP

Computational Chemistry Tom Grimes 12/13/2001 The Basics Input a molecular structure In some cases, electronic configuration may need to be known Three basic types of calculations Single-point energy Geometry optimization Frequency calculation Interpret the data Single-point Energy In the simplest terms, it is the energy intrinsic to the structure Useful for determining the stability of a compound The structure may be in an excited state Defines a potential energy surface (PES) Potential Energy Surface PES of HO* Geometry Optimization Determination of the equilibrium geometry Generally, the geometry associated with the lowest single-point energy Can also be used to find transition state geometry by minimizing the energy in all coordinates on the PES except for one SCF theory finds a stationary point, a place where the energy gradient is zero May correspond to either a minimum or a saddlepoint Frequency Calculation Predicts the intensities of the vibrations associated with a molecule This is useful for predicting the absorption spectra of compounds It can also be used to verify whether the structure was fully optimized If it was not fully optimized, reaction coordinates appear as imaginary frequencies. NMR spectra can also be predicted IR Spectrum of Ethanol Computational Methods:Molecular Mechanics Treats molecules classically Ball-and-spring model Assumes “ideal” bond angles and lengths Fastest method Predicts geometries well For normal systems, the bond angles and lengths will be close to ideal Relatively poor prediction of energies Total energy only takes into account deviation from ideal bond length, bond angles, dihedrals, and van der Waals interactions Computational Methods:Semi-empirical Based on quantum mechanics, but uses empirical data to simplify the calculations Fast, but not as fast as molecular mechanics Produces good energies and good geometries for simple organic compounds Computational Methods:Ab Initio Calculations based on quantum mechanics, w