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Course contents
Overview: O i Wh What t is i Computational C t ti l Chemistry Ch i t 1: ab initio method 2: Density Functional Theory 3: Molecular mechanics method 4: Introduction to some programs
Continuum M th d Methods
Mesoscale methods
Lattice Monte Carlo Brownian dynamics Dissipative particle dyn
(s) 10-6
9 (ns) 10-9
(ps) 10-12
(fs)
10-15
10-10
10-9
(nm)
10-8
10-7
(m)
10-6
10-5
10-4
LENGTH /meters
Figure 1. Schematic illustration of the simulation methods for different length and time scales
Introduction to Computational Chemistry
Methods
Ab initio i iti quantum t chemistry h i t methods th d Density functional theory (DFT) methods Semi-empirical quantum chemistry method Molecular mechanics method Specially treatment for periodic boundary condition
Plane waves implementation Ewald summation for long-range interaction
Molecular dynamics and Monte Carlo simulation Hybrid quantum mechanics/molecular mechanics method
Introduction to Computational Chemistry
Post-Hartree-Fock methods
o o o o o
Multi-reference methods
o o o Multi-configurational self-consistent field (MCSCF) Multi-reference configuration interaction (MRCI) Complete Active Space Perturbation Theory (CASPTn)
HOMO
LUMO
HOMO-1
LUMO+1
HOMO-2
LUMO+2
HOMO-3
LUMO 3 LUMO+3
HOMO-4
LUMO+4
L N (1) L N ( 2) L L
i = ci
=1
L N ( N)
i = ci
=1
Variation Principle
Hartree-Fock (HF)
Post-Hartree-Fock Method
Basis Set
STO
i = ci
=1
GTO
r Minimal basis sets: STO-3G Split-valence basis sets: 3-21G, 6-31G Polarisation functions are denoted with * (3-21G*, 6-31G*) Diffuse Diff f functions ti are denoted d t db by + (6 (6-31+G*) 31 G*) * The selection of basis set is a key factor to the accuracy of the numeric solution.
Level of Theory
Methods
Ab initio i iti quantum t chemistry h i t methods th d Density functional theory (DFT) methods Semi-empirical quantum chemistry method Molecular mechanics method Specially treatment for periodic boundary condition
Plane waves implementation Ewald summation for long-range interaction
Molecular dynamics and Monte Carlo simulation Hybrid quantum mechanics/molecular mechanics method
Introduction to Computational Chemistry
Exchange-Correlation Functional
Exc can be determined using homogeneous electron gas model or using quantum Monte Carlo methods
Correlation-Exchange Functional
VWN5 BLYP HCTH BP86
Increasing qualit ty and com mputationa al cost
LDA local density GGA gradient corrected Meta-GGA M t GGA kinetic energy density included Hybrid exact HF exchange component Hybrid-meta-GGA
MPWB1K M06
http://en.wikipedia.org/wiki/Density_functional_theory
Introduction to Computational Chemistry
Methods
Ab initio i iti quantum t chemistry h i t methods th d Density functional theory (DFT) methods Semi-empirical quantum chemistry method Molecular mechanics method Specially treatment for periodic boundary condition
Plane waves implementation Ewald summation for long-range interaction
Molecular dynamics and Monte Carlo simulation Hybrid quantum mechanics/molecular mechanics method
Introduction to Computational Chemistry
CNDO (1965, Pople et al) MINDO (1975, Dewar ) MNDO (1977, Thiel) Thiel) INDO (1967, Pople et al) ZINDO SINDO1
STOSTO -basis (/S (/S-spectra,/2 d d-orbitals) orbitals) /1/2/3, organics /d, organics, transition metals O Organics i Electronic spectra, transition metals 1-3 row binding energies, photochemistry and transition metals
Further improvement
AM1
Modified nuclear repulsion terms model to account for H-bonding (1985 (1985, Dewar et al) Widely used today (transition metals, inorganics inorganics) )
Larger data set for parameterization compared to AM1 Widely used today (transition metals, inorganics inorganics) )
Methods
Ab initio i iti quantum t chemistry h i t methods th d Density functional theory (DFT) methods Semi-empirical quantum chemistry method Molecular mechanics method Specially treatment for periodic boundary condition
Plane waves implementation Ewald summation for long-range interaction
Molecular dynamics and Monte Carlo simulation Hybrid quantum mechanics/molecular mechanics method
Introduction to Computational Chemistry
Common tasks
Sampling conformational spaces (Structure and dynamics) Free energy calculation (Binding energy) Structural refinement (based on NMR data) Reaction path (Transition Path Sampling) Molecular interaction (Ligand-Protein) ( g ) Investigate mutational effects etc. t
Applications
Speed of method opens up a wide range of systems Amorphous condensed phase liquids, liquid crystals, glasses Biological systems Biopolymers, membranes Nanotubes and molecular machines
Fast calculations allow large numbers of conformers to be screened Drug docking analysis Global minimum searches
Statistical data can be collected Access to bulk properties (via statistical mechanics) Simulation of finite temperature behaviour and phase changes
Methods
Ab initio i iti quantum t chemistry h i t methods th d Density functional theory (DFT) methods Semi-empirical quantum chemistry method Molecular mechanics method Specially treatment for periodic boundary condition
Periodic Electronic Structure Calculations Ewald summation for long-range interaction
Molecular dynamics and Monte Carlo simulation Hybrid quantum mechanics/molecular mechanics method
Introduction to Computational Chemistry
Blochs Theorem
The electronic Th l t i wave function f ti i in a periodic i di potential t ti l expressed as
nk
(r ) can b be
nk k
( r ) = k c ik exp p ( ik .r )
nk
(r )
Application of pseudopotential can effectively: reduce the size of basis set ; reduce the size of the system (less electrons) take into account of the relativistic and other effects
Ewald summation Fast Multipole Method Particle Mesh Ewald Multi-grid summation
Ewald, 1921 Greengard, 1987 Darden, , 1993 Brandt et al., 1990 Skeel et al., 2002 Izaguirre et al., 2003
Others
VMD
GAMESS
General Atomic and Molecular Electronic Structure System Primary focus is on ab initio quantum chemistry calculations Also includes DFT, , semi-empirical p ( (AM1, , PM3) ) and QM/MM capabilities
Early version of GAMESS is available under /usr/global/gamess scripts need to execute the program
GAUSSIAN
Gaussian 03 is a general electronic structure programs. Gaussian 03 is used by chemists, chemical engineers, biochemists, physicists and others for research in established and emerging areas of chemical i t interest. t
IRCMax
++ ++ ++
Molecular Specification
Molecules can be specified by ZZ matrix or Cartesian coordinate. The Z-matrix is a way to represent a system t built b ilt of f atoms. t It provides id a description of each atom in a molecule in terms of its atomic number, bond length bond angle length, angle, and dihedral angle, the so-called internal coordinates.
Molecular builders Some softwares provide sketcher and fragment library to build molecules with ease i ease, i.e. e GaussView GaussView, Accerlyss Accerlys s Discovery Studio Studio, Materials Studio Studio, Java Molecular Editor, HyperChem, Gabedit, etc. Some softwares provide interface to write out z-matrix or Cartesian coordinates, i.e. Molden
Introduction to Computational Chemistry
NWCHEM
NWChem is a computational chemistry package with many capabilities, including: Molecular electronic structure calculations Pseudopotential plane-wave electronic structure calaculations Ab intio and classical molecular dynamics and more
End Basis * library 3-21G End MP2; freeze atomic; END Task mp2 energy
Job name determines names for temporary files <module> end blocks change settings for future calculations task directive triggers calculation input is handled strictly top top-toto input bottom (only settings above a task have an impact) Python procedures for more complicated structures
VASP Input
INPUT Files POSCAR POTCAR KPOINTS INCAR OUPUT Files OUTCAR OSZICAR CONTCAR CHGCAR WAVECAR EIGENVAL PROCAR XDATCAR LOCPOT DOSCAR CHG
Pseudopotential File
KPOINT Sampling
CONTROL File
Result analysis
CPMD
The CPMD code Th d is i a plane l wave/pseudopotential / d t ti l implementation i l t ti of f Density Functional Theory, particularly designed for ab-initio molecular dynamics.
isolated systems and system with periodic boundary conditions; k-points molecular and crystal symmetry wavefunction optimization: direct minimization and diagonalization geometry optimization: local optimization and simulated annealing molecular dynamics: constant energy, constant temperature and constant pressure path integral MD response functions excited it d states t t many electronic properties time-dependent DFT (excitations, molecular dynamics in excited states)
1.609250000 14.986109219 4 4.827750000 827750000 5 5.749109219 749109219 4.827750000 3.487890781 1.609250000 12.724890781
1.609250000 1 1.609250000 609250000 1.609250000 1.609250000 1.609250000 4.827750000 4 4.827750000 827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 1.609250000 1.609250000 1 1.609250000 609250000 1.609250000 1.609250000
1.089966007 -0.147792007 0 147792007 2.032139989 3.491585919 17.051501595 10.326966007 9 9.089207993 089207993 11.269139989 12.728585919 7.814501595 17.384033993 18.621792007 16.441860011 14.982414081 19.896498405 8.147033993 9.384792007 7 7.204860011 204860011 5.745414081 10.659498405
1.609250000 0.568999197 4.827750000 9.805999197 4 4.827750000 827750000 17 17.905000803 905000803 1.609250000 8.668000803
1.609250000 1.609250000 1.609250000 1.609250000 1 1.609250000 609250000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 4.827750000 1 1.609250000 609250000 1.609250000 1.609250000 1.609250000 1.609250000
1.089966007 -0.147792007 2.032139989 3.491585919 17 17.051501595 051501595 10.326966007 9.089207993 11.269139989 12.728585919 7.814501595 17.384033993 18.621792007 16.441860011 14.982414081 19.896498405 8 8.147033993 147033993 9.384792007 7.204860011 5.745414081 10.659498405
1.609250000
2.026597833
ABINIT
ABINIT is a package whose main program allows one to find the total energy, charge density and electronic structure of systems made of electrons and nuclei (molecules and periodic solids) within Density F Functional ti l Th Theory (DFT), (DFT) using i pseudopotentials d t ti l and d a planewave l basis.
ABINIT Input
To run abinis you need four things: (1) Access to the executable, abinis/abinip. (2) ( ) An input p file. (3) A files file (list of file names in a file). (4) A pseudopotential input file for each kind of element in the unit cell.
c3, c4 h33s h33p p k11p, k22p, k33p h33d k11d, k22d, k33d h33f k11f k11f, k22f k22f, k33f
PDB File
LEaP antechamber
Ptraj MM/PBSA
Analysis P Programs
Sander Input
Other Packages
3D-DOCK AUTODOCK Gaussview HADDOCK Molden M ld Pymol Rosetta VMD
# oniom(blyp/3-21g:amber) geom=connectivity ti it
# oniom(blyp/3-21g/dga1:amber) geom=connectivity opt=loose
0 1 0 1 0 blyp/3-21g:amber 1 0 1 with density fitting from Luecke 0.000000000000 0.066754956170 H 0.000000000000 1.308239478983 H 3 1 1 1 N-N3-0.181200 22.076181 24.563316 -13.077047 L 0.000000000000 -0.507359536461 H C-CT-0.003400 20.736756 0.000000000000 -0.766510748030 M H 1 24.514869 0.723886 -13.699982 0.723886 L0.723886 C-C-0.616300 20.734957 25.313129 -14.988472 L 0.000000000000 -2.301387120377 L H 4 24.680955 0.723886 -16.030293 0.723886 L0.723886 O-O--0.572200 20.731825 -0.885256630266 -0.468844831106 M 0.885256630266 -0.468844831106 M C-CT--0.043900 19.775830 32.473200 7.920456 L C 842389774687 CT 0 015800 18 18.776883 33.512258 512258 7 7.403331 403331 L H H-HC HC 0 0 0. 0 0. 0 0.000000000000 000000000000 -2.842389774687 2C-CT--0.015800 L776883 33 C-CT--0.082400 17.966350 32.942557 6.232525 H 0.881286097766 -2.591806824941 L C-CT-0.377886 16.928731 33.900731 5.689445 H -0.881286097766 -2.591806824941 L N-N2--0.693824 17.521649 35.160530 5.191031 H
N-N--0.415700 22.301376 31.316157 8.955475 L H-HW-0.417000 H HW 0.417000 10.154733 46.125705 25.662719 L H-HW-0.417000 11.339041 47.039598 25.433539 L H-H-0.274700 21.866560 34.137178 7.953109 L H-H-0.377886 17.847763 35.188083 4.238902 H H-H-0.341200 18.066775 49.503351 -1.731201 L H-HO-0.474700 15.931300 31.668829 17.328019 L 1772 1.0
1771 1.0 2 3 1.0 5 1.0 1769 1.0 3 4 2.0 8 2.0 4 5 6 1.0 7 Chemistry 1.0 1764 1.0 Computational 6 1768 1.0
Visualization tools
Molecules Gaussview Molden M ld Molekel Pymol ECCE ArgusLab VMD VegaZZ DeepView Discovery Studio JMol Periodic Systems
Materials Studio Crystal y Maker VMD
MOLDEN
Gaussview
VMD
ArgusLab
Acknowledgement
Some slides have used pictures and graphics from other authors.