Professional Documents
Culture Documents
Gaussian Calculations of
Gaussian Calculations of
Gaussian Calculations of
Simple Organometallic
Molecules: technical aspects
Practical theoretical chemistry
Presentation
Prof. Agustn Galindo (galindo@us.es )
http://personal.us.es/galindo/
Research Group:
Organometallics and Homogeneous Catalysis
http://grupo.us.es/gfqm223/
Inorganic Chemistry Department
http://departamento.us.es/dinorganica/
University of Sevilla
http://www.us.es
- Gaussian program
- Metal carbonyls
- Input file
Introduction
Selected Bibliography:
- Molecular Orbitals of Transition Metal Complexes, Y. Jean, Oxford
Univ. Press, 2005.
- Orbital Interactions in Chemistry, T.A. Albright, J.K. Burdett, M.H.
Whangbo, Wiley, 1985.
- An Introduction to Molecular Orbitals, Y. Jean, F. Volatron, J. Burdett,
Oxford Univ. Press, 1993.
- Problems in Molecular Orbital Theory, T.A. Albright, J.K. Burdett,
Oxford Univ. Press, 1992.
- Computational Chemistry, D. Young, Wiley, 2001.
- Introduction to Computational Chemistry, F. Jensen, Wiley, 1999.
- Exploring Chemistry with Electronic Structure Methods, J. B.
Foresman, . Frish, Gaussian, 1996.
- Density-Functional Theory of Atoms and Molecules, R. G. Parr, W.
Yang, Oxford University Press, 1989.
Introduction
Introduction
BACK
Every attempt to employ mathematical methods in the study of
chemical questions must be considered profoundly irrational and
contrary to the spirit of chemistry.
Auguste Compte, French philosopher, 1830
TODAY
Computational chemistry is a standard tool of science. For example,
there are now >20 journals devoted to the subject.
Chemometrics and Intelligent Laboratory Systems
Computational and Theoretical Polymer Science
Electronic Journal of Theoretical Chemistry
International Journal of Quantum Chemistry
Journal of Chemical Information and Computer Sciences
Journal of Chemical Theory and Computation
Journal of Chemometrics
Journal of Computational Chemistry
Journal of Computer Aided Chemistry
Journal of Mathematical Chemistry
Theoretical Chemistry Accounts (Theoretical Chimica Acta)
Introduction
Computational Chemistry, D. Young, Wiley, 2001.
At
one
time,
computational
chemistry
TODAY
I am
any chemist
You are
any chemists
Introduction
Introduction
http://nobelprize.org/
"for his development of
computational methods in
quantum chemistry"
Walter Kohn
John A. Pople
USA
United Kingdom
University of California
Santa Barbara, CA, USA
Northwestern University
Evanston, IL, USA
b. 1923
(in Vienna, Austria)
b. 1925
d. 2004
Introduction
References from SciFinder database for Quantum Chemistry and
Density Functional Theory (last 10 years).
Number
of hits
2001
2002 2003
2004
2005 2006
2007
2008
2009 2010
2011
Introduction
Introduction
Percentage share of papers with the topic density functional theory
or DFT in the more general areas of organometallic and
homogeneous catalysis (19962008, Web of Science).
Introduction
RMS Deviation ()
HF
MP2
0.15
SVWN
BLYP
B3P86
0.10
B3LYP
0.05
Oxides
Fluorides
Carbonyls
Introduction
Introduction
Gaussview
http://www.gaussian.com/gv_plat.htm
Graphical interface for Gaussian
build molecules or reactive systems
setup Gaussian input files
graphically examine results
Additional information about
Overview of Capabilities and Features
See: http://www.gaussian.com/g_prod/gv5b.htm
Introduction
Where?
Introduction
Where?
Camerino
SSH
CICA
PC room
protocol
pool.cica.es
- Gaussian program
- Metal carbonyls
- Input file
Login:
- From your terminal, open the SSH program
Login:
- In the SSH window open Quick Connect
Login:
- In the SSH window open Quick Connect
Login:
- Write:
Host name:
User Name
pool.cica.es
eucheme#
(where # is 01-25)
Click
eucheme01
Login:
- Write your password:
acaoc#0809
(where # is 01-25)
Login:
- You are at CICA (Sevilla) in your account:
eucheme#@pool.cica.es
(where # is 01-25)
Policy:
- Each student must work exclusively on the assigned account.
- The system works with queues (it is forbidden to run interactively
any program) and it is necessary to create the specific script file
lanza.sge (example in your account) to run the Gaussian program.
- For working on the CICA system (pool.cica.es), it is necessary to
known a few UNIX commands and also to know the use of vi editor.
Selected UNIX and vi commands are available at:
http://personal.us.es/galindo/Commands.pdf
ls
pwd
cp f1 f2
rm f2
more f1
* NiCO4.com
lanza.sge
- Edit the file NiCO4.com and practice a few minutes with vi commands:
> vi NiCO4.com
move to the last line in the file
delete character under cursor
delete line under cursor
replace character under cursor with
next character typed
finds a word going backwards
finds a word going forwards
undoes last command issued
G
x
dd
r
?word
/word
u
IMPORTANT:
Do not use the mouse with the vi mode.
Do not change now the files, exit with :q!
To exit vi and save changes
To exit vi without saving changes
:wq
:q!
- Edit the file lanza.sge and practice a few minutes with vi commands:
> vi lanza.sge
Inserting
insert before cursor
[esc]
IMPORTANT:
Do not use the mouse with the vi mode.
Do not change now the files, exit with :q!
-S /bin/bash
-N pruebaGaussian
-cwd
-q acaoc
-o IP.out
-pe make 2
export
export
export
export
g03root=/home/deposito/G03Linda/
G03BASIS=/home/deposito/G03Linda/g03/basis
GAUSS_ARCHDIR=/home/deposito/G03Linda/g03/arch
GAUSS_EXEDIR=/home/deposito/G03Linda/g03/bsd:/home/deposito/G03Linda/g03
/home/deposito/G03Linda/g03/g03 /home/eucheme01/NiCO4.com
Gaussian program
Gaussian files:
Input
Gaussian
Output
0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458
0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
Gaussian program
Input file structure
Filename.com
(or Filename.inp or Filename.gjf)
Free format, case insensitive
Spaces, commas, tabs as delimiters between keywords
! as comment line/section
Divided into sections (in order)
Link 0 commands (%)
Route section what calculation is to do
Title
Molecular specification
Optional additional sections
Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O
0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458
Link 0 commands
Route section
Title
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458
0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
Molecular
Specification
Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Link 0 commands
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O
0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458
0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
Gaussian program
Link 0 commands
Locate and name scratch files; System Resources Required
Not blank line terminated
Some Link 0 options (Examples)
%chk
%chk=name.chk
(Location and name of checkpoint file)
%mem
%mem=1Gb
(Sets the amount of dynamic memory, default is 32Mb.
Units allowed: kb, mb, gb, kw, mw, or gw.)
%nproc
%nproc=2
(Sets the number of processors to use)
Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Route section
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O
0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458
0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
Gaussian program
Route section
Basis Set
Job type
Route section
Gaussian program
Route section
Some basis sets:
Gaussian program
Route section
Gaussian program
Gaussian program
Route section
#N
#P
TEST
Geom
Guess
Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O
0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458
Title section
Brief description of
calculation (cannot
exceed five lines)
Title
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458
Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O
0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458
0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
Molecular
Specification
Gaussian program
Molecular Geometry
1st line: Charge and spin multiplicity (2S+1)
Element label and location
Cartesian coordinates
Label x y z
Z-matrix
Label atoms bondlength atom2 angle atom3 dihedral
Blank line terminated
Gaussian program
System Resources
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Checkpoint File
Computational Model
Calculation Type
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O
Title
Charge & Multiplicity
0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458
0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
Structure
Cartesian
Coordinates
EXERCISE 1:
Ni(CO)4
Input
Output
name
user
state
submit/start at
queue
--------------------------------------------------------------------------------------351443
pruebaGaus eucheme08
07/06/2012 18:05:51
running
eucheme@nodo14.hpc.cica.es
- When the program is running there are several files (type Gau-*.*)
that disappear when the work is correctly finished. Type:
> ls
to see these files.
- type ?YES
Optimization completed.
-- Stationary point found.
From the SSH program, open the SSH File Transfer Client
CICA (Sevilla)
Go to Open file
EXERCISE 2:
Run frequency calculations on the optimize Ni(CO)4
compound.
Gaussian program
Checkpoint file
For example: NiCO4.chk
Gaussian program
Use of Checkpoint file. Example: Frequency calculations:
- At CICA: copy the files NiCO4.com and NiCO4.chk to NiCO4f.com and
NiCO4f.chk :
> cp NiCO4.com NiCO4f.com
EXERCISE 3:
Optimize the following compounds
corresponding frequency calculation:
http://www.3dchem.com/3dinorgmolecule.asp?ID=948
and
run
the
http://www.3dchem.com/3dinorgmolecule.asp?ID=979
Cr(CO)6
CrCO6
FeCO5
Suggestion:
- Build up the new molecules with Gaussview.
Fe(CO)5
respectively
Select
Select:
octahedral Cr
atom
IMPORTANT!:
Symmetrize the
molecule
Oh = octahedral
IMPORTANT
Thick
Write Cartesians
%mem=1Gb
%nproc=2
%CHK=CrCO6.chk
# B3LYP 6-31G* opt freq
CrCO6.com file
Cr(CO)6 Oh
0 1
Cr
C
C
C
C
C
C
O
O
O
O
O
O
0.00000000
0.00000000
0.00000000
1.90000000
-0.00000000
0.00000000
-1.90000000
0.00000000
-3.01540000
0.00000000
-0.00000000
3.01540000
0.00000000
0.00000000
0.00000000
1.90000000
0.00000000
0.00000000
-1.90000000
0.00000000
0.00000000
0.00000000
3.01540000
0.00000000
0.00000000
-3.01540000
-0.00000000
1.90000000
0.00000000
-0.00000000
-1.90000000
-0.00000000
0.00000000
3.01540000
0.00000000
0.00000000
-3.01540000
-0.00000000
-0.00000000
- Repeat
the
(FeCO5.com file).
%mem=1Gb
%nproc=2
%CHK=FeCO5.chk
# B3LYP 6-31G*
FeCO5.com file
opt freq
Fe(CO)5 D3h
0 1
Fe
C
C
C
C
C
O
O
O
O
O
-0.00000000
-1.67142903
0.00000000
0.00000000
1.67142903
-0.00000000
-0.00000000
2.63739377
0.00000000
-0.00000000
-2.63739377
-0.00000000
0.96500000
-1.93000000
-0.00000000
0.96500000
-0.00000000
-0.00000000
1.52270000
-3.04540000
-0.00000000
1.52270000
0.00000000
-0.00000000
-0.00000000
1.93000000
-0.00000000
-1.93000000
3.04540000
0.00000000
0.00000000
-3.04540000
0.00000000
EXERCISE 4:
Draw the following molecular orbitals:
HOMO
HOMO-1
HOMO-2
HOMO
HOMO-1
HOMO
HOMO-1
HOMO-2
Gaussian program
Open the
MO editor
Click:
Visualize
Click:
Update
- Gaussian program
- Metal carbonyls
- Input file
Metal carbonyls
Selected examples:
http://www.3dchem.com/3dinorgmolecule.asp?ID=979
http://www.3dchem.com/3dinorgmolecule.asp?ID=948
http://www.3dchem.com/3dmolecule.asp?ID=96
Frontier orbitals
Symmetry-adapted
orbitals for an
octahedral complex
ML6
d orbitals (t2g)
-interactions
-donor
-acceptor
Cr(CO)6
HOMO
d6
d-block
MO diagram of a Td compound
d-block
EXERCISE 5:
[Fe(CO)4(C2H4)]
[Cr(CO)4(C2H4)2]
CrC2H42CO4
- Gaussian program
- Metal carbonyls
- Input file
[PtCl3(C2H4)]http://www.3dchem.com/3dinorgmolecule.asp?ID=581
[Fe(CO)4(C2H4)]
[Cr(CO)4(C2H4)2]
Donation
Back-donation
Oh, d6
Conformational preferences
Conformational preferences
Conformational preferences
Diagram for the interaction between the nonbonding d orbitals (in the
centre) and the * orbitals on the ethylene ligands in the coplanar (D2h, on
the left) and perpendicular (D2d, on the right) conformations of an
octahedral trans-[ML4(2-C2H4)2] complex with a d6 electronic configuration.