I am working with synthesis of metal complexes. I am interested to use computational chemistry such as geometry optimization methods to support my metal complexes. But I am not aware of those techniques. I would be grateful to you if you can please suggest me to progress with this issue.
Mr. Rangasamy,
It is very complex matter. At first which metal ions you would like to optimize? How many atoms are your systems? Which properties you would like to optimize? Which softwares have you available? How big is the capacity of your computational centre? How long computational time have you available? And, many, may other related questions you should clarify before starting to compute properties of inorganic compounds.
Nevertheless, more recent studies noted M06, M06-2X, M05 (or related) functionals in a combination with SDD (SDDall), or LANL2DZ basis set as among best ones in precise prediction of electronic structures, optical and/or magnetic properties.
These are available for example in Gaussian09 and/or Dalton 2011 program
packages. But also in many other quantum chemical softwares.
A comprehensive literature research about your exact systems in respect best theoretical levels is obligatory. Because of the computational chemistry of inorganic compounds is among the prominent and currently widely developed area of the quantum chemistry. And have available variety of methods, which offer of one site very accurate and reliable information, and in parallel at relatively low cost.
The following refs I personally found as very useful:
1. Zhao, Y., Truhlar, D.: The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06–class functionals and 12 other functionals. Theor. Chem. Acc. 120, 215–241 (2008) (on the functionals)
2. Schleyer, PvR., Schreiner P. 1998. (Eds.-in-Chief), N. Allinger, T. Clark, J. Gasteiger, P. Kollman, H. Schaefer III (Eds.), Encyclopedia of Computational Chemistry, Wiley, Vols. 1–5 (quantum chemistry common)
3. For basis sets, this web-link:
http://www.cup.uni-muenchen.de/oc/zipse/los-alamos-national-laboratory-lanl-ecps.html
4. Cramer, Ch., Truhlar, D.: Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics, Chem. Rev. 99, 2161–2200 (1999)
5. Tomasi, J., Persico, M.: Molecular Interactions in Solution: An Overview of Methods Based on
Continuous Distributions of the Solvent, Chem. Rev. 94, 2027–2094 (1994)
But, have many, many other ones, which described the theoretical quantum chemical methods in a very comprehensive level.
Success with the copmputations!
Mr. Rangasamy,
It is very complex matter. At first which metal ions you would like to optimize? How many atoms are your systems? Which properties you would like to optimize? Which softwares have you available? How big is the capacity of your computational centre? How long computational time have you available? And, many, may other related questions you should clarify before starting to compute properties of inorganic compounds.
Nevertheless, more recent studies noted M06, M06-2X, M05 (or related) functionals in a combination with SDD (SDDall), or LANL2DZ basis set as among best ones in precise prediction of electronic structures, optical and/or magnetic properties.
These are available for example in Gaussian09 and/or Dalton 2011 program
packages. But also in many other quantum chemical softwares.
A comprehensive literature research about your exact systems in respect best theoretical levels is obligatory. Because of the computational chemistry of inorganic compounds is among the prominent and currently widely developed area of the quantum chemistry. And have available variety of methods, which offer of one site very accurate and reliable information, and in parallel at relatively low cost.
The following refs I personally found as very useful:
1. Zhao, Y., Truhlar, D.: The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06–class functionals and 12 other functionals. Theor. Chem. Acc. 120, 215–241 (2008) (on the functionals)
2. Schleyer, PvR., Schreiner P. 1998. (Eds.-in-Chief), N. Allinger, T. Clark, J. Gasteiger, P. Kollman, H. Schaefer III (Eds.), Encyclopedia of Computational Chemistry, Wiley, Vols. 1–5 (quantum chemistry common)
3. For basis sets, this web-link:
http://www.cup.uni-muenchen.de/oc/zipse/los-alamos-national-laboratory-lanl-ecps.html
4. Cramer, Ch., Truhlar, D.: Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics, Chem. Rev. 99, 2161–2200 (1999)
5. Tomasi, J., Persico, M.: Molecular Interactions in Solution: An Overview of Methods Based on
Continuous Distributions of the Solvent, Chem. Rev. 94, 2027–2094 (1994)
But, have many, many other ones, which described the theoretical quantum chemical methods in a very comprehensive level.
Success with the copmputations!
Dear Bojidarka Ivanova,
Thanks for your very detailed and valuable explanation. I didn't know about the basics and I don't have any computational background and facilities.
As I am working on synthesis of Vanadium metal complexes for the biological applications thought of exploring of computational studies to support the structural determination of metal complexes in addition to NMR, IR and Elemental analysis. Also, I am not getting the single crystals for the proper structural determination.
To begin with, I am not aware where to start, how to start and what factors should be considered for optimizing the geometry.
Thanks for your suggestions.
Mr. Rangasamy,
The vanadate complexes may computed in the already shown theoretical levels. But other questions remain. Taking into account that you have not any experience with the computational chemistry, if you would like to performe a reliable study, which to have scientific contribution, not only an quantum chemical exercise, than for you would be more useful to contact with groups in the field in your University, and/or other groups at the Unis world-wide, which to have collaborative interest. Because of, I would like to illustrate you what represent actually the OUTPUT and INPUT files of fully isolated V4+ ion in ethanol, a NPA analysis which is fast one (34 s, below).
It is obtained by GAUSSIAN. If you operate with the same software you may try to optimize your molecule, of couse, nevertheless, that I am mentioned again it is very complex procedure.
In this file you should:
1. Input the coordinates of your complex, due to absence of crystallographic coordinates. For V4+ it is not any problem, they are just 0.000000 0.000000 0.000000. But for your complex...Not!
2. You should replace the theoretical level (in the example it is B3PW91)
3. The 'SCRF=PCM' should deleted, because of the minimize energy test should be in the gas-phase
4. 'NPA' sould replace with 'Freq'. This is the so-called Freq-test. According to the obtained frequency values, you may concluded is your optimization is at the 'energy minimum' or 'not'. If it is, than, you may performe analysis of the geometry parameters.
5. If you change the basis set SDD with some of those of the Dunning's group, they are also very recommended, than you should add duffuse and polarization function after the basis set. In this respect the Gaussian manual is highly recommended. It contains all keywords for inputs as well as it is Internet available free of charge.
The corresponding technical instructions for preparing of your Inputs you may found in the manual file to your quantum chemical program.
Success with the exercise!
INPUT FILE
%Chk=Untitled-13.chk
# UB3PW91/SDD SCRF=PCM Pop=(NPA) Test
Untitled-13
4 2
V 0 0.000000 0.000000 0.000000
36.200 3
OUTPUT-FILE
-------------------------------------
# UB3PW91/SDD SCRF=PCM Pop=(NPA) Test
-------------------------------------
1/38=1/1;
2/17=6,18=5/2;
3/5=17,6=7,11=2,16=1,25=1,30=1/1,2,3;
4/7=2,11=1/1;
5/5=2,32=1,38=4,40=2000,42=-6,53=1/2;
6/7=2,8=2,9=2,10=2,28=1,40=-1/1,7;
99/5=1,9=1/99;
-----------
Untitled-13
-----------
Symbolic Z-matrix:
Charge = 4 Multiplicity = 2
V 0 0. 0. 0.
------------------------------------------------------------------------
Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1 Length/X N2 Alpha/Y N3 Beta/Z J
------------------------------------------------------------------------
1 1 V 0 0.000000 0.000000 0.000000
------------------------------------------------------------------------
Z-Matrix orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 23 0 0.000000 0.000000 0.000000
---------------------------------------------------------------------
Symmetry turned off:
Atomic calculation.
Stoichiometry V(4+,2)
Framework group KH
Deg. of freedom 0
Full point group KH NOp 1
Standard basis: SDD (6D, 10F)
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned off.
49 basis functions 75 primitive gaussians
5 alpha electrons 4 beta electrons
nuclear repulsion energy 0.0000000000 Hartrees.
One-electron integrals computed using PRISM.
1 Symmetry operations used in ECPInt.
ECPInt: NShTT= 120 NPrTT= 264 LenC2= 121 LenP2D= 264.
LDataN: DoStor=F MaxTD1= 6 Len= 172
LDataN: DoStor=T MaxTD1= 6 Len= 172
NBasis= 49 RedAO= T NBF= 49
NBsUse= 49 1.00D-04 NBFU= 49
Projected Huckel Guess.
of initial guess= 1.1525
Requested convergence on RMS density matrix=1.00D-04 within 64 cycles.
Requested convergence on MAX density matrix=1.00D-02.
Requested convergence on energy=5.00D-05.
Virtual orbitals will be shifted by 0.200 hartree.
Keep R1 and R2 integrals in memory in canonical form, NReq= 2654375.
------------------------------------------------------------------------------
Solvent: WATER
Model : PCM/UAHF, Icomp = 4
Version: MATRIX INVERSION
Cavity : PENTAKISDODECAHEDRA with 60 initial tesserae
------------------------------------------------------------------------------
Nord Group Hybr Charge Alpha Radius Bonded to
1 V * 4.00 1.20 1.572
------------------------------------------------------------------------------
FIRST ITERATION
Escaped Charge= 0.00072
Error on NUCLEAR pol.charges =-0.00001 Error on ELECTR. pol.charges =-0.00118
------------------------------------------------------------------------------
Warning: ignores DISREP for atom 1
------------------------------------------------------------------------------
AT CONVERGENCE
60 Tesserae over a maximum of 1500
Surface Area (Ang**2) = 44.71749
Volume (Ang**3) = 28.11836
Escaped Charge= 0.00083
Error on NUCLEAR pol.charges =-0.00001 Error on ELECTR. pol.charges =-0.00128
------------------------------------------------------------------------------
------------------------------------------------------------------------------
IN VACUO Dipole moment (Debye):
X= 0.0000 Y= 0.0000 Z= 0.0000 Tot= 0.0000
IN SOLUTION Dipole moment (Debye):
X= 0.0000 Y= 0.0000 Z= 0.0000 Tot= 0.0000
SCF Done: E(UB+HF-PW91) = -70.1688495037 A.U. after 2 cycles
Convg = 0.1460D-04 -V/T = 3.5453
S**2 = 0.7503
------------------------------------------------------
-------------- VARIATIONAL PCM RESULTS -------------
------------------------------------------------------
(a.u.) = -67.953092
(a.u.) = -70.168850
(a.u.) = -70.168848
(a.u.) = -67.953078
(a.u.) = -70.168850
Total free energy in sol.
(with non electrost.terms) (a.u.) = -70.162467
------------------------------------------------------
(Unpol.Solute)-Solvent (kcal/mol) = -1390.41
(Polar.Solute)-Solvent (kcal/mol) = -1390.42
Solute Polarization (kcal/mol) = 0.01
Total Electrostatic (kcal/mol) = -1390.41
------------------------------------------------------
Cavitation energy (kcal/mol) = 4.00
Dispersion energy (kcal/mol) = 0.00
Repulsion energy (kcal/mol) = 0.00
Total non electr. (kcal/mol) = 4.00
------------------------------------------------------
DeltaG (solv) (kcal/mol) = -1386.40
------------------------------------------------------
Annihilation of the first spin contaminant:
S**2 before annihilation 0.7503, after 0.7500
**********************************************************************
Population analysis using the SCF density.
**********************************************************************
Alpha occ. eigenvalues -- -3.66470 -2.58481 -2.58479 -2.57508 -1.05326
Alpha virt. eigenvalues -- -0.89351 -0.89344 -0.85019 -0.84963 -0.28623
Alpha virt. eigenvalues -- -0.03812 -0.03811 -0.03799 0.00486 0.06832
Alpha virt. eigenvalues -- 0.06833 0.06853 0.07066 0.14732 0.15548
Alpha virt. eigenvalues -- 0.15549 0.16087 0.16095 0.23284 0.42861
Alpha virt. eigenvalues -- 0.44234 0.44235 0.45485 0.45496 0.99171
Alpha virt. eigenvalues -- 0.99173 0.99852 1.23360 1.43176 1.43178
Alpha virt. eigenvalues -- 1.43371 1.43756 1.43779 1.46399 1.46402
Alpha virt. eigenvalues -- 2.45449 6.92904 6.92907 6.94287 22.93904
Alpha virt. eigenvalues -- 32.48113 32.53676 32.53844 58.35835
Beta occ. eigenvalues -- -3.61411 -2.55071 -2.54968 -2.47856
Beta virt. eigenvalues -- -0.85965 -0.85964 -0.83338 -0.83301 -0.78067
Beta virt. eigenvalues -- -0.26843 -0.03015 -0.02999 -0.01965 0.00497
Beta virt. eigenvalues -- 0.06925 0.06932 0.07141 0.07292 0.15921
Beta virt. eigenvalues -- 0.15921 0.16162 0.16276 0.16281 0.23803
Beta virt. eigenvalues -- 0.45313 0.45313 0.46072 0.46082 0.46888
Beta virt. eigenvalues -- 1.01014 1.01062 1.04421 1.25200 1.45792
Beta virt. eigenvalues -- 1.45795 1.46853 1.46856 1.49095 1.49124
Beta virt. eigenvalues -- 1.50280 2.46867 6.95458 6.95533 7.00775
Beta virt. eigenvalues -- 23.00557 32.59727 32.59785 32.64328 58.48270
Condensed to atoms (all electrons):
1
1 V 9.000000
Total atomic charges:
1
1 V 4.000000
Sum of Mulliken charges= 4.00000
Atomic charges with hydrogens summed into heavy atoms:
1
1 V 4.000000
Sum of Mulliken charges= 4.00000
Atomic-Atomic Spin Densities.
1
1 V 1.000000
Total atomic spin densities:
1
1 V 1.000000
Sum of Mulliken spin densities= 1.00000
Isotropic Fermi Contact Couplings
Atom a.u. MegaHertz Gauss 10(-4) cm-1
1 V(51) 0.00000 -0.00247 -0.00088 -0.00082
Electronic spatial extent (au): = 10.0795
Charge= 4.0000 electrons
Dipole moment (Debye):
X= 0.0000 Y= 0.0000 Z= 0.0000 Tot= 0.0000
Quadrupole moment (Debye-Ang):
XX= -4.3401 YY= -4.3500 ZZ= -4.8673
XY= 0.0017 XZ= -0.0063 YZ= 0.0377
Octapole moment (Debye-Ang**2):
XXX= 0.0000 YYY= 0.0000 ZZZ= 0.0000 XYY= 0.0000
XXY= 0.0000 XXZ= 0.0000 XZZ= 0.0000 YZZ= 0.0000
YYZ= 0.0000 XYZ= 0.0000
Hexadecapole moment (Debye-Ang**3):
XXXX= -1.4252 YYYY= -1.4307 ZZZZ= -1.8376 XXXY= 0.0005
XXXZ= 0.0001 YYYX= 0.0005 YYYZ= -0.0009 ZZZX= -0.0051
ZZZY= 0.0305 XXYY= -0.4760 XXZZ= -0.4724 YYZZ= -0.4745
XXYZ= -0.0003 YYXZ= 0.0001 ZZXY= 0.0004
N-N= 0.000000000000D+00 E-N=-1.258741703992D+02 KE= 2.756825336937D+01
******************************Gaussian NBO Version 3.1******************************
N A T U R A L A T O M I C O R B I T A L A N D
N A T U R A L B O N D O R B I T A L A N A L Y S I S
******************************Gaussian NBO Version 3.1******************************
/RESON / : Allow strongly delocalized NBO set
Analyzing the SCF density
Job title: Untitled-13
Storage needed: 7723 in NPA ( 6291456 available)
NATURAL POPULATIONS: Natural atomic orbital occupancies
NAO Atom No lang Type(AO) Occupancy
-------------------------------------------
1 V 1 s Cor( 3s) 1.99964
2 V 1 s Val( 4s) 0.00000
3 V 1 s Ryd( 5s) 0.00000
4 V 1 s Ryd( 6s) 0.00000
5 V 1 s Ryd( 7s) 0.00000
6 V 1 s Ryd( 8s) 0.00000
7 V 1 s Ryd( 9s) 0.00000
8 V 1 s Ryd(10s) 0.00000
9 V 1 s Ryd(11s) 0.00000
10 V 1 px Cor( 3p) 1.99996
11 V 1 px Ryd( 4p) 0.00000
12 V 1 px Ryd( 5p) 0.00000
13 V 1 px Ryd( 7p) 0.00000
14 V 1 px Ryd( 6p) 0.00000
15 V 1 px Ryd( 8p) 0.00000
16 V 1 py Cor( 3p) 1.99996
17 V 1 py Ryd( 4p) 0.00000
18 V 1 py Ryd( 5p) 0.00000
19 V 1 py Ryd( 6p) 0.00000
20 V 1 py Ryd( 7p) 0.00000
21 V 1 py Ryd( 8p) 0.00000
22 V 1 pz Cor( 3p) 1.99981
23 V 1 pz Ryd( 4p) 0.00005
24 V 1 pz Ryd( 5p) 0.00000
25 V 1 pz Ryd( 6p) 0.00000
26 V 1 pz Ryd( 7p) 0.00000
27 V 1 pz Ryd( 8p) 0.00000
28 V 1 dxy Val( 3d) 0.00000
29 V 1 dxy Ryd( 4d) 0.00000
30 V 1 dxy Ryd( 5d) 0.00000
31 V 1 dxz Val( 3d) 0.00044
32 V 1 dxz Ryd( 4d) 0.00000
33 V 1 dxz Ryd( 5d) 0.00000
34 V 1 dyz Val( 3d) 0.01570
35 V 1 dyz Ryd( 4d) 0.00000
36 V 1 dyz Ryd( 5d) 0.00000
37 V 1 dx2y2 Val( 3d) 0.00000
38 V 1 dx2y2 Ryd( 4d) 0.00000
39 V 1 dx2y2 Ryd( 5d) 0.00000
40 V 1 dz2 Val( 3d) 0.98419
41 V 1 dz2 Ryd( 4d) 0.00001
42 V 1 dz2 Ryd( 5d) 0.00000
43 V 1 f(0) Ryd( 4f) 0.00013
44 V 1 f(C1) Ryd( 4f) 0.00001
45 V 1 f(S1) Ryd( 4f) 0.00001
46 V 1 f(C2) Ryd( 4f) 0.00000
47 V 1 f(S2) Ryd( 4f) 0.00000
48 V 1 f(C3) Ryd( 4f) 0.00002
49 V 1 f(S3) Ryd( 4f) 0.00002
[ 10 electrons found in the effective core potential]
Summary of Natural Population Analysis:
Natural Population
Natural -----------------------------------------------
Atom No Charge Core Valence Rydberg Total
-----------------------------------------------------------------------
V 1 4.00000 17.99938 1.00034 0.00028 19.00000
=======================================================================
* Total * 4.00000 17.99938 1.00034 0.00028 19.00000
Natural Population
--------------------------------------------------------
Effective Core 10.00000
Core 7.99938 ( 99.9922% of 8)
Valence 1.00034 (100.0340% of 1)
Natural Minimal Basis 18.99972 ( 99.9985% of 19)
Natural Rydberg Basis 0.00028 ( 0.0015% of 19)
--------------------------------------------------------
Atom No Natural Electron Configuration
----------------------------------------------------------------------------
V 1 [core]3d( 1.00)
***************************************************
******* Alpha spin orbitals *******
***************************************************
NATURAL POPULATIONS: Natural atomic orbital occupancies
NAO Atom No lang Type(AO) Occupancy Energy
---------------------------------------------------------
1 V 1 s Cor( 3s) 1.00000 -3.66463
2 V 1 s Val( 5s) 0.00000 0.61127
3 V 1 s Ryd( 6s) 0.00000 1.39667
4 V 1 s Ryd( 8s) 0.00000 2.16050
5 V 1 s Ryd( 9s) 0.00000 10.12676
6 V 1 s Ryd(10s) 0.00000 32.73871
7 V 1 s Ryd(11s) 0.00000 36.08019
8 V 1 s Ryd( 7s) 0.00000 1.88701
9 V 1 s Ryd( 4s) 0.00000 0.00649
10 V 1 px Cor( 3p) 0.99998 -2.58467
11 V 1 px Ryd( 7p) 0.00000 8.78871
12 V 1 px Ryd( 6p) 0.00000 1.60592
13 V 1 px Ryd( 5p) 0.00000 0.29275
14 V 1 px Ryd( 8p) 0.00000 24.79843
15 V 1 px Ryd( 4p) 0.00000 0.05885
16 V 1 py Cor( 3p) 0.99997 -2.58459
17 V 1 py Ryd( 7p) 0.00000 8.78877
18 V 1 py Ryd( 6p) 0.00000 1.60620
19 V 1 py Ryd( 5p) 0.00000 0.29278
20 V 1 py Ryd( 8p) 0.00000 24.79655
21 V 1 py Ryd( 4p) 0.00000 0.05882
22 V 1 pz Cor( 3p) 0.99999 -2.57504
23 V 1 pz Ryd( 7p) 0.00000 8.97610
24 V 1 pz Ryd( 6p) 0.00000 1.60717
25 V 1 pz Ryd( 5p) 0.00000 0.29161
26 V 1 pz Ryd( 8p) 0.00000 24.74057
27 V 1 pz Ryd( 4p) 0.00000 0.05852
28 V 1 dxy Val( 3d) 0.00000 -0.89295
29 V 1 dxy Ryd( 5d) 0.00000 0.40798
30 V 1 dxy Ryd( 4d) 0.00000 0.18963
31 V 1 dxz Val( 3d) 0.00044 -0.84985
32 V 1 dxz Ryd( 5d) 0.00000 0.42085
33 V 1 dxz Ryd( 4d) 0.00000 0.19419
34 V 1 dyz Val( 3d) 0.01570 -0.85243
35 V 1 dyz Ryd( 5d) 0.00000 0.42058
36 V 1 dyz Ryd( 4d) 0.00000 0.19387
37 V 1 dx2y2 Val( 3d) 0.00000 -0.89288
38 V 1 dx2y2 Ryd( 5d) 0.00000 0.40797
39 V 1 dx2y2 Ryd( 4d) 0.00000 0.18962
40 V 1 dz2 Val( 3d) 0.98385 -1.05003
41 V 1 dz2 Ryd( 5d) 0.00000 0.39326
42 V 1 dz2 Ryd( 4d) 0.00000 0.18330
43 V 1 f(0) Ryd( 4f) 0.00000 6.21302
44 V 1 f(C1) Ryd( 4f) 0.00001 3.33202
45 V 1 f(S1) Ryd( 4f) 0.00001 3.33198
46 V 1 f(C2) Ryd( 4f) 0.00000 1.46339
47 V 1 f(S2) Ryd( 4f) 0.00000 1.46339
48 V 1 f(C3) Ryd( 4f) 0.00001 4.48252
49 V 1 f(S3) Ryd( 4f) 0.00001 4.48242
[ 5 electrons found in the effective core potential]
WARNING: Population inversion found on atom V 1
Summary of Natural Population Analysis:
Natural Population
Natural -----------------------------------------------
Atom No Charge Core Valence Rydberg Total
-----------------------------------------------------------------------
V 1 1.50000 8.99994 1.00000 0.00006 10.00000
=======================================================================
* Total * 1.50000 8.99994 1.00000 0.00006 10.00000
Natural Population
--------------------------------------------------------
Effective Core 5.00000
Core 3.99994 ( 99.9985% of 4)
Valence 1.00000 ( 99.9996% of 1)
Natural Minimal Basis 9.99994 ( 99.9994% of 10)
Natural Rydberg Basis 0.00006 ( 0.0006% of 10)
--------------------------------------------------------
Atom No Natural Electron Configuration
----------------------------------------------------------------------------
V 1 [core]3d( 1.00)
NBO analysis skipped by request.
***************************************************
******* Beta spin orbitals *******
***************************************************
NATURAL POPULATIONS: Natural atomic orbital occupancies
NAO Atom No lang Type(AO) Occupancy Energy
---------------------------------------------------------
1 V 1 s Cor( 3s) 0.99965 -3.61309
2 V 1 s Ryd( 5s) 0.00000 0.61364
3 V 1 s Ryd( 6s) 0.00000 1.40551
4 V 1 s Ryd( 8s) 0.00000 2.16427
5 V 1 s Val( 9s) 0.00000 10.17491
6 V 1 s Ryd(10s) 0.00000 32.80579
7 V 1 s Ryd(11s) 0.00000 36.18919
8 V 1 s Ryd( 7s) 0.00000 1.89557
9 V 1 s Ryd( 4s) 0.00000 0.00626
10 V 1 px Cor( 3p) 0.99999 -2.55059
11 V 1 px Ryd( 7p) 0.00000 8.81454
12 V 1 px Ryd( 6p) 0.00000 1.63082
13 V 1 px Ryd( 5p) 0.00000 0.29788
14 V 1 px Ryd( 8p) 0.00000 24.86145
15 V 1 px Ryd( 4p) 0.00000 0.05863
16 V 1 py Cor( 3p) 0.99999 -2.54926
17 V 1 py Ryd( 7p) 0.00000 8.81512
18 V 1 py Ryd( 6p) 0.00000 1.63179
19 V 1 py Ryd( 5p) 0.00000 0.29796
20 V 1 py Ryd( 8p) 0.00000 24.86238
21 V 1 py Ryd( 4p) 0.00000 0.05868
22 V 1 pz Cor( 3p) 0.99982 -2.47820
23 V 1 pz Ryd( 7p) 0.00005 9.02763
24 V 1 pz Ryd( 6p) 0.00000 1.68405
25 V 1 pz Ryd( 5p) 0.00000 0.30298
26 V 1 pz Ryd( 8p) 0.00000 24.91136
27 V 1 pz Ryd( 4p) 0.00000 0.05991
28 V 1 dxy Val( 3d) 0.00000 -0.85898
29 V 1 dxy Ryd( 5d) 0.00000 0.41950
30 V 1 dxy Ryd( 4d) 0.00000 0.19238
31 V 1 dxz Val( 3d) 0.00000 -0.83276
32 V 1 dxz Ryd( 5d) 0.00000 0.42688
33 V 1 dxz Ryd( 4d) 0.00000 0.19581
34 V 1 dyz Val( 3d) 0.00001 -0.83161
35 V 1 dyz Ryd( 5d) 0.00000 0.42711
36 V 1 dyz Ryd( 4d) 0.00000 0.19582
37 V 1 dx2y2 Val( 3d) 0.00000 -0.85898
38 V 1 dx2y2 Ryd( 5d) 0.00000 0.41950
39 V 1 dx2y2 Ryd( 4d) 0.00000 0.19238
40 V 1 dz2 Val( 3d) 0.00034 -0.78095
41 V 1 dz2 Ryd( 5d) 0.00001 0.43531
42 V 1 dz2 Ryd( 4d) 0.00000 0.19329
43 V 1 f(0) Ryd( 4f) 0.00013 6.26350
44 V 1 f(C1) Ryd( 4f) 0.00000 3.37827
45 V 1 f(S1) Ryd( 4f) 0.00000 3.37890
46 V 1 f(C2) Ryd( 4f) 0.00000 1.46876
47 V 1 f(S2) Ryd( 4f) 0.00000 1.46876
48 V 1 f(C3) Ryd( 4f) 0.00001 4.50818
49 V 1 f(S3) Ryd( 4f) 0.00001 4.50821
[ 5 electrons found in the effective core potential]
WARNING: Population inversion found on atom V 1
Summary of Natural Population Analysis:
Natural Population
Natural -----------------------------------------------
Atom No Charge Core Valence Rydberg Total
-----------------------------------------------------------------------
V 1 2.50000 8.99944 0.00034 0.00022 9.00000
=======================================================================
* Total * 2.50000 8.99944 0.00034 0.00022 9.00000
Natural Population
--------------------------------------------------------
Effective Core 5.00000
Core 3.99944 ( 99.9859% of 4)
Valence 0.00034 ( 0.0000% of 0)
Natural Minimal Basis 8.99978 ( 99.9976% of 9)
Natural Rydberg Basis 0.00022 ( 0.0024% of 9)
--------------------------------------------------------
Atom No Natural Electron Configuration
----------------------------------------------------------------------------
V 1 [core]
NBO analysis skipped by request.
Test job not archived.
1|1|UNPC-UNK|SP|UB3PW91|SDD|V1(4+,2)|PCUSER|08-Dec-2013|0||# UB3PW91/S
DD SCRF=PCM POP=(NPA) TEST||Untitled-13||4,2|V,0,0.,0.,0.||Version=x86
-Win32-G98RevA.7|HF=-70.1624673|S2=0.750255|S2-1=0.|S2A=0.75|RMSD=1.46
0e-005|Dipole=0.,0.,0.|PG=KH||@
IT IS IMPOSSIBLE TO MEDITATE ON TIME AND THE MYSTERY
OF NATURE WITHOUT AN OVERWHELMING EMOTION AT THE
LIMITATIONS OF HUMAN INTELLIGENCE.
ALFRED NORTH WHITEHEAD
Job cpu time: 0 days 0 hours 0 minutes 34.0 seconds.
File lengths (MBytes): RWF= 33 Int= 0 D2E= 0 Chk= 10 Scr= 1
Dear Rangasamyy,
I am attaching a file relating the PtBr]6(2-)
Probably it will help you. I uses Gaussian System
%chk=C:\G03W\PRACTICE\ptbr6\bvp opt ptbr6-4.chk
%chk=1gb
# opt freq b3lyp/gen scrf=pcm pseudo=read test
bvp opt ptbr6-2
-2 1
Pt 0.00000000 0.00000000 0.00000000
Br 2.62905345 0.00000000 0.00000000
Br -2.62905345 0.00000000 0.00000000
Br 0.00000000 2.62905345 0.00000000
Br 0.00000000 -2.62905345 0.00000000
Br 0.00000000 0.00000000 2.62905345
Br 0.00000000 0.00000000 -2.62905345
pt br 0
lanl2dz
****
pt br 0
lanl2dz
Dear Rangasamy,
There is significant literature for QM studies of transition metals.
You should do a literature search for work carried out by the research groups of Michael Buhl and/or Robert Deeth. This should give you an idea of suitable density functionals, pseudo potentials and basis sets for transition metal studies.
Be careful is my advice, I used to use ADF a lot with Mike Drew.
You need to be careful about symmetry, if you set the complex as having some form of symmetry to reduce the number of atoms in the asymmetric unit then it is possible to get a different answer to a calculation where no such symmetry constraints are applied.
Think long and hard before you calculate to make sure that you do not bias the computational experiment to a given outcome.
Can density functional theory do this job, I used VASP to perform the calculation of transition metal oxide, and others.
Though it is not a direct help for Mr Rangasamy, I just want to add that I recently implemented with co-authors the energy gradients for the Random Phase Approximation (RPA) of the Correlation Energy, which is a correlated, parameter-free, ab initio method yielding promising results (general citations for RPA may be found in [1]).
A prototype version for RPA geometry optimizations is now implemented for closed shells in the Turbomole package (commercial code) and will become publicly available with the next release in February. Test calculations have shown that, in contrast to MP2, it correctly describes metal-ligand bonds in transition metal complexes with a comparable computational cost, which IS THE REASON WHY I POST THIS HERE.
Again this is preliminary work and the removal of bugs and further tuning (e.g., extension to open shells) by developers is most likely. But it is a reliable alternative for DFT and I just wanted you to keep an eye on this in the future.
For completeness, I also have to mention that there exists another preliminary RPA gradient work.[2] In addition, there exist slides in the internet from Bastien Mussard and Janos G. Angyan (please google these names together with 'RPA gradients') so that we may have another piece of code around soon.
---
citations:
[1] Burow J. Chem. Theory Comput. 2014 10 180.
[2] Rekkedal, J. Chem. Phys. 2013 139 081101.
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