Chemistry 373

Friday, March 31, 2000

University of Calgary

Prof. Tom Ziegler - Department of Chemistry University of Calgary-Calgary,Alberta,Canada T2N 1N4

Computational Chemistry As A Practical Tool in Molecular Science"

Early Atomic theory 400 b.c.

John Dalton (1766 - 1844 )

Joseph Louis Gay-Lussac, Memoires de la Societe d'Arcueil 2:207 (1808)

"We are perhaps not far removed from the time when we shall be able to submit the bulk of chemical phenomena to calculation." -

- A. Comte, Philosophie Positive, 1830.

"Every attempt to employ mathematical methods in the study of chemical questions must be considered profoundly irrational and contrary to the spirit of chemistry.

Quantum Wave-Mechanics 1926

H(ri)(ri)= E(ri) i=1,3N Erwin Rudolf Josef Alexander Schrdinger 1 8 8 7 -1 9 6 1 Wer ner Kar l Heisenberg 1901-1976

H(ri)(ri)= E(ri) i=1,3N

`P.A.M. Dirac (1929)

"The underlying physical laws necessary for the mathematical theory of..the whole of chemistry are thus completely known, and the difficulty is only that the exact application of these laws leads to equations much to complicated to solve."

n!

Exact Quantum Wave-Mechanics

H(ri)(ri)= E(ri) i=1,3N H2 (1956) He (1930) Time required n! with number H2+ (1929) of electrons n H (1926)
Development

C6H6 (2000)

Electron Correlation ?

Exchange-correlation hole ? ? ?

Molecular Orbital Theory Diatomics Comparing MO and VB Theory

H H

A=1sA

B=1sB

Both terms describe 1 (1, 2)VB = [A(1)B (2) + A(2)B (1)] a covalent Bond 2
el. 1 H el. 2 H
el. 2 H el. 1 H

1 (1, 2)MO = [(A(1) + B (1)(A(2) + B (2)] 2 Equal 1 1 1 1 = A(1)B(2) + B (1)A(2) + A(1)A(2) + B(1)B(2) mixture of 2 2 2 2 el. 2 ionic and el. 2 el. 1 el. 2 el. 1 el. 2 covalent H H H H H H bond H H el. 1 el. 1 ov . ov . Ionic Ionic

Approximate Quantum Wave-Mechanics

Some theories are too true to be good

Hartree Atomic Theory

R.K.Mullikan Molecular Orbital theory

Some too good to be true

L.Pauling Valence Bond theory

J. Pople Systematic Improvements

Approximate Wave mechanics

log(t) Quadratic CI ( 10 atoms)

Dead End

Mller-Plesset (100 atoms)

Hartree Fock (2000 atoms)

Density Functional theory

Th omas-Fer mi-Dirac (1929)
Model expression of total energy in terms of electron density Fermi

E() Kohn-H ohenberg-Sham (1964)

Exact relationship between electron density and molecular energy .. ..but, form of relationship not known

E()
W. Kohn

Exchange-correlation hole ? ? ?

Approximate density functional theories for exchange and correlation

HFS
Local exchange

Exchange energy from electron gas Exchange+correlation from electron gas

Nonlocal Exchange: Becke,A.D. Phys.Rev. 1988,A38 Nonlocal Correlaion Perdew,J. Phys.Rev. 1986,B33

LSD
Local exchange + Local correlation

LSD/NL
Local exchange + Local correlation
+ Nonlocal corrections

Second generation Gradient Corrected Functionals

Axel Becke Queens University

John Perdew Tulane

1983-1992

Approximate density functional theories for exchange and correlation

HFS
Local exchange

Exchange energy from electron gas Exchange+correlation from electron gas

Nonlocal Exchange: Becke,A.D. Phys.Rev. 1988,A38 Nonlocal Correlaion Perdew,J. Phys.Rev. 1986,B33

LSD
Local exchange + Local correlation

LSD/NL
Local exchange + Local correlation
+ Nonlocal corrections

Nobel Prizes in Chemistry 1998

Walter Kohn

John Pople

E()

E = <||> E()

ACCURATE STRUCTURES FOR ACCURATE EXPECTATION VALUES

Transition State

Product(s) Reactant(s)

CO CO

Fe

Metal-ligand bond distances from HF and Xa calculations Bond Fe-Cp Fe-COax Fe-COeq HF 1.88 2.04 1.874 1.921 2.00 Xa 1.60 1.774 1.798 1.794 1.868

OC OC

Cr CO

CO

Mol Fe(Cp)2 Fe(CO)5

EXP 1.65 1.80 1.827 1.838 1.914

Ni(CO)4 Cr(CO)6

Ni-CO Cr-C

Fan and Ziegler ,J.Chem.Phys. 1991,95,7401

Metal-ligand bond distances from LDA and LDA/NL calculations Mol Fe(Cp)2 Fe(CO)5 Bond Fe-Cp Fe-COax Fe-COeq Ni(CO)4 Cr(CO)6 Ni-CO Cr-C LDA(HFS) 1.59 1.768 1.769 1.795 1.872 LDA/NL 1.65 1.817 1.814 1.841 1.909 EXP 1.66 1.807 1.827 1.838 1.914

Fan and Ziegler ,J.Chem.Phys. , 1991,95,7401

77.7 77.6
C

116.8 117.6
C O C O

96.0 96.1
C

Fe

252.3 252.3
C O

Fe

201.1 201.6

182.5 183.6
C

114.8 115.6
O

NL - SCF Experiment

Activation of catalyst
C
C

Al
C O

Al
O

Al
O

Al
C

Al
O

Al
O C

C
C

C
C

Zr

C C C

Biological molecul es Metal Sur faces Solids

ACCURATE ENERGETICS Transition State

Product(s) Reactant(s)

First metal-Carbon Dissociation Energy Molecule Cr(CO) 6 Mo(CO)6 W(CO)6 Fe(CO)5 Ni(CO)4 HFS 278 226 247 267 194 LDA 276 226 249 263 192 LDA/NL 193 166 183 192 121 Exp 192/155 170 192 176 104

Li+Schreckenbach+Ziegler J.Am.Chem.Soc,Sunmitted

Relativistic influence
40
E (kcal/mol)

O O

a 40 30 20 10

30 20 10
Ni Pd Pt

Ni

Pd

Pt

c
40
E (kcal/mol)

d
40 30 20 10

30 20 10

Ni

Pd

Pt

Fe

Ru

Os

: non-relativistic Li+Ziegler, Inorg.Chem, submitted

: relativistic

Energetics ???

Spin-flip

Vibrations

Conformations

Bond Breaking

Excitations

Ionizations and Affinities

Biological molecul es ( Hudrogen Bond Strength) Metal Sur faces (Adsorption Energies) Solids (Cohesive Energy)

Inorganic Spectroscopy hv
C C C C Cl C

Si

Zr
C C C C C

E H

Cl

EXCITED STATES
Photo Chemistry Electron Transfer

Excitations

hv

Ziegler,Rauk,Baerends Theor.Chim.Acta 1977,43,261

eV 6 a1-5t2 3t2-e 4t2-5t2 5

2 1T 2 1T 1 1T 1 1T 2 1T 1T

50 000 broad broad

Charge Transfer Spectrum of Permanganate

40 000 O O Mn 30 000 O
5t2 e t1 4t2 a1

t1-5t2 4t2-e

1T 2 1T 1 1T 2 1T 2 1T 1 3T 1 3T 2

sharp broad

3 t1-e 2
Determinants only Determinants and integrals

sharp weak

20 000

Metal-d

}
cm

Oxygen

Experiment

10 000 Orbital Diagram -1 cm -1

AOC

Ground state

R.Dickson + T.Ziegler, Int. J. Quantum Chem., 1995

ACCURATE FORCE FIELDS

Entropy of activation Spectroscopic finger printing Molecular Mechanics Force Fields

Vibrations

A.Berces and T.Ziegler Topics in Current Chemistry Springer 1996

no. 1 ' A1 3 2 4 A 1" 5 6 A 2' 7 A 2" 8 10 9 11 E1" 12 13 15 14 16

LDA

Exp.

3161 1086 791 305 1209 44 1210 3162 1088 777 458 3153 1370 966 770 362

3110 1102 814 309 1255 44 1250 3103 1110 820 478 3086 1410 998 844 389

no. E1' 17 18 20 19 21 22 E2' 23 26 24 25 27 28 E2" 29 32 30 31 33 34

LDA

Exp.

3155 1371 978 808 489 163 3138 1318 1014 838 790 562 3139 1337 1025 845 814 560

3077 1410 1005 855 492 179 3100 1356 1058 897d d 597 3085 1351 1055 885 d d 569

Calculated and observed vibrational frequ ncies of ferrocene

Fe

A.Berces+T.Ziegler J.Phys.Chem 1994

NMR-SPECTROSCOPY
Spectroscopic Finger printing

Spin-flip NMR/ESR

Spin-Spin Coupling Dickson+Ziegler Phys.Chem. 1996

Spin-spin coupling NMR/ESR

SHIFTS: Schreckenbach+Ziegler Phys.Chem. 1995

17O

shieldings in transition metal oxides [MO4]n-

O absolute shielding (ppm)

0 rel non-rel rel non-rel Experiment Experiment rel non-rel Experiment [MnO4]- [TcO4]- [ReO4]RuO4 OsO4

-200 -400 -600 -800

17

-1000 22[CrO4]2- [MoO4] [WO4]

Inorganic Tellurium shifts

3000 2500

Te=P(CH 3) 3 TeF 6 [TeBr 6] 2[Te 4] 2+(cyclic) TeSe 32[TeCl 6] 2Te(OH) 6 CH3OTeF6 500 1000 1500 2000 2500 3000

Calculated (ppm)

2000 1500 1000 500 0 -500 -1000 -1000-500 0

Experiment (ppm) Te=P( iPr)3 [Te 6] 4+(cyclic)

Organometallic Tellurium shifts

Me3P Me3P Te M Te Te PMe 3 Te PMe 3 Cl Pd Cl

3000 2500
Calculated (ppm)

2000 1500 1000 500 0 -500

M=W M=Mo Fe2(CO)6(-TeMe) 2 [Cp*Re(CO)2H(TeH)]

OC OC OC

trans-[Pd{Te(CH 2 )4}2Cl 2]
CH3 Te Fe Te CH3 H3 C Fe CO CO CO CH3 CH3

-1000 -1000 -500 0

H3 C

500 1000 1500 2000 2500 3000 Experiment (ppm)

H OC

Re

CH3 CO TeH

METAL-NMR SHIFTS

Compound

NMR Chemical Shifts Calculated NonRel Rel -1.810 -1.965 -3.619 -1.795 -1.857 -3.505 Exp

Cr(CO)6 Mo(CO)6 W(CO)6

-1.824 -1.807 -4.030

Schreckenbach+Ziegler Int.J.Quant.Chem. , 1997,61,899

Reduced K(M-C) Coupling Constants

Mo le cu le

K( M-C) Exp . 146 239 380 344 319 778 997

Khandogin+Ziegler Spectrochim. Acta 1999,55,607

Cal. V( CO) 6 129 Fe ( CO) 6 2 2 0 Co( CO)4 - 3 4 8 Mo ( CO) 6 2 9 3 Nb( CO) 6 - 2 6 2 Rh ( CO) 4 - 7 1 3 W( CO) 6 8 1 6
1019 Kg m-2 s -2 A -2

EPR g tensors in d1 porphyrine complexes of 3d transition metals

g|| g g

E: O, N, S, Se

M: V, Cr

L: Cl, H2O, none

Isotropic g values

M E

Biological molecules ( ESR of metal lo-proteins) Metal Surfaces (Ir of absorbed molecules) Solids (NMR of Solids) Astronomy (Molecules in out-space)

Static DFT Calculations

Transition State Tracing Reaction Path Localizing Stationary Points Reactant(s) Product(s)

ADF-Program by Baerends et al. Calgary extensions Local Spin Density Approximation +BP86

Alcohol Oxidation
O-H Addition CrCl2O2 + CH3OH CrCl2(OH)2+ CH2O

#
a e d c h f b g
Ha

+
Reactants TS1

Addition Product

b e g d c h f Ha

IRC for O-H Bond Addition Deng+Ziegler, Jacs 1996 hca i fcb
40 140

Distances (ngstroms)

3.0

Angles (Degrees)

2.0

c b

1.0 -10.0

f
0.0

g
10.0

-20

b e g d c h f Ha

IRC for O-H Bond Addition Deng+Ziegler, Jacs 1996 hca i fcb
40 140

Distances (ngstroms)

3.0

Angles (Degrees)

2.0

c b

1.0 -10.0

f
0.0

g
10.0

-20

Dynamic DFT Calculations

First principle dynamics by Car-Parrinello procedure Slow-growths Dynamics: Draging system along reaction coordinate. Full dynamics perpendicular to reaction coordinate Transition State

Reactant(s) Product(s)

Projector Augmented wave method P.Blchl Phys.Rev B 1994,B 50, 17953 Local Spin Density Approximation +BP86

Alkane Carbonylation
Cl H3P CO PH 3 Rh CH 3 # H CH 3 O 14-e PH 3 Cl Rh -C H3P O

h -CO

14-e PH 3 Cl Rh H3P

13
O

H O

1
+ CH 4 PH 3 Cl Rh H H C H3P H 3 H

CH 3 PH 3 Rh H CO CH 3 PH 3 Rh

Cl H3P + CO

CO+CH4
H CH 3 O

12
O Cl H3P

Cl Rh H3P

PH 3 H CH 3

11

4
Cl H3P # O C PH 3 Rh CH 3 H CO Cl Rh H3P H PH 3 CH 3 + CO Cl Rh H3P CH 3 H PH 3

10

Alkane Carbonylation
Cl H3P CO PH 3 Rh CH 3 # H CH 3 O 14-e PH 3 Cl Rh -C H3P O

h -CO

14-e PH 3 Cl Rh H3P

13
O

H O

1
+ CH 4 PH 3 Cl Rh H H C H3P H 3 H

CH 3 PH 3 Rh H CO CH 3 PH 3 Rh

Cl H3P + CO

CO+CH4
H CH 3 O

12
O Cl H3P

Cl Rh H3P

PH 3 H CH 3

11

4
Cl H3P # O C PH 3 Rh CH 3 H CO Cl Rh H3P H PH 3 CH 3 + CO Cl Rh H3P CH 3 H PH 3

10

Alkane Carbonylation
Cl H3P CO PH 3 Rh CH 3 # H CH 3 O 14-e PH 3 Cl Rh -C H3P O

h -CO

14-e PH 3 Cl Rh H3P

13
O

H O

1
+ CH 4 PH 3 Cl Rh H H C H3P H 3 H

CH 3 PH 3 Rh H CO CH 3 PH 3 Rh

Cl H3P + CO

CO+CH4
H CH 3 O

12
O Cl H3P

Cl Rh H3P

PH 3 H CH 3

11

4
Cl H3P # O C PH 3 Rh CH 3 H CO Cl Rh H3P H PH 3 CH 3 + CO Cl Rh H3P CH 3 H PH 3

10

Alkane Carbonylation
Cl H3P CO PH 3 Rh CH 3 # H CH 3 O 14-e PH 3 Cl Rh -C H3P O

h -CO

14-e PH 3 Cl Rh H3P

13
O

H O

1
+ CH 4 PH 3 Cl Rh H H C H3P H 3 H

CH 3 PH 3 Rh H CO CH 3 PH 3 Rh

Cl H3P + CO

CO+CH4
H CH 3 O

12
O Cl H3P

Cl Rh H3P

PH 3 H CH 3

11

4
Cl H3P # O C PH 3 Rh CH 3 H CO Cl Rh H3P H PH 3 CH 3 + CO Cl Rh H3P CH 3 H PH 3

10

Alkane Carbonylation Alkane Carbonylation

Cl

Cl

CO PH CO PH 3 3 Rh CH Rh CH 3
3

# #

H
O

CH 3
3

CH

Cl

Cl

14-e 14-e PH PH 3 Rh Rh- C

-C
3

h h -CO -CO

Cl
3

Cl

14-e 14-e -PH 3 PH 3

Rh

Rh

H P H 3P
3

13 13
O

H O H O CH CH 3
3

3 H3P

H P

OO

H P H 3P

2 2
+ CH + CH 4
4

1 1

O Rh Rh
CO

Cl

Cl

PH PH 3
3

H 3P
3

H P

+ CO

+ CO

12 12
O O
Cl

CO CH 3 CH 3

Cl Rh Rh

PH 3 PH 3
H

3 H3P

H P

11 11

Relative energies and structures of all sCO+CH4 olved pecies inv Rate dHter min3ing step e CH Insight forOmodifications and improvements
Cl

PH 3 PH 3 Cl Cl H Rh H H Rh C H H P HC H 3P 3 3 H H H 3

Cl

Cl Rh Rh

PH PH 3
3

3 H 3P

H P

H H

CH CH 3
3

Cl

O C C

O PH PH 3
3

#
Cl

CO

CO PH PH 3
3

4 4
Cl

Cl
Rh H

Cl
Rh

3 H 3P

H P

CH Rh CH 3 Rh 3
H

Rh H

Rh H H

PH 3 PH 3 CH 3 CH 3

3 H3P

H P

CH 3 CH 3
+ CO

3 H3P

H P

10

+ CO

5 5

Scope of Catalytic Investigation

1. CO + C2H 4 + H2 2. CO + C2H 4
Pd,Ni O H3C Rh,Ir OH H3C Rh O H3 C Rh,Co O C O H O

Hydroformylati on

3. MeOH + CO

Acetic Acid

4. CH4 + CO

C H

H H

5. C2H4 + HX
R

Rh

H H

Olefin additionX=H,B(OR)2:TeR
H

6.
'R

Cr,Mo

+
R 'R

Metathesis

Olefin Polymerization Catalysis Propagation Cp2M-R CH2 =CHCH3

Cp2M-CH CH(CH )R 2 3

Termination and Chain Transfer H2 Cp2M-R Termination and Chain Transfer H Cp2M-CH 2CH(CH 3)R Termination by CH activation Cp2M-R CH2=CHCH3

Cp2M-H + RH

Cp2M-H + CH2=C(CH 3)R

Cp2M-CH=C(CH3)R + RH

T.K.Woo,L.Fan,T.Ziegler:Organometallics 1994,13,432; 13,2253

Cobalt
Computers on benches all linked together