Research Activities of the Morokuma Group

1
Research Activities of the Morokuma Group

• Cherry L. Emerson Center for Scientific
  Computation
• and Department of Chemistry,
• Cherry Logan Emerson Hall, Emory University
• Updated 3/28/2002

2
The Principle Theme of Research
Theoretical/Computational Studies of Chemical
Reactions and Electronic Structure of Molecular
Systemsfrom Elementary Reaction Dynamics
through Catalyses to Enzyme Reactions

• Theoretical Tools
• Ab initio Molecular Orbital Method
• Integrated Methods, Classical and Quantum
  Molecular Dynamics, Statistical Theory of
  Chemical Reactions
• Funding
• National Science Foundation, Air Force Office of
  Scientific Research, American Chemical Society
  Petroleum Research Fund, Gaussian, Inc.

3

• EC Visiting Fellows
• Postdoctoral Fellows
• Dr. Marcin Hoffmann
• Undergraduate Research Student
• Ms. Heather Abbott (sr.)
• Ms. Ji Yeon Ku (jr.)

• Graduate Students
• Mr. Dmitry V. Khoroshun(4th yr.)
• Mr. Ilja Khavruskii(3rd yr.)
• Mr. Sung J. Mo(3rd yr.)
• Mr. Graham Phillips (pmacs, ms)
• Mr. Peng Zhang (2nd yr.)
• Ms. Taraneh Nowroozi (1st yr.)
• Ms. Qingfang Wang (1st yr.)
• Mr. Guishan Zhang (1st yr.)
• Ms. Suwipa Saen-oon (visiting)

Emerson Center Collaborators Dr. Jamal Musaev
(Principal Scientist Manager) Dr. Stephan Irle
(associate Scientist System Manager)
4
Area 1. Gas Phase Elementary ReactionsDr.
Irle, Mr. Khoroshun, Mr. Phillips, Mr. Zhang, Ms.
Wang (past Dr. Eisfeld, Dr. Tschumper, Dr.
Kaledin) Potential energy surfaces and their
crossing for photodissociation and ion-molecule
reactions of small gas phase molecules.

• Excited States - Photodissociation Reaction
  Mechanism and Non-adiabatic Processes
• ClOOCl hn ? ClO ClO, Cl OOCl (air
  pollution, Dr. Kaledin 441)
• CH2CO hn ? CH2 CO (Dr. Kaledin 452, Mr.
  Phillips more)
• CH2CH hn ? CH?CH H, CH2C (air pollution
  Mr. Zhang)
• CH2CHO hn ? CH3 CO, CH2CO H (air
  pollution, Mr. Khoroshun)
• NO3 hn ? NO2 O (air pollution, Dr. Eisfeld
  442, 461 more)
• I(2P3/2) O2(a1?g) ? I(2P1/2) O2(X3??g)
  (chemical laser Dr. Kaledin 449)
• N3Cl ? NCl (singlet) or NCl(triplet) N2
  (chemical laser Mr. Phillips
• CH3CH2CH3 hn ? CH3CHCH3 H, CH3CH2CH2 H,
  CH2CHCH3 H2 , CHCH2CH3 H2 , CH3CHCH3 H2
  (Dr. Irle 443)
• refers the publication number in our
  publication list

5
Ion-Molecule Reactions O(4S) HCCH ? O(3P, 1D,
1S) HCCH (space shuttle reentry, Dr. Fukuzawa
465 more) O2 CH4 ? CH2OOH H, CH3
HOO, CH4 O2 (upper atmosphere, Dr. Irle,
453 ) Electronic, Photoelectron and Other
Spectroscopy Photoelectron spectra of IHBr
anion (Dr. Kaledin, 447) Isomerization state of
HCN ? HNC (Dr. Irle, Prof. Bowman 460)
Chemical Reactions in Cluster Micro-solvated
cluster reaction (H2O)nCH3Cl OH(H2O)m,
(nm1,2). (ONIOM application Dr. Re 463)
6
Photochemical Reactions and Ion-Molecule
Reactions Potential Energy Surfaces and their
Seam of Crossing
7
Ion - Molecule ReactionsFor Ionosphere Processes
8
Chemical Lasers the COILI O2(excited) ?
I(excited) O2I(excited) ? I light(laser)
9
Photodissociation Reactions Ozone Depletion
Event Cl O3 ??ClO O2
Cause
10
Vinoxy Excited States
11
Area 2. The ONIOM (Our own N-layered Integrated
molecular Orbital and molecular Mechanics)
Method--- Development and Applications Mr. Mo,
Dr. Irle (Past Dr. Vreven, Dr. Tschumper, Dr.
Liu, Dr. Karadakov) Develop the theory and code
for our own method for integrating different
levels of MO and MM methods for study of large
molecular systems

• Development and Enhancement of the ONIOM Code in
  Gaussian Package
• Development of new Gaussian code for ONIOM (Dr.
  Vreven 445)
• Enhancement of the Gaussian ONIOM with molecular
  mechanics
• ONIOM-PCM Polarized continuum model for
  solvation with the ONIOM method (Dr. Vreven
  462)

12
Calibration and Applications of ONIOM for
Accurate Bond Energies IMOMO-G2MS prediction of
bond dissociation energies of large
molecules ONIOM calculation of the bond breaking
energies on C60 Properties Other Than the
Energies with the ONIOM Method Calculating NMR
chemical shift and nuclear coupling (435,
more) Effects of Solvent on Chemical
Reactions Solvent effects in reactions in
cluster and solution (Mr. Mo, Dr.
Tschumper) Molecular Dynamics of Solution (Dr.
Kerdcharoen, 477) Other Applications Applicat
ion of ONIOM to fullerenes and nanomaterials (See
area 3) Homogenous catalysis control of
stereochemistry (See area 4) Enzymatic
reactions (See area 5)
13
(No Transcript)
14

15
Area 3. Computational Study of Nanomaterials
with ONIOM as Main Tool Dr. Irle, Mr. Zheng, Ms.
Ku (Past Dr. Vreven) Study of the structure,
energies, properties, reactivities and electronic
structure of nanomaterials, mainly using the
ONIOM method.
Application of ONIOM to Fullerenes and Their
DerivativesOpening the fullerene ring and
putting metal inside (Dr. Irle 470) Structure
and energies of cluster complexes (C60)m(Si)n
(Dr. Irle, Ms. Ku) Application of ONIOM to Carbon
Nanotubes Interactions and reactions between
carbon nanotubes, towards the design
of nanotube-based transistors Raman
spectroscopy of pristine and oxidized carbon
nanotubes
16
Inserting metal inside C60
Polymerizing C60 with Si atom
17
Model for molecular wire junctions in computer
circuits
Interaction between two (5,5) carbon nanotubes
being studied using the ONIOM method
18
Area 4. Structure and Reactions of Transition
Metal Complexes and Homogeneous CatalysesDr.
Musaev, Mr. Khoroshun, Mr. Khavruskii, Ms.
Nowrooozi (Past Dr. Sheng, Dr. Takao, Dr.
Torrent, Dr. Mori, Dr. Liu, Dr. Basch, Dr.
Moc)Electronic state, structure and energetics
of reactants, intermediates and transition
states of transition metal complexes in
organometallic and homogenous catalytic reactions.

• Olefin Polymerization Catalysts
• Olefin polymerization by Ni and Pd diimide
  catalysts
• Propylene and ethylene polymerization by
  zirconocene (Cp2ZrR) catalysts
• Search for new non-cyclopentadienyl catalysts
  (Dr. Musaev 450)
• Search for new titanium-chelating bridged
  catalysts for olefin polymerization
• Mechanism of olefin polymerization by
  bis(imino)pyridyl-Fe(II) catalysts (an ONIOM
  project) (Mr. Khoroshun 458, 472)
• Zn(II)-Catalyzed Alternating Copolymerization of
  CO2 with Epoxide
• (an ONIOM Project) (Dr. Liu, 473)

19
Molecular Nitrogen Activation and Related
Reactions Activation of N2 and H2 by
P2N2Zr(m-?2-N2)ZrP2N2, P2N2PhP(CH2SiMe2
NSiMe2CH2)2PPh (Dr. Musaev 440) Various
Organometallic and Homogenous Catalysis Systems
Oxidative Addition of Allyl-Ammonium Salts to
Low-Valent Metal Complexes (444) Vinyl-Vinyl
Reductive Coupling by Pt(IV) Complexes (Dr.
Ananikov 455 474) Ortho Selective Addition of
Aromatic CH Bond to Olefin by Ru(H)2(CO)(PR3)2
(434) Tungsten-catalyzed Endo- and
Exo-selective Cyclization of 1-Alkyn-5-ol (Dr.
Sheng 476) Hydrogen Scrambling in
(C5Me5)Os(dmpm) CH3H (ONIOM Study, Dr.Szilagyi
471)Reactivities of Bare Metal Clusters and
Their Ions Adsorption of Multiple H2 Molecules
on Pd3 and Pd4 Cluster (Dr.Moc 446)Reactivities
of Organocopper Complexes SN2 Alkylation of
Lithium Organocuprate Clusters with Alkyl Halides
and Epoxide (439) Asymmetric Reactions
Involving Transition Metal Complexes (an
ONIOM application)
20
Stepwise endo-cycloisomerization pathway most
favorable.
21
(No Transcript)
22
ONIOM Study of High-Activity Zn(II)-based
Catalysts for Alternating Copolymerization of
Carbon Dioxide and Epoxides
23
Area 5. Biomolecular Applications Structure
and Reactions of Enzymatic SystemsDr. Musaev,
Mr. Khavrtskii, Dr. Hoffmann (Past Dr. Torrent,
Dr. Sheng, Dr. Szylagyi, Dr. Basch, Dr. Vreven)
Application of quantum chemical and ONIOM methods
for structure, spectroscopy and reaction
mechanisms of biological systems, with emphasis
on metalloenzymes

• Reaction Mechanisms of Methane Monooxygenase
  (MMO) and Ribonucleotide Reductase (RNR) (Review
  468)
• Mechanism of the methane ? methanol conversion
  catalyzed by MMO (Dr. Basch 454, 466)
• Mechanism of carboxylate shift in MMO and RNR
  (Dr. Torrent 448)
• Mechanism of O2 activation in MMO and RNR (Dr.
  Torrent, Dr. Sheng 459 467)
• Structure and Mechanism in the Protein
  Environment (ONIOM Study) (Dr. Torrent, Mr.
  Khavrutskii, Dr. Hoffmann)

24
Nitrogenase Hydrogen bonded networks for
reactant and product channels (Dr. Szilagyi
437) Molybdenum-site and homocitrate ligand of
the FeMo-cofactor (Dr. Szilagyi
451)Bacteriorhodopsin, bR (OINOM
Studies) Excited states of retinal protonated
Schiff base with ONIOM (Dr. Vreven 434)
Excitation energy of bR in the protein with
ONIOM (Dr. Vreven) ONIOM study of the retinal
photoisomerization in bR Spectroscopy and
Structure in B12 Coenzyme System (collaboration
with Prof. Warnke of Physics) N nuclear
quadrupole parameters in imidazole derivatives
(Dr. Torrent) Nuclear Quadrupole Resonance for
Polypeptides (collaboration with Prof. Day of
Physics) Can alpha-helix and beta-sheet be
distinguished in N nuclear quadrupole resonance
spectroscopy? (Dr. Torrent 457)
25
Reaction Mechanism of Methane Monooxygenase (MMO)
26
Reaction Mechanism of Methane Monooxygenase (MMO)
27
Mainly by Maricel Torrent and Thom Vreven
28
(No Transcript)
29
(No Transcript)
30
(No Transcript)
31
ONIOM Potential Applications (Shopping List) The
IMOMM/IMOMO/ONIOM3 methods are very general and
flexible, and are applicable to a wide variety
of problems. Most promising High accuracy
combination ONIOM3(CCSD(T) or G2 MP2 or HF
MM) // IMOMM(MP2 or DFT MM) Most promising
Medium accuracy combination ONIOM3(DFT
semi-emp. MO MM)/ / IMOMM(DFT
MM) Thermochemistry Bond energies in large
molecules (nanomaterial) IMOMO Homogeneous
Catalysts IMOMM, ONIOM3 Heterogeneous
Catalysts (Surfaces, Zeolites) IMOMO, IMOMM,
ONIOM3 Regio- and Stereo-Selectivity in Organic
Reactions IMOMM, ONIOM3 Chemical Reactions in
Solution ONIOM3, ONIOM-PCM Biological Systems
(Enzyme Reactions) IMOMM, ONIOM3,
ONIOM-PCM Organic and Inorganic Material IMOMO,
IMOMM, ONIOM3
32
Chemical reactions are the heart of chemistry

• Avoid routine number-crunching!!
• (e.g., structure and reactions of the ground
  state of small molecules )
• Take a Challenge!!
• Multiple potential energy surfaces
• Large and complicated molecular systems
• (e.g., catalyses, biological, material, solution)
• Need Challenging Graduate Students and Postdocs!!

33