Applications of ETSNOCV method in description of various

Applications of ETS-NOCV method in description of various types of chemical bonds Mariusz P. Mitoraj Jagiellonian University Cracow, Poland Department of Theoretical Chemistry ADF webinar, Kraków-rest-of-the-world, 28 th Feb. , 2014

Examples of theoretical quantities for visualization of chemical bond ADF webinar, Kraków-restoftheworld, 28 th Feb. , 2014

Formation of chemical bond in H 2 – based picture 1. Start from promolecular state (atom/fragments) H H H 2 H=1 s 2 H Deformation density (Differential density) (1) qualitative data by inspection of the sign of : negative (outflow), positive (inflow) of density due to bond formation ADF webinar, Kraków-restoftheworld, 28 th Feb. , 2014

The Natural Orbitals for Chemical Valence (NOCV) NOCV’s ( ) diagonalize the deformation density matrix: where P=P-P 0 , density matrix of the combined molecule, P 0 - density matrix of the considered molecular fragments. NOCV’s also decompose the deformation density : NOCV’s are in pairs: useful qualitative data by inspection of the sign of : negative (outflow), positive (inflow) of density Radoń, M. Theor Chem Account 2008, 120, 337. Mitoraj, M. ; Michalak, A. Organometallics 2007, 26(26); 6576. , Michalak, A. ; Mitoraj, M. ; Ziegler, T. J. Phys. Chem. A. 2008, 112 (9), 1933, Mitoraj, M. ; Michalak, A. J. Mol. Model. , 2008, 14, 681, Mitoraj, M. ; Zhu, H. ; Michalak, A. ; Ziegler, T. 2008, International Journal of Quantum Chemistry, DOI: 10. 1002/qua. 21910. , Mitoraj, M. ; Michalak, A. J. Mol. Model. 2008, 14, 681.

The contours of the deformation density ( ) and the contributions from the pairs of complementary orbitals for the heme/CO system q = 0. 74 q = 1. 04 donation back donation

A combination of ETS and NOCV - (ETS-NOCV) ETS: -De= Etotal= Edist + Eelstat + EPauli + Eorb electronic factor NOCV: ETS-NOCV: Energetic estimation of k Mariusz P. Mitoraj, Artur Michalak and Tom Ziegler „A combined charge and energy decom. Position scheme for bond analysis” J. Chem. Theory Comput. , 2009, 5 (4), pp 962– 975.

Dative bonds – systems with symmetry (CO)5 Cr=CH 2 donation back donation Donor/acceptor properties of ligands for Ni(NH 3)3 X complexes: : CN- > PH 3 > NH 3 > C 2 H 4 > CS > CO > N 2 > NO+ : NO+ > CS > CO > N 2 > C 2 H 4 > PH 3 > CN- > NH 3 Mitoraj Mariusz, Michalak A (2007) „ Donor-Acceptor Properties of Ligands from the Natural Orbitals for Chemical Valence” Organometallics, 26, 6576 -6580

Dative Bond NH 3 BH 3 - Calculations • Define closed shell fragments, NH 3 and BH 3 • Run SP calculations to get the fragment MO’s • Run SP ETS-NOCV calculations for whole molecule in the basis of previously calculated fragment MO’s

Dative Bond NH 3 BH 3 - Calculations M. Mitoraj J. Phys. Chem. A, 2011, 115 (51), pp 14708– 14716

Crystal of Ammonia Borane, NH 3 BH 3 M. Mitoraj J. Phys. Chem. A, 2011, 115 (51), pp 14708– 14716

Inter-Molecular-Hydrogen Bonds Adenine-Thymine kcal/mol, (BP 86/TZ 2 P) A-T Eint -13. 0 Eorb -22. 0 EPauli 38. 7 Eprep 2. 1 Eelstat -31. 9 Etotalexperiment 99 -12. 1 Etotal – other theoretical results Eorb=-22. 0 -13. 2 O *(H-N) N *(H-N) O-H H-N covalency! Rafał Kurczab, Mariusz P. Mitoraj, Artur Michalak and Tom Ziegler J. Phys. Chem. A, 2010, 114, 8581.

Hydrogen Bond A-T Calculations • Define closed shell fragments, Adenine and Thymine • Run SP calculations to get the fragment MO’s • Run SP ETS-NOCV calculations for whole molecule in the basis of previously calculated fragment MO’s ADF webinar, Kraków-restoftheworld, 28 th Feb. , 2014

Covalent bonds CH 3 -CH 3 CH 2=CH 2 Ge. H 2=Ge. H 2 H 3 CC CCH 3

Quadruple bond; Re 2 Cl 82 [-84. 3 kcal/mol] 2[-65. 5 kcal/mol] 1[-65. 5 kcal/mol] [-1. 3 kcal/mol]

Typical-Multiple bonds-TM Cr 2, formally sixtuple bond, b. Cr 2 -Nal = 6. 01 Etotal=-31. 3 kcal/mol Eorb=-242. 7 Esteric=211. 4 Eorb=-242. 7 kcal/mol J. Chem. Theory Comput. , 2009, 5 (4), pp 962– 975.

Ethane Built from two methyl radicals 1. Define CH 3 regions (uneven number of electrons); 2. Run SP RESTRICTED ! Calculations for CH 3 fragments to get the fragment MO’s; (1/2 + 1/2 electrons for SOMO of CH 3) 3. Use fragoccupations keyword in order to keep the right occupations for each CH 3 fragoccupations f 1 A 5 // 4 subend f 2 A 4 // 5 subend End 4. Run SP ETS-NOCV calculations for whole molecule in the basis of previously calculated fragment MO’s -alpha-and beta-NOCV’s

Typical-Multiple bonds-TM Cr 2, sextuple bond, b. Cr 2 -Nal = 6. 01 Etotal=-31. 3 kcal/mol Eorb=-242. 7 Esteric=211. 4 Eorb=-242. 7 kcal/mol J. Chem. Theory Comput. , 2009, 5 (4), pp 962– 975.

Cr 2 Built from two Cr + Cr 1. Define Cr regions (uneven number of electrons); 2. Run SP RESTRICTED ! Calculations for Cr fragments using OCCUPATION keyword (A 18 1 1 1); Should be like Cr but it is Cr 6* (1/2 + 1/2 ) so we must: 3. Use fragoccupations keyword in order to keep the right occupations for each Cr. fragoccupations Region_1 A 15//9 subend Region_2 A 9//15 subend End Cr 4. Run SP ETS-NOCV calculations for whole molecule in the basis of previously calculated fragment MO’s

Better Fragment MO’s from unrestriced run: advanced ’manual’ usage ADF uses in principle only ‚rectricted’ fragments, however, one might cheat him 1. Run open shell calculations for a given fragment; 2. Save tape 21 ascii (dmpkf) copy the final MO’s (from the section Eig-Core. SFO_A, MO’s expressed in SFO); 3. Run fragment calculations by setting SCF=0 wrong MO’s save tape 21 ascii find Eig-Core. SFO_A section, then: 4. Take MO’s and occupations, energies, from step 2 and paste them to Tape 21 from step 3…. . it gives you right fragment MO’s Transform ascii binary(udmpkf); 5. Rerun final ETSNOCV calculations (do not recalculate the fragments!)

Agostic intramolecular RH---Metal interaction Ni-diimine cationic Brookhart model catalyst Cb-H polarization Ni-Ca Ca-Cb Mariusz P. Mitoraj, Artur Michalak and Tom Ziegler „On the Nature of the Agostic Bond between Metal Centers and -Hydrogen Atoms in Alkyl Complexes. An Analysis Based on the Extended Transition State Method and the Natural Orbitals for Chemical Valence Scheme (ETS-NOCV)” Organometallics, 2009, 28 (13), pp 3727

Halogen Bonding CF 3 I---NH 3 from ETS-NOCV perspective Charge outflow, increase positive charge ETSNOCV(red-outflow, blue-inflow) N-I covalency -8. 3 kcal/mol N *(C-F) charge accumulation, increase s-character (pointed out by prof. Grabowski) Grabowski S. Chem. Rev. , 2011, 111 (4), pp 2597– 2625

Halogen Bonding CF 3 I---NH 3 from ETS-NOCV perspective Domination of the electrostatic factor is due to the presense of σ-hole on iodine atom: F F I F (Politzer P, Lane P, Concha MC, Ma Y, Murray J (2007) JMol. Model, 13, 305, „An Overview of Halogen Bonding”

Halogen Bonding CF 3 I---NH 3 from ETS-NOCV perspective Prof. Politzer, „Program & Book of Abstracts”, MIB 2011, „…. The weakness of this interpretation (electrostatic) is that it is simple and straightforward, and therefore is viewed by some with suspicion. (C-F) bond F F I -hole F Electrostatic potential picture Charge Anisotropy ETS-NOCV picture

Can ETS-NOCV discriminate between halogen and hydrogen bonding within the same molecule? Anion receptor based on urea, which involve hydrogen and halogen Bonding at the same time|: Chudzinski, et all, JACS, 2011, 133, 10559

Can ETS-NOCV discriminate between halogen and hydrogen bonding within the same molecule? -22. 3 kcal/mol -6. 3 kcal/mol Yes: ETS-NOCV can separate halogen and hydrogen connections

Cl- / rest • Define closed shell fragments, Cl minus + rest of the complex • Run SP calculations to get the fragment MO’s • Run SP ETS-NOCV calculations for whole molecule in the basis of previously calculated fragment MO’s ADF webinar, Kraków-restoftheworld, 28 th Feb. , 2014

Thank You very much for Your Attention! ADF webinar, Kraków-restoftheworld, 28 th Feb. , 2014