TY  - JOUR
AU  - Milovanović, Milan R.
AU  - Dohm, Sebastian
AU  - Hansen, Andreas
AU  - Djukic, Jean-Pierre
AU  - Zarić, Snežana D.
AU  - Grimme, Stefan
PY  - 2017
UR  - https://akcongress.com/jtacc
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6364
AB  - The London forces [1–3], or dispersion, are omnipresent in the nature. It constitutes an important part of the energy contribution to the stabilization of the tertiary structure of peptides, other natural polymers and the spontaneous coalescence of atomic aggregates or apolar molecules. The specifi city of the force of London is that it acts at long distances and it is always attractive, and it is therefore effective intramolecularly and determines in many situations the conformational behaviour of organic molecules and organometallics as well. It plays an essential role in chiral recognition and discrimination processes.
The understanding of certain still unknown aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for Dispersion. These allow to account for in a physically relevant way the effects of dispersion at medium and long distance [4]. For the further assessing the accuracy of static DFT-D calculations providing a referential of experimental data was found essential.
It has been shown that ITC techniques can provide reliable reaction enthalpy ΔHr, Gibbs free energy of reaction ΔGr and reaction entropy ΔSr as well [5]. Some recent studies showed good agreement between experimental and theoretical results [6–8]. This study will shed some light on the thermochemistry of the reactions in solution by preforming ITC experiments in chlorobenzene, from one side, and static DFT-D calculations at different levels of theory, from another side (Fig. 1). By comparison of obtained results one could conclude on the
excellent agreement between experimental and theoretical data, which could be promising for the further development and application of static DFT-D computational methods. As examples, the results of various organometallic reactions will be presented in some details [9].
T2  - 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary
T1  - Benchmarking to DFT-d calculations by ITC experimental data
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6364
ER  - 

@article{
author = "Milovanović, Milan R. and Dohm, Sebastian and Hansen, Andreas and Djukic, Jean-Pierre and Zarić, Snežana D. and Grimme, Stefan",
year = "2017",
abstract = "The London forces [1–3], or dispersion, are omnipresent in the nature. It constitutes an important part of the energy contribution to the stabilization of the tertiary structure of peptides, other natural polymers and the spontaneous coalescence of atomic aggregates or apolar molecules. The specifi city of the force of London is that it acts at long distances and it is always attractive, and it is therefore effective intramolecularly and determines in many situations the conformational behaviour of organic molecules and organometallics as well. It plays an essential role in chiral recognition and discrimination processes.
The understanding of certain still unknown aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for Dispersion. These allow to account for in a physically relevant way the effects of dispersion at medium and long distance [4]. For the further assessing the accuracy of static DFT-D calculations providing a referential of experimental data was found essential.
It has been shown that ITC techniques can provide reliable reaction enthalpy ΔHr, Gibbs free energy of reaction ΔGr and reaction entropy ΔSr as well [5]. Some recent studies showed good agreement between experimental and theoretical results [6–8]. This study will shed some light on the thermochemistry of the reactions in solution by preforming ITC experiments in chlorobenzene, from one side, and static DFT-D calculations at different levels of theory, from another side (Fig. 1). By comparison of obtained results one could conclude on the
excellent agreement between experimental and theoretical data, which could be promising for the further development and application of static DFT-D computational methods. As examples, the results of various organometallic reactions will be presented in some details [9].",
journal = "1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary",
title = "Benchmarking to DFT-d calculations by ITC experimental data",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6364"
}

Milovanović, M. R., Dohm, S., Hansen, A., Djukic, J., Zarić, S. D.,& Grimme, S.. (2017). Benchmarking to DFT-d calculations by ITC experimental data. in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary.
https://hdl.handle.net/21.15107/rcub_cherry_6364

Milovanović MR, Dohm S, Hansen A, Djukic J, Zarić SD, Grimme S. Benchmarking to DFT-d calculations by ITC experimental data. in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary. 2017;.
https://hdl.handle.net/21.15107/rcub_cherry_6364 .

Milovanović, Milan R., Dohm, Sebastian, Hansen, Andreas, Djukic, Jean-Pierre, Zarić, Snežana D., Grimme, Stefan, "Benchmarking to DFT-d calculations by ITC experimental data" in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary (2017),
https://hdl.handle.net/21.15107/rcub_cherry_6364 .

TY  - JOUR
AU  - Hansen, Andreas
AU  - Bannwarth, Christoph
AU  - Grimme, Stefan
AU  - Petrovic, Predrag V.
AU  - Werle, Christophe
AU  - Djukic, Jean-Pierre
PY  - 2014
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/5371
AB  - Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes
in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative
and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by
bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies
were measured by isotherm titration calorimetry (ITC) and theoretically ‘back-corrected’ to yield 0 K gas-phase reaction energies (DE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source
of error in theoretical thermochemistry protocols. The (‘backcorrected’) experimental reaction energies were used to
benchmark (dispersion-corrected) density functional and wave
function theory methods. Particularly, we investigated whether
the atom-pairwise D3 dispersion correction is also accurate for
transition metal chemistry, and how accurately recently developed local coupled-cluster methods describe the important
long-range electron correlation contributions. Both, modern
dispersion-corrected density functions (e.g., PW6B95-D3(BJ) or
B3LYP-NL), as well as the now possible DLPNO-CCSD(T) calculations, are within the ‘experimental’ gas phase reference value.
The remaining uncertainties of 2–3 kcalmol1 can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising
PB  - Wiley-VCH Verlag GmbH & Co. KGaA
T2  - ChemistryOpen
T1  - The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’
VL  - 3
SP  - 177
EP  - 189
DO  - 10.1002/open.201402017
ER  - 

@article{
author = "Hansen, Andreas and Bannwarth, Christoph and Grimme, Stefan and Petrovic, Predrag V. and Werle, Christophe and Djukic, Jean-Pierre",
year = "2014",
abstract = "Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes
in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative
and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by
bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies
were measured by isotherm titration calorimetry (ITC) and theoretically ‘back-corrected’ to yield 0 K gas-phase reaction energies (DE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source
of error in theoretical thermochemistry protocols. The (‘backcorrected’) experimental reaction energies were used to
benchmark (dispersion-corrected) density functional and wave
function theory methods. Particularly, we investigated whether
the atom-pairwise D3 dispersion correction is also accurate for
transition metal chemistry, and how accurately recently developed local coupled-cluster methods describe the important
long-range electron correlation contributions. Both, modern
dispersion-corrected density functions (e.g., PW6B95-D3(BJ) or
B3LYP-NL), as well as the now possible DLPNO-CCSD(T) calculations, are within the ‘experimental’ gas phase reference value.
The remaining uncertainties of 2–3 kcalmol1 can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
journal = "ChemistryOpen",
title = "The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’",
volume = "3",
pages = "177-189",
doi = "10.1002/open.201402017"
}

Hansen, A., Bannwarth, C., Grimme, S., Petrovic, P. V., Werle, C.,& Djukic, J.. (2014). The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’. in ChemistryOpen
Wiley-VCH Verlag GmbH & Co. KGaA., 3, 177-189.
https://doi.org/10.1002/open.201402017

Hansen A, Bannwarth C, Grimme S, Petrovic PV, Werle C, Djukic J. The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’. in ChemistryOpen. 2014;3:177-189.
doi:10.1002/open.201402017 .

Hansen, Andreas, Bannwarth, Christoph, Grimme, Stefan, Petrovic, Predrag V., Werle, Christophe, Djukic, Jean-Pierre, "The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’" in ChemistryOpen, 3 (2014):177-189,
https://doi.org/10.1002/open.201402017 . .

TY  - JOUR
AU  - Petrović, Predrag
AU  - Grimme, Stefan
AU  - Zarić, Snežana D.
AU  - Pfeffer, Michel
AU  - Đukić, Jean-Pierre
PY  - 2014
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1806
AB  - Self-aggregation in water of anti-cancer agents such as oxaliplatin (1) or its palladium-containing parent (2) is suspected to be the main reason for the exceptional resistance of concentrated infusions of these complexes to hydrolysis; this hypothesis, i.e. the self-association of metal chelates, was investigated in a systematic manner by experimental and theoretical means. H-1 diffusion-ordered NMR spectroscopy (DOSY NMR) and UV-visible absorption titration were inconclusive as to the formation of a dimer of 1 in water or DMSO. Further isothermal titration calorimetry (ITC) methods allowed the accurate determination of the enthalpy of formation of only the homodimer [2](2) and putative heterodimer [1.2] together with an estimation of the formation constants, which indicate that dimer formation is not a spontaneous process in solution, whereas electrospray ESI mass spectroscopy tends to suggest the contrary in the gas phase. A dispersion-corrected DFT method, i. e. DFT-D (BLYP-D3), was used to model the aggregation in solution (COSMO) and to investigate the assisting role of London force in the cohesion of bimolecular aggregates. The concordance of experimental and theoretical thermodynamic parameters was judged reasonably even though the treatment of solvation by conventional continuum models does not account for specific interactions of the solute with molecules of solvent; nonetheless these results outline the importance of dispersion, a.k.a. London force. The role of the latter was further stressed by computing the affinities of 1 and 2 for the lipophilic cavity of cucurbit[7]uril in modeled water (COSMO-RS), which were preliminarily determined experimentally by ITC methods using pure water as solvent. From our investigations carried out in pure water the connection between the notorious chemical stability of "concentrated'' infusions of 1 in aqueous media and the formation of oligomers remains unsettled.
PB  - Royal Soc Chemistry, Cambridge
T2  - Physical Chemistry Chemical Physics
T1  - Experimental and theoretical investigations of the self-association of oxaliplatin
VL  - 16
IS  - 28
SP  - 14688
EP  - 14698
DO  - 10.1039/c4cp01500b
ER  - 

@article{
author = "Petrović, Predrag and Grimme, Stefan and Zarić, Snežana D. and Pfeffer, Michel and Đukić, Jean-Pierre",
year = "2014",
abstract = "Self-aggregation in water of anti-cancer agents such as oxaliplatin (1) or its palladium-containing parent (2) is suspected to be the main reason for the exceptional resistance of concentrated infusions of these complexes to hydrolysis; this hypothesis, i.e. the self-association of metal chelates, was investigated in a systematic manner by experimental and theoretical means. H-1 diffusion-ordered NMR spectroscopy (DOSY NMR) and UV-visible absorption titration were inconclusive as to the formation of a dimer of 1 in water or DMSO. Further isothermal titration calorimetry (ITC) methods allowed the accurate determination of the enthalpy of formation of only the homodimer [2](2) and putative heterodimer [1.2] together with an estimation of the formation constants, which indicate that dimer formation is not a spontaneous process in solution, whereas electrospray ESI mass spectroscopy tends to suggest the contrary in the gas phase. A dispersion-corrected DFT method, i. e. DFT-D (BLYP-D3), was used to model the aggregation in solution (COSMO) and to investigate the assisting role of London force in the cohesion of bimolecular aggregates. The concordance of experimental and theoretical thermodynamic parameters was judged reasonably even though the treatment of solvation by conventional continuum models does not account for specific interactions of the solute with molecules of solvent; nonetheless these results outline the importance of dispersion, a.k.a. London force. The role of the latter was further stressed by computing the affinities of 1 and 2 for the lipophilic cavity of cucurbit[7]uril in modeled water (COSMO-RS), which were preliminarily determined experimentally by ITC methods using pure water as solvent. From our investigations carried out in pure water the connection between the notorious chemical stability of "concentrated'' infusions of 1 in aqueous media and the formation of oligomers remains unsettled.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Physical Chemistry Chemical Physics",
title = "Experimental and theoretical investigations of the self-association of oxaliplatin",
volume = "16",
number = "28",
pages = "14688-14698",
doi = "10.1039/c4cp01500b"
}

Petrović, P., Grimme, S., Zarić, S. D., Pfeffer, M.,& Đukić, J.. (2014). Experimental and theoretical investigations of the self-association of oxaliplatin. in Physical Chemistry Chemical Physics
Royal Soc Chemistry, Cambridge., 16(28), 14688-14698.
https://doi.org/10.1039/c4cp01500b

Petrović P, Grimme S, Zarić SD, Pfeffer M, Đukić J. Experimental and theoretical investigations of the self-association of oxaliplatin. in Physical Chemistry Chemical Physics. 2014;16(28):14688-14698.
doi:10.1039/c4cp01500b .

Petrović, Predrag, Grimme, Stefan, Zarić, Snežana D., Pfeffer, Michel, Đukić, Jean-Pierre, "Experimental and theoretical investigations of the self-association of oxaliplatin" in Physical Chemistry Chemical Physics, 16, no. 28 (2014):14688-14698,
https://doi.org/10.1039/c4cp01500b . .