TY  - JOUR
AU  - Stepanović, Stepan
AU  - Lai, Rui
AU  - Elstner, Marcus
AU  - Gruden, Maja
AU  - Garcia-Fernandez, Pablo
AU  - Cui, Qiang
PY  - 2020
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/4299
AB  - To improve the description of interactions among the localized d, f electrons in transition metals, we have introduced a ligand-field motivated contribution into the Density Functional Tight Binding (DFTB) model. Referred to as DFTB3+U, the approach treats the d, f electron repulsions with rotationally invariant orbital–orbital interactions and a Hartree–Fock model; this represents a major conceptual improvement over the original DFTB3 approach, which treats the d, f-shell interactions in a highly averaged fashion without orbital level of description. The DFTB3+U approach is tested using a series of nickel compounds that feature Ni(II) and Ni(III) oxidation states. By using parameters developed with the original DFTB3 Hamiltonian and empirical +U parameters (F0/2/4 Slater integrals), we observe that the DFTB3+U model indeed provides substantial improvements over the original DFTB3 model for a number of properties of the nickel compounds, including the population and spin polarization of the d-shell, nature of the frontier orbitals, ligand field splitting and the energy different between low and high spin states at OPBE optimized structures. This proof-of-concept study suggests that with self-consistent parameterization of the electronic and +U parameters, the DFTB3+U model can develop into a promising model that can be used to efficiently study reactive events involving transition metals ion condensed phase systems. The methodology can be integrated with other approximate QM methods as well, such as the extended tight binding (xTB) approach.
PB  - American Chemical Society
T2  - Physical Chemistry Chemical Physics
T2  - Physical Chemistry Chemical PhysicsPhys. Chem. Chem. Phys.
T1  - Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds
VL  - 22
IS  - 46
SP  - 27084
EP  - 27095
DO  - 10.1039/D0CP04694A
ER  - 

@article{
author = "Stepanović, Stepan and Lai, Rui and Elstner, Marcus and Gruden, Maja and Garcia-Fernandez, Pablo and Cui, Qiang",
year = "2020",
abstract = "To improve the description of interactions among the localized d, f electrons in transition metals, we have introduced a ligand-field motivated contribution into the Density Functional Tight Binding (DFTB) model. Referred to as DFTB3+U, the approach treats the d, f electron repulsions with rotationally invariant orbital–orbital interactions and a Hartree–Fock model; this represents a major conceptual improvement over the original DFTB3 approach, which treats the d, f-shell interactions in a highly averaged fashion without orbital level of description. The DFTB3+U approach is tested using a series of nickel compounds that feature Ni(II) and Ni(III) oxidation states. By using parameters developed with the original DFTB3 Hamiltonian and empirical +U parameters (F0/2/4 Slater integrals), we observe that the DFTB3+U model indeed provides substantial improvements over the original DFTB3 model for a number of properties of the nickel compounds, including the population and spin polarization of the d-shell, nature of the frontier orbitals, ligand field splitting and the energy different between low and high spin states at OPBE optimized structures. This proof-of-concept study suggests that with self-consistent parameterization of the electronic and +U parameters, the DFTB3+U model can develop into a promising model that can be used to efficiently study reactive events involving transition metals ion condensed phase systems. The methodology can be integrated with other approximate QM methods as well, such as the extended tight binding (xTB) approach.",
publisher = "American Chemical Society",
journal = "Physical Chemistry Chemical Physics, Physical Chemistry Chemical PhysicsPhys. Chem. Chem. Phys.",
title = "Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds",
volume = "22",
number = "46",
pages = "27084-27095",
doi = "10.1039/D0CP04694A"
}

Stepanović, S., Lai, R., Elstner, M., Gruden, M., Garcia-Fernandez, P.,& Cui, Q.. (2020). Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds. in Physical Chemistry Chemical Physics
American Chemical Society., 22(46), 27084-27095.
https://doi.org/10.1039/D0CP04694A

Stepanović S, Lai R, Elstner M, Gruden M, Garcia-Fernandez P, Cui Q. Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds. in Physical Chemistry Chemical Physics. 2020;22(46):27084-27095.
doi:10.1039/D0CP04694A .

Stepanović, Stepan, Lai, Rui, Elstner, Marcus, Gruden, Maja, Garcia-Fernandez, Pablo, Cui, Qiang, "Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds" in Physical Chemistry Chemical Physics, 22, no. 46 (2020):27084-27095,
https://doi.org/10.1039/D0CP04694A . .

TY  - JOUR
AU  - Vujović, M.
AU  - Huynh, M.
AU  - Steiner, S.
AU  - Garcia-Fernandez, Pablo
AU  - Elstner, Marcus
AU  - Cui, Qiang
AU  - Gruden-Pavlović, Maja
PY  - 2019
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/353
AB  - In this work, we explore the applicability and limitations of the current third order density functional tight binding (DFTB3) formalism for treating transition metal ions using nickel as an example. To be consistent with recent parameterization of DFTB3 for copper, the parametrization for nickel is conducted in a spin-polarized formulation and with orbital-resolved Hubbard parameters and their charge derivatives. The performance of the current parameter set is evaluated based on structural and energetic properties of a set of nickel-containing compounds that involve biologically relevant ligands. Qualitatively similar to findings in previous studies of copper complexes, the DFTB3 results are more reliable for nickel complexes with neutral ligands than for charged ligands; nevertheless, encouraging agreement is noted in comparison to the reference method, B3LYP/aug-cc-pVTZ, especially for structural properties, including cases that exhibit Jahn–Teller distortions; the structures also compare favorably to available X-ray data in the Cambridge Crystallographic Database for a number of nickel-containing compounds. As to limitations, we find it is necessary to use different d shell Hubbard charge derivatives for Ni(I) and Ni(II), due to the distinct electronic configurations for the nickel ion in the respective complexes, and substantial errors are observed for ligand binding energies, especially for charged ligands, d orbital splitting energies and splitting between singlet and triplet spin states for Ni(II) compounds. These observations highlight that future improvement in intra-d correlation and ligand polarization is required to enable the application of the DFTB3 model to complex transition metal ions. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.
T2  - Journal of Computational Chemistry
T1  - Exploring the applicability of density functional tight binding to transition metal ions. Parameterization for nickel with the spin-polarized DFTB3 model
VL  - 40
SP  - 400
EP  - 413
DO  - 10.1002/jcc.25614
ER  - 

@article{
author = "Vujović, M. and Huynh, M. and Steiner, S. and Garcia-Fernandez, Pablo and Elstner, Marcus and Cui, Qiang and Gruden-Pavlović, Maja",
year = "2019",
abstract = "In this work, we explore the applicability and limitations of the current third order density functional tight binding (DFTB3) formalism for treating transition metal ions using nickel as an example. To be consistent with recent parameterization of DFTB3 for copper, the parametrization for nickel is conducted in a spin-polarized formulation and with orbital-resolved Hubbard parameters and their charge derivatives. The performance of the current parameter set is evaluated based on structural and energetic properties of a set of nickel-containing compounds that involve biologically relevant ligands. Qualitatively similar to findings in previous studies of copper complexes, the DFTB3 results are more reliable for nickel complexes with neutral ligands than for charged ligands; nevertheless, encouraging agreement is noted in comparison to the reference method, B3LYP/aug-cc-pVTZ, especially for structural properties, including cases that exhibit Jahn–Teller distortions; the structures also compare favorably to available X-ray data in the Cambridge Crystallographic Database for a number of nickel-containing compounds. As to limitations, we find it is necessary to use different d shell Hubbard charge derivatives for Ni(I) and Ni(II), due to the distinct electronic configurations for the nickel ion in the respective complexes, and substantial errors are observed for ligand binding energies, especially for charged ligands, d orbital splitting energies and splitting between singlet and triplet spin states for Ni(II) compounds. These observations highlight that future improvement in intra-d correlation and ligand polarization is required to enable the application of the DFTB3 model to complex transition metal ions. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.",
journal = "Journal of Computational Chemistry",
title = "Exploring the applicability of density functional tight binding to transition metal ions. Parameterization for nickel with the spin-polarized DFTB3 model",
volume = "40",
pages = "400-413",
doi = "10.1002/jcc.25614"
}

Vujović, M., Huynh, M., Steiner, S., Garcia-Fernandez, P., Elstner, M., Cui, Q.,& Gruden-Pavlović, M.. (2019). Exploring the applicability of density functional tight binding to transition metal ions. Parameterization for nickel with the spin-polarized DFTB3 model. in Journal of Computational Chemistry, 40, 400-413.
https://doi.org/10.1002/jcc.25614

Vujović M, Huynh M, Steiner S, Garcia-Fernandez P, Elstner M, Cui Q, Gruden-Pavlović M. Exploring the applicability of density functional tight binding to transition metal ions. Parameterization for nickel with the spin-polarized DFTB3 model. in Journal of Computational Chemistry. 2019;40:400-413.
doi:10.1002/jcc.25614 .

Vujović, M., Huynh, M., Steiner, S., Garcia-Fernandez, Pablo, Elstner, Marcus, Cui, Qiang, Gruden-Pavlović, Maja, "Exploring the applicability of density functional tight binding to transition metal ions. Parameterization for nickel with the spin-polarized DFTB3 model" in Journal of Computational Chemistry, 40 (2019):400-413,
https://doi.org/10.1002/jcc.25614 . .

TY  - DATA
AU  - Zlatar, Matija
AU  - Gruden-Pavlović, Maja
AU  - Vassilyeva, Olga Yu
AU  - Buvaylo, Elena A.
AU  - Ponomarev, A. N.
AU  - Zvyagin, S. A.
AU  - Wosnitza, J.
AU  - Krzystek, J.
AU  - Garcia-Fernandez, Pablo
AU  - Duboc, Carole
PY  - 2016
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/3587
PB  - Amer Chemical Soc, Washington
T2  - Inorganic Chemistry
T1  - Supplementary material for the article: Zlatar, M.; Gruden, M.; Vassilyeva, O. Y.; Buvaylo, E. A.; Ponomarev, A. N.; Zvyagin, S. A.; Wosnitza, J.; Krzystek, J.; Garcia-Fernandez, P.; Duboc, C. Origin of the Zero-Field Splitting in Mononuclear Octahedral MnIV Complexes: A Combined Experimental and Theoretical Investigation. Inorganic Chemistry 2016, 55 (3), 1192–1201. https://doi.org/10.1021/acs.inorgchem.5b02368
UR  - https://hdl.handle.net/21.15107/rcub_cherry_3587
ER  - 

@misc{
author = "Zlatar, Matija and Gruden-Pavlović, Maja and Vassilyeva, Olga Yu and Buvaylo, Elena A. and Ponomarev, A. N. and Zvyagin, S. A. and Wosnitza, J. and Krzystek, J. and Garcia-Fernandez, Pablo and Duboc, Carole",
year = "2016",
publisher = "Amer Chemical Soc, Washington",
journal = "Inorganic Chemistry",
title = "Supplementary material for the article: Zlatar, M.; Gruden, M.; Vassilyeva, O. Y.; Buvaylo, E. A.; Ponomarev, A. N.; Zvyagin, S. A.; Wosnitza, J.; Krzystek, J.; Garcia-Fernandez, P.; Duboc, C. Origin of the Zero-Field Splitting in Mononuclear Octahedral MnIV Complexes: A Combined Experimental and Theoretical Investigation. Inorganic Chemistry 2016, 55 (3), 1192–1201. https://doi.org/10.1021/acs.inorgchem.5b02368",
url = "https://hdl.handle.net/21.15107/rcub_cherry_3587"
}

Zlatar, M., Gruden-Pavlović, M., Vassilyeva, O. Y., Buvaylo, E. A., Ponomarev, A. N., Zvyagin, S. A., Wosnitza, J., Krzystek, J., Garcia-Fernandez, P.,& Duboc, C.. (2016). Supplementary material for the article: Zlatar, M.; Gruden, M.; Vassilyeva, O. Y.; Buvaylo, E. A.; Ponomarev, A. N.; Zvyagin, S. A.; Wosnitza, J.; Krzystek, J.; Garcia-Fernandez, P.; Duboc, C. Origin of the Zero-Field Splitting in Mononuclear Octahedral MnIV Complexes: A Combined Experimental and Theoretical Investigation. Inorganic Chemistry 2016, 55 (3), 1192–1201. https://doi.org/10.1021/acs.inorgchem.5b02368. in Inorganic Chemistry
Amer Chemical Soc, Washington..
https://hdl.handle.net/21.15107/rcub_cherry_3587

Zlatar M, Gruden-Pavlović M, Vassilyeva OY, Buvaylo EA, Ponomarev AN, Zvyagin SA, Wosnitza J, Krzystek J, Garcia-Fernandez P, Duboc C. Supplementary material for the article: Zlatar, M.; Gruden, M.; Vassilyeva, O. Y.; Buvaylo, E. A.; Ponomarev, A. N.; Zvyagin, S. A.; Wosnitza, J.; Krzystek, J.; Garcia-Fernandez, P.; Duboc, C. Origin of the Zero-Field Splitting in Mononuclear Octahedral MnIV Complexes: A Combined Experimental and Theoretical Investigation. Inorganic Chemistry 2016, 55 (3), 1192–1201. https://doi.org/10.1021/acs.inorgchem.5b02368. in Inorganic Chemistry. 2016;.
https://hdl.handle.net/21.15107/rcub_cherry_3587 .

Zlatar, Matija, Gruden-Pavlović, Maja, Vassilyeva, Olga Yu, Buvaylo, Elena A., Ponomarev, A. N., Zvyagin, S. A., Wosnitza, J., Krzystek, J., Garcia-Fernandez, Pablo, Duboc, Carole, "Supplementary material for the article: Zlatar, M.; Gruden, M.; Vassilyeva, O. Y.; Buvaylo, E. A.; Ponomarev, A. N.; Zvyagin, S. A.; Wosnitza, J.; Krzystek, J.; Garcia-Fernandez, P.; Duboc, C. Origin of the Zero-Field Splitting in Mononuclear Octahedral MnIV Complexes: A Combined Experimental and Theoretical Investigation. Inorganic Chemistry 2016, 55 (3), 1192–1201. https://doi.org/10.1021/acs.inorgchem.5b02368" in Inorganic Chemistry (2016),
https://hdl.handle.net/21.15107/rcub_cherry_3587 .

TY  - JOUR
AU  - Fitzpatrick, Anthony J.
AU  - Stepanović, Stepan
AU  - Mueller-Bunz, Helge
AU  - Gruden-Pavlović, Maja
AU  - Garcia-Fernandez, Pablo
AU  - Morgan, Grace G.
PY  - 2016
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1912
AB  - Magnetic, structural and computational data of four complex salts with the same mononuclear high spin octahedral Mn(III) complex cation are reported. The manifestation of Jahn-Teller-like distortions in the Mn(III) cation is dependent on the nature of the charge-balancing anion, with small anions yielding a planar elongation and large anions freezing out a preferential axial elongation along one of the amine-Mn-imine directions within that same plane. Modulation of the lattice by changing the charge balancing anion results in mixing of the orbital symmetry due to vibrational perturbation.
PB  - Royal Soc Chemistry, Cambridge
T2  - Dalton Transactions
T1  - Challenges in assignment of orbital populations in a high spin manganese(III) complex
VL  - 45
IS  - 15
SP  - 6702
EP  - 6708
DO  - 10.1039/c5dt03914b
ER  - 

@article{
author = "Fitzpatrick, Anthony J. and Stepanović, Stepan and Mueller-Bunz, Helge and Gruden-Pavlović, Maja and Garcia-Fernandez, Pablo and Morgan, Grace G.",
year = "2016",
abstract = "Magnetic, structural and computational data of four complex salts with the same mononuclear high spin octahedral Mn(III) complex cation are reported. The manifestation of Jahn-Teller-like distortions in the Mn(III) cation is dependent on the nature of the charge-balancing anion, with small anions yielding a planar elongation and large anions freezing out a preferential axial elongation along one of the amine-Mn-imine directions within that same plane. Modulation of the lattice by changing the charge balancing anion results in mixing of the orbital symmetry due to vibrational perturbation.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Dalton Transactions",
title = "Challenges in assignment of orbital populations in a high spin manganese(III) complex",
volume = "45",
number = "15",
pages = "6702-6708",
doi = "10.1039/c5dt03914b"
}

Fitzpatrick, A. J., Stepanović, S., Mueller-Bunz, H., Gruden-Pavlović, M., Garcia-Fernandez, P.,& Morgan, G. G.. (2016). Challenges in assignment of orbital populations in a high spin manganese(III) complex. in Dalton Transactions
Royal Soc Chemistry, Cambridge., 45(15), 6702-6708.
https://doi.org/10.1039/c5dt03914b

Fitzpatrick AJ, Stepanović S, Mueller-Bunz H, Gruden-Pavlović M, Garcia-Fernandez P, Morgan GG. Challenges in assignment of orbital populations in a high spin manganese(III) complex. in Dalton Transactions. 2016;45(15):6702-6708.
doi:10.1039/c5dt03914b .

Fitzpatrick, Anthony J., Stepanović, Stepan, Mueller-Bunz, Helge, Gruden-Pavlović, Maja, Garcia-Fernandez, Pablo, Morgan, Grace G., "Challenges in assignment of orbital populations in a high spin manganese(III) complex" in Dalton Transactions, 45, no. 15 (2016):6702-6708,
https://doi.org/10.1039/c5dt03914b . .

TY  - JOUR
AU  - Fitzpatrick, Anthony J.
AU  - Stepanović, Stepan
AU  - Mueller-Bunz, Helge
AU  - Gruden-Pavlović, Maja
AU  - Garcia-Fernandez, Pablo
AU  - Morgan, Grace G.
PY  - 2016
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/3395
AB  - Magnetic, structural and computational data of four complex salts with the same mononuclear high spin octahedral Mn(III) complex cation are reported. The manifestation of Jahn-Teller-like distortions in the Mn(III) cation is dependent on the nature of the charge-balancing anion, with small anions yielding a planar elongation and large anions freezing out a preferential axial elongation along one of the amine-Mn-imine directions within that same plane. Modulation of the lattice by changing the charge balancing anion results in mixing of the orbital symmetry due to vibrational perturbation.
PB  - Royal Soc Chemistry, Cambridge
T2  - Dalton Transactions
T1  - Challenges in assignment of orbital populations in a high spin manganese(III) complex
VL  - 45
IS  - 15
SP  - 6702
EP  - 6708
DO  - 10.1039/c5dt03914b
ER  - 

@article{
author = "Fitzpatrick, Anthony J. and Stepanović, Stepan and Mueller-Bunz, Helge and Gruden-Pavlović, Maja and Garcia-Fernandez, Pablo and Morgan, Grace G.",
year = "2016",
abstract = "Magnetic, structural and computational data of four complex salts with the same mononuclear high spin octahedral Mn(III) complex cation are reported. The manifestation of Jahn-Teller-like distortions in the Mn(III) cation is dependent on the nature of the charge-balancing anion, with small anions yielding a planar elongation and large anions freezing out a preferential axial elongation along one of the amine-Mn-imine directions within that same plane. Modulation of the lattice by changing the charge balancing anion results in mixing of the orbital symmetry due to vibrational perturbation.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Dalton Transactions",
title = "Challenges in assignment of orbital populations in a high spin manganese(III) complex",
volume = "45",
number = "15",
pages = "6702-6708",
doi = "10.1039/c5dt03914b"
}

Fitzpatrick, A. J., Stepanović, S., Mueller-Bunz, H., Gruden-Pavlović, M., Garcia-Fernandez, P.,& Morgan, G. G.. (2016). Challenges in assignment of orbital populations in a high spin manganese(III) complex. in Dalton Transactions
Royal Soc Chemistry, Cambridge., 45(15), 6702-6708.
https://doi.org/10.1039/c5dt03914b

Fitzpatrick AJ, Stepanović S, Mueller-Bunz H, Gruden-Pavlović M, Garcia-Fernandez P, Morgan GG. Challenges in assignment of orbital populations in a high spin manganese(III) complex. in Dalton Transactions. 2016;45(15):6702-6708.
doi:10.1039/c5dt03914b .

Fitzpatrick, Anthony J., Stepanović, Stepan, Mueller-Bunz, Helge, Gruden-Pavlović, Maja, Garcia-Fernandez, Pablo, Morgan, Grace G., "Challenges in assignment of orbital populations in a high spin manganese(III) complex" in Dalton Transactions, 45, no. 15 (2016):6702-6708,
https://doi.org/10.1039/c5dt03914b . .

TY  - DATA
AU  - Fitzpatrick, Anthony J.
AU  - Stepanović, Stepan
AU  - Mueller-Bunz, Helge
AU  - Gruden-Pavlović, Maja
AU  - Garcia-Fernandez, Pablo
AU  - Morgan, Grace G.
PY  - 2016
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/3396
PB  - Royal Soc Chemistry, Cambridge
T2  - Dalton Transactions
T1  - Supplementary data for the article: Fitzpatrick, A. J.; Stepanovic, S.; Müller-Bunz, H.; Gruden-Pavlović, M. A.; García-Fernández, P.; Morgan, G. G. Challenges in Assignment of Orbital Populations in a High Spin Manganese(Iii) Complex. Dalton Transactions 2016, 45 (15), 6702–6708. https://doi.org/10.1039/c5dt03914b
UR  - https://hdl.handle.net/21.15107/rcub_cherry_3396
ER  - 

@misc{
author = "Fitzpatrick, Anthony J. and Stepanović, Stepan and Mueller-Bunz, Helge and Gruden-Pavlović, Maja and Garcia-Fernandez, Pablo and Morgan, Grace G.",
year = "2016",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Dalton Transactions",
title = "Supplementary data for the article: Fitzpatrick, A. J.; Stepanovic, S.; Müller-Bunz, H.; Gruden-Pavlović, M. A.; García-Fernández, P.; Morgan, G. G. Challenges in Assignment of Orbital Populations in a High Spin Manganese(Iii) Complex. Dalton Transactions 2016, 45 (15), 6702–6708. https://doi.org/10.1039/c5dt03914b",
url = "https://hdl.handle.net/21.15107/rcub_cherry_3396"
}

Fitzpatrick, A. J., Stepanović, S., Mueller-Bunz, H., Gruden-Pavlović, M., Garcia-Fernandez, P.,& Morgan, G. G.. (2016). Supplementary data for the article: Fitzpatrick, A. J.; Stepanovic, S.; Müller-Bunz, H.; Gruden-Pavlović, M. A.; García-Fernández, P.; Morgan, G. G. Challenges in Assignment of Orbital Populations in a High Spin Manganese(Iii) Complex. Dalton Transactions 2016, 45 (15), 6702–6708. https://doi.org/10.1039/c5dt03914b. in Dalton Transactions
Royal Soc Chemistry, Cambridge..
https://hdl.handle.net/21.15107/rcub_cherry_3396

Fitzpatrick AJ, Stepanović S, Mueller-Bunz H, Gruden-Pavlović M, Garcia-Fernandez P, Morgan GG. Supplementary data for the article: Fitzpatrick, A. J.; Stepanovic, S.; Müller-Bunz, H.; Gruden-Pavlović, M. A.; García-Fernández, P.; Morgan, G. G. Challenges in Assignment of Orbital Populations in a High Spin Manganese(Iii) Complex. Dalton Transactions 2016, 45 (15), 6702–6708. https://doi.org/10.1039/c5dt03914b. in Dalton Transactions. 2016;.
https://hdl.handle.net/21.15107/rcub_cherry_3396 .

Fitzpatrick, Anthony J., Stepanović, Stepan, Mueller-Bunz, Helge, Gruden-Pavlović, Maja, Garcia-Fernandez, Pablo, Morgan, Grace G., "Supplementary data for the article: Fitzpatrick, A. J.; Stepanovic, S.; Müller-Bunz, H.; Gruden-Pavlović, M. A.; García-Fernández, P.; Morgan, G. G. Challenges in Assignment of Orbital Populations in a High Spin Manganese(Iii) Complex. Dalton Transactions 2016, 45 (15), 6702–6708. https://doi.org/10.1039/c5dt03914b" in Dalton Transactions (2016),
https://hdl.handle.net/21.15107/rcub_cherry_3396 .

TY  - JOUR
AU  - Zlatar, Matija
AU  - Gruden-Pavlović, Maja
AU  - Vassilyeva, Olga Yu
AU  - Buvaylo, Elena A.
AU  - Ponomarev, A. N.
AU  - Zvyagin, S. A.
AU  - Wosnitza, J.
AU  - Krzystek, J.
AU  - Garcia-Fernandez, Pablo
AU  - Duboc, Carole
PY  - 2016
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/2038
AB  - The aim of this work was to determine and understand the origin of the electronic properties of Mn-IV complexes, especially the zero-field splitting (ZFS), through a combined experimental and theoretical investigation on five well-characterized mononuclear octahedral Mn-IV compounds, with various coordination spheres (N-6, N3O3, N2O4 in both trans (trans-N2O4) and cis configurations (cis-N2O4) and O4S2). High-frequency and -field EPR (HFEPR) spectroscopy has been applied to determine the ZFS parameters of two of MnLtrans-N2O4 and Mn(LO4S)2 these compounds,. While at X-band EPR, the axial-component of the ZFS tensor, D, was estimated to be +0.47 cm(-1) for MnLO4S2, and a D-value of +2.289(5) cm(-1) was determined by HFEPR, which is the largest D-magnitude ever measured for a Mn-IV complex. A moderate D value of -0.997(6) cm(-1) has been found for MnLtrans-N2O4. Quantum chemical calculations based on two theoretical frameworks (the Density Functional Theory based on a coupled perturbed approach (CP-DFT) and the hybrid Ligand-Field DFT (LF-DFT)) have been performed to define appropriate methodologies to calculate the ZFS tensor for Mn-IV centers, to predict the orientation of the magnetic axes with respect to the molecular ones, and to define and quantify the physical origin of the different contributions to the ZFS. Except in the case of MnLtrans-N2O4, the experimental and calculated D values are in good agreement, and the sign of D is well predicted, LF-DFT being more satisfactory than CP-DFT. The calculations performed on MnLcis-N2O4 are consistent with the orientation of the principal anisotropic axis determined by single-crystal EPR, validating the calculated ZFS tensor orientation. The different contributions to D were analyzed demonstrating that the d-d transitions mainly govern D in Mn-IV ion. However, a deep analysis evidences that many factors enter into the game, explaining why no obvious magnetostructural correlations can be drawn in this series of Mn-IV complexes.
PB  - Amer Chemical Soc, Washington
T2  - Inorganic Chemistry
T1  - Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation
VL  - 55
IS  - 3
SP  - 1192
EP  - 1201
DO  - 10.1021/acs.inorgchem.5b02368
ER  - 

@article{
author = "Zlatar, Matija and Gruden-Pavlović, Maja and Vassilyeva, Olga Yu and Buvaylo, Elena A. and Ponomarev, A. N. and Zvyagin, S. A. and Wosnitza, J. and Krzystek, J. and Garcia-Fernandez, Pablo and Duboc, Carole",
year = "2016",
abstract = "The aim of this work was to determine and understand the origin of the electronic properties of Mn-IV complexes, especially the zero-field splitting (ZFS), through a combined experimental and theoretical investigation on five well-characterized mononuclear octahedral Mn-IV compounds, with various coordination spheres (N-6, N3O3, N2O4 in both trans (trans-N2O4) and cis configurations (cis-N2O4) and O4S2). High-frequency and -field EPR (HFEPR) spectroscopy has been applied to determine the ZFS parameters of two of MnLtrans-N2O4 and Mn(LO4S)2 these compounds,. While at X-band EPR, the axial-component of the ZFS tensor, D, was estimated to be +0.47 cm(-1) for MnLO4S2, and a D-value of +2.289(5) cm(-1) was determined by HFEPR, which is the largest D-magnitude ever measured for a Mn-IV complex. A moderate D value of -0.997(6) cm(-1) has been found for MnLtrans-N2O4. Quantum chemical calculations based on two theoretical frameworks (the Density Functional Theory based on a coupled perturbed approach (CP-DFT) and the hybrid Ligand-Field DFT (LF-DFT)) have been performed to define appropriate methodologies to calculate the ZFS tensor for Mn-IV centers, to predict the orientation of the magnetic axes with respect to the molecular ones, and to define and quantify the physical origin of the different contributions to the ZFS. Except in the case of MnLtrans-N2O4, the experimental and calculated D values are in good agreement, and the sign of D is well predicted, LF-DFT being more satisfactory than CP-DFT. The calculations performed on MnLcis-N2O4 are consistent with the orientation of the principal anisotropic axis determined by single-crystal EPR, validating the calculated ZFS tensor orientation. The different contributions to D were analyzed demonstrating that the d-d transitions mainly govern D in Mn-IV ion. However, a deep analysis evidences that many factors enter into the game, explaining why no obvious magnetostructural correlations can be drawn in this series of Mn-IV complexes.",
publisher = "Amer Chemical Soc, Washington",
journal = "Inorganic Chemistry",
title = "Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation",
volume = "55",
number = "3",
pages = "1192-1201",
doi = "10.1021/acs.inorgchem.5b02368"
}

Zlatar, M., Gruden-Pavlović, M., Vassilyeva, O. Y., Buvaylo, E. A., Ponomarev, A. N., Zvyagin, S. A., Wosnitza, J., Krzystek, J., Garcia-Fernandez, P.,& Duboc, C.. (2016). Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation. in Inorganic Chemistry
Amer Chemical Soc, Washington., 55(3), 1192-1201.
https://doi.org/10.1021/acs.inorgchem.5b02368

Zlatar M, Gruden-Pavlović M, Vassilyeva OY, Buvaylo EA, Ponomarev AN, Zvyagin SA, Wosnitza J, Krzystek J, Garcia-Fernandez P, Duboc C. Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation. in Inorganic Chemistry. 2016;55(3):1192-1201.
doi:10.1021/acs.inorgchem.5b02368 .

Zlatar, Matija, Gruden-Pavlović, Maja, Vassilyeva, Olga Yu, Buvaylo, Elena A., Ponomarev, A. N., Zvyagin, S. A., Wosnitza, J., Krzystek, J., Garcia-Fernandez, Pablo, Duboc, Carole, "Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation" in Inorganic Chemistry, 55, no. 3 (2016):1192-1201,
https://doi.org/10.1021/acs.inorgchem.5b02368 . .

TY  - DATA
AU  - Perić, Marko
AU  - Garcia-Fuente, Amador
AU  - Zlatar, Matija
AU  - Daul, Claude
AU  - Stepanović, Stepan
AU  - Garcia-Fernandez, Pablo
AU  - Gruden-Pavlović, Maja
PY  - 2015
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/3382
PB  - Wiley-V C H Verlag Gmbh, Weinheim
T2  - Chemistry. A European Journal
T1  - Supplementary data for article: Perić, M.; García-Fuente, A.; Zlatar, M.; Daul, C.; Stepanović, S.; García-Fernández, P.; Gruden-Pavlović, M. Magnetic Anisotropy in “Scorpionate” First-Row Transition-Metal Complexes: A Theoretical Investigation. Chemistry - A European Journal 2015, 21 (9), 3716–3726. https://doi.org/10.1002/chem.201405480
UR  - https://hdl.handle.net/21.15107/rcub_cherry_3382
ER  - 

@misc{
author = "Perić, Marko and Garcia-Fuente, Amador and Zlatar, Matija and Daul, Claude and Stepanović, Stepan and Garcia-Fernandez, Pablo and Gruden-Pavlović, Maja",
year = "2015",
publisher = "Wiley-V C H Verlag Gmbh, Weinheim",
journal = "Chemistry. A European Journal",
title = "Supplementary data for article: Perić, M.; García-Fuente, A.; Zlatar, M.; Daul, C.; Stepanović, S.; García-Fernández, P.; Gruden-Pavlović, M. Magnetic Anisotropy in “Scorpionate” First-Row Transition-Metal Complexes: A Theoretical Investigation. Chemistry - A European Journal 2015, 21 (9), 3716–3726. https://doi.org/10.1002/chem.201405480",
url = "https://hdl.handle.net/21.15107/rcub_cherry_3382"
}

Perić, M., Garcia-Fuente, A., Zlatar, M., Daul, C., Stepanović, S., Garcia-Fernandez, P.,& Gruden-Pavlović, M.. (2015). Supplementary data for article: Perić, M.; García-Fuente, A.; Zlatar, M.; Daul, C.; Stepanović, S.; García-Fernández, P.; Gruden-Pavlović, M. Magnetic Anisotropy in “Scorpionate” First-Row Transition-Metal Complexes: A Theoretical Investigation. Chemistry - A European Journal 2015, 21 (9), 3716–3726. https://doi.org/10.1002/chem.201405480. in Chemistry. A European Journal
Wiley-V C H Verlag Gmbh, Weinheim..
https://hdl.handle.net/21.15107/rcub_cherry_3382

Perić M, Garcia-Fuente A, Zlatar M, Daul C, Stepanović S, Garcia-Fernandez P, Gruden-Pavlović M. Supplementary data for article: Perić, M.; García-Fuente, A.; Zlatar, M.; Daul, C.; Stepanović, S.; García-Fernández, P.; Gruden-Pavlović, M. Magnetic Anisotropy in “Scorpionate” First-Row Transition-Metal Complexes: A Theoretical Investigation. Chemistry - A European Journal 2015, 21 (9), 3716–3726. https://doi.org/10.1002/chem.201405480. in Chemistry. A European Journal. 2015;.
https://hdl.handle.net/21.15107/rcub_cherry_3382 .

Perić, Marko, Garcia-Fuente, Amador, Zlatar, Matija, Daul, Claude, Stepanović, Stepan, Garcia-Fernandez, Pablo, Gruden-Pavlović, Maja, "Supplementary data for article: Perić, M.; García-Fuente, A.; Zlatar, M.; Daul, C.; Stepanović, S.; García-Fernández, P.; Gruden-Pavlović, M. Magnetic Anisotropy in “Scorpionate” First-Row Transition-Metal Complexes: A Theoretical Investigation. Chemistry - A European Journal 2015, 21 (9), 3716–3726. https://doi.org/10.1002/chem.201405480" in Chemistry. A European Journal (2015),
https://hdl.handle.net/21.15107/rcub_cherry_3382 .

TY  - JOUR
AU  - Perić, Marko
AU  - Garcia-Fuente, Amador
AU  - Zlatar, Matija
AU  - Daul, Claude
AU  - Stepanović, Stepan
AU  - Garcia-Fernandez, Pablo
AU  - Gruden-Pavlović, Maja
PY  - 2015
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1667
AB  - In this work we have analyzed in detail the magnetic anisotropy in a series of hydrotris(pyrazolyl)borate (Tp(-)) metal complexes, namely [VTpCl](+), [CrTpCl](+), [MnTpCl](+), [FeTpCl], [CoTpCl], and [NiTpCl], and their substituted methyl and tert-butyl analogues with the goal of observing the effect of the ligand field on the magnetic properties. In the [VTpCl](+), [CrTpCl](+), [CoTpCl], and [NiTpCl] complexes, the magnetic anisotropy arises as a consequence of out-of-state spin-orbit coupling, and covalent changes induced by the substitution of hydrogen atoms on the pyrazolyl rings does not lead to drastic changes in the magnetic anisotropy. On the other hand, much larger magnetic anisotropies were predicted in complexes displaying a degenerate ground state, namely [MnTpCl](+) and [FeTpCl], due to in-state spin-orbit coupling. The anisotropy in these systems was shown to be very sensitive to perturbations, for example, chemical substitution and distortions due to the Jahn-Teller effect. We found that by substituting the hydrogen atoms in [MnTpCl](+) and [FeTpCl] by methyl and tert-butyl groups, certain covalent contributions to the magnetic anisotropy energy (MAE) could be controlled, thereby achieving higher values. Moreover, we showed that the selection of ion has important consequences for the symmetry of the ground spin-orbit term, opening the possibility of achieving zero magnetic tunneling even in non-Kramers ions. We have also shown that substitution may also contribute to a quenching of the Jahn-Teller effect, which could significantly reduce the magnetic anisotropy of the complexes studied.
PB  - Wiley-V C H Verlag Gmbh, Weinheim
T2  - Chemistry. A European Journal
T1  - Magnetic Anisotropy in "Scorpionate" First-Row Transition-Metal Complexes: A Theoretical Investigation
VL  - 21
IS  - 9
SP  - 3716
EP  - 3726
DO  - 10.1002/chem.201405480
ER  - 

@article{
author = "Perić, Marko and Garcia-Fuente, Amador and Zlatar, Matija and Daul, Claude and Stepanović, Stepan and Garcia-Fernandez, Pablo and Gruden-Pavlović, Maja",
year = "2015",
abstract = "In this work we have analyzed in detail the magnetic anisotropy in a series of hydrotris(pyrazolyl)borate (Tp(-)) metal complexes, namely [VTpCl](+), [CrTpCl](+), [MnTpCl](+), [FeTpCl], [CoTpCl], and [NiTpCl], and their substituted methyl and tert-butyl analogues with the goal of observing the effect of the ligand field on the magnetic properties. In the [VTpCl](+), [CrTpCl](+), [CoTpCl], and [NiTpCl] complexes, the magnetic anisotropy arises as a consequence of out-of-state spin-orbit coupling, and covalent changes induced by the substitution of hydrogen atoms on the pyrazolyl rings does not lead to drastic changes in the magnetic anisotropy. On the other hand, much larger magnetic anisotropies were predicted in complexes displaying a degenerate ground state, namely [MnTpCl](+) and [FeTpCl], due to in-state spin-orbit coupling. The anisotropy in these systems was shown to be very sensitive to perturbations, for example, chemical substitution and distortions due to the Jahn-Teller effect. We found that by substituting the hydrogen atoms in [MnTpCl](+) and [FeTpCl] by methyl and tert-butyl groups, certain covalent contributions to the magnetic anisotropy energy (MAE) could be controlled, thereby achieving higher values. Moreover, we showed that the selection of ion has important consequences for the symmetry of the ground spin-orbit term, opening the possibility of achieving zero magnetic tunneling even in non-Kramers ions. We have also shown that substitution may also contribute to a quenching of the Jahn-Teller effect, which could significantly reduce the magnetic anisotropy of the complexes studied.",
publisher = "Wiley-V C H Verlag Gmbh, Weinheim",
journal = "Chemistry. A European Journal",
title = "Magnetic Anisotropy in "Scorpionate" First-Row Transition-Metal Complexes: A Theoretical Investigation",
volume = "21",
number = "9",
pages = "3716-3726",
doi = "10.1002/chem.201405480"
}

Perić, M., Garcia-Fuente, A., Zlatar, M., Daul, C., Stepanović, S., Garcia-Fernandez, P.,& Gruden-Pavlović, M.. (2015). Magnetic Anisotropy in "Scorpionate" First-Row Transition-Metal Complexes: A Theoretical Investigation. in Chemistry. A European Journal
Wiley-V C H Verlag Gmbh, Weinheim., 21(9), 3716-3726.
https://doi.org/10.1002/chem.201405480

Perić M, Garcia-Fuente A, Zlatar M, Daul C, Stepanović S, Garcia-Fernandez P, Gruden-Pavlović M. Magnetic Anisotropy in "Scorpionate" First-Row Transition-Metal Complexes: A Theoretical Investigation. in Chemistry. A European Journal. 2015;21(9):3716-3726.
doi:10.1002/chem.201405480 .

Perić, Marko, Garcia-Fuente, Amador, Zlatar, Matija, Daul, Claude, Stepanović, Stepan, Garcia-Fernandez, Pablo, Gruden-Pavlović, Maja, "Magnetic Anisotropy in "Scorpionate" First-Row Transition-Metal Complexes: A Theoretical Investigation" in Chemistry. A European Journal, 21, no. 9 (2015):3716-3726,
https://doi.org/10.1002/chem.201405480 . .

TY  - DATA
AU  - Garcia-Fernandez, Pablo
AU  - Antonio Aramburu, Jose
AU  - Moreno, Miguel
AU  - Zlatar, Matija
AU  - Gruden-Pavlović, Maja
PY  - 2014
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/3667
PB  - Amer Chemical Soc, Washington
T2  - Journal of Chemical Theory and Computation
T1  - Supplementary data for the article: García-Fernández, P.; Aramburu, J. A.; Moreno, M.; Zlatar, M.; Gruden-Pavlović, M. A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect. Journal of Chemical Theory and Computation 2014, 10 (4), 1824–1833. https://doi.org/10.1021/ct4011097
UR  - https://hdl.handle.net/21.15107/rcub_cherry_3667
ER  - 

@misc{
author = "Garcia-Fernandez, Pablo and Antonio Aramburu, Jose and Moreno, Miguel and Zlatar, Matija and Gruden-Pavlović, Maja",
year = "2014",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of Chemical Theory and Computation",
title = "Supplementary data for the article: García-Fernández, P.; Aramburu, J. A.; Moreno, M.; Zlatar, M.; Gruden-Pavlović, M. A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect. Journal of Chemical Theory and Computation 2014, 10 (4), 1824–1833. https://doi.org/10.1021/ct4011097",
url = "https://hdl.handle.net/21.15107/rcub_cherry_3667"
}

Garcia-Fernandez, P., Antonio Aramburu, J., Moreno, M., Zlatar, M.,& Gruden-Pavlović, M.. (2014). Supplementary data for the article: García-Fernández, P.; Aramburu, J. A.; Moreno, M.; Zlatar, M.; Gruden-Pavlović, M. A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect. Journal of Chemical Theory and Computation 2014, 10 (4), 1824–1833. https://doi.org/10.1021/ct4011097. in Journal of Chemical Theory and Computation
Amer Chemical Soc, Washington..
https://hdl.handle.net/21.15107/rcub_cherry_3667

Garcia-Fernandez P, Antonio Aramburu J, Moreno M, Zlatar M, Gruden-Pavlović M. Supplementary data for the article: García-Fernández, P.; Aramburu, J. A.; Moreno, M.; Zlatar, M.; Gruden-Pavlović, M. A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect. Journal of Chemical Theory and Computation 2014, 10 (4), 1824–1833. https://doi.org/10.1021/ct4011097. in Journal of Chemical Theory and Computation. 2014;.
https://hdl.handle.net/21.15107/rcub_cherry_3667 .

Garcia-Fernandez, Pablo, Antonio Aramburu, Jose, Moreno, Miguel, Zlatar, Matija, Gruden-Pavlović, Maja, "Supplementary data for the article: García-Fernández, P.; Aramburu, J. A.; Moreno, M.; Zlatar, M.; Gruden-Pavlović, M. A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect. Journal of Chemical Theory and Computation 2014, 10 (4), 1824–1833. https://doi.org/10.1021/ct4011097" in Journal of Chemical Theory and Computation (2014),
https://hdl.handle.net/21.15107/rcub_cherry_3667 .

TY  - JOUR
AU  - Garcia-Fernandez, Pablo
AU  - Antonio Aramburu, Jose
AU  - Moreno, Miguel
AU  - Zlatar, Matija
AU  - Gruden-Pavlović, Maja
PY  - 2014
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1765
AB  - Vibronic coupling theory shows that the cause for spontaneous instability in systems presenting a nondegenerate ground state is the so-called pseudo-Jahn-Teller effect, and thus its study can be extremely helpful to understand the structure of many molecules. While this theory, based on the mixing of the ground and excited states with a distortion, has been long studied, there are two obscure points that we try to clarify in the present work. First, the operators involved in both the vibronic and nonvibronic parts of the force constant take only into account electron nuclear and nuclear nuclear interactions, apparently leaving electron electron repulsions and the electron's kinetic energy out of the chemical picture. Second, a fully quantitative computational appraisal of this effect has been up to now problematic. Here, we present a reformulation of the pseudo-Jahn-Teller theory that explicitly shows the contributions of all operators in the molecular Hamiltonian and allows connecting the results obtained with this model to other chemical theories relating electron distribution and geometry. Moreover, we develop a practical approach based on Hartree-Fock and density functional theory that allows quantification of the pseudo-Jahn-Teller effect. We demonstrate the usefulness of our method studying the pyramidal distortion in ammonia and its absence in borane, revealing the strong importance of the kinetic energy of the electrons in the lowest a(2)'' orbital to trigger this instability. The present tool opens a window for exploring in detail the actual microscopic origin of structural instabilities in molecules and solids.
PB  - Amer Chemical Soc, Washington
T2  - Journal of Chemical Theory and Computation
T1  - A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect
VL  - 10
IS  - 4
SP  - 1824
EP  - 1833
DO  - 10.1021/ct4011097
ER  - 

@article{
author = "Garcia-Fernandez, Pablo and Antonio Aramburu, Jose and Moreno, Miguel and Zlatar, Matija and Gruden-Pavlović, Maja",
year = "2014",
abstract = "Vibronic coupling theory shows that the cause for spontaneous instability in systems presenting a nondegenerate ground state is the so-called pseudo-Jahn-Teller effect, and thus its study can be extremely helpful to understand the structure of many molecules. While this theory, based on the mixing of the ground and excited states with a distortion, has been long studied, there are two obscure points that we try to clarify in the present work. First, the operators involved in both the vibronic and nonvibronic parts of the force constant take only into account electron nuclear and nuclear nuclear interactions, apparently leaving electron electron repulsions and the electron's kinetic energy out of the chemical picture. Second, a fully quantitative computational appraisal of this effect has been up to now problematic. Here, we present a reformulation of the pseudo-Jahn-Teller theory that explicitly shows the contributions of all operators in the molecular Hamiltonian and allows connecting the results obtained with this model to other chemical theories relating electron distribution and geometry. Moreover, we develop a practical approach based on Hartree-Fock and density functional theory that allows quantification of the pseudo-Jahn-Teller effect. We demonstrate the usefulness of our method studying the pyramidal distortion in ammonia and its absence in borane, revealing the strong importance of the kinetic energy of the electrons in the lowest a(2)'' orbital to trigger this instability. The present tool opens a window for exploring in detail the actual microscopic origin of structural instabilities in molecules and solids.",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of Chemical Theory and Computation",
title = "A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect",
volume = "10",
number = "4",
pages = "1824-1833",
doi = "10.1021/ct4011097"
}

Garcia-Fernandez, P., Antonio Aramburu, J., Moreno, M., Zlatar, M.,& Gruden-Pavlović, M.. (2014). A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect. in Journal of Chemical Theory and Computation
Amer Chemical Soc, Washington., 10(4), 1824-1833.
https://doi.org/10.1021/ct4011097

Garcia-Fernandez P, Antonio Aramburu J, Moreno M, Zlatar M, Gruden-Pavlović M. A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect. in Journal of Chemical Theory and Computation. 2014;10(4):1824-1833.
doi:10.1021/ct4011097 .

Garcia-Fernandez, Pablo, Antonio Aramburu, Jose, Moreno, Miguel, Zlatar, Matija, Gruden-Pavlović, Maja, "A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect" in Journal of Chemical Theory and Computation, 10, no. 4 (2014):1824-1833,
https://doi.org/10.1021/ct4011097 . .

TY  - JOUR
AU  - Gruden-Pavlović, Maja
AU  - Perić, Marko
AU  - Zlatar, Matija
AU  - Garcia-Fernandez, Pablo
PY  - 2014
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1512
AB  - Magnetic molecules that present a slow decay of their magnetization (molecular magnets) are very interesting both from a fundamental and applied points of view. While many approaches focus strongly on finding systems with strong magnetic anisotropy giving rise to large spin-reversal barriers, less is known on the behavior of magnetic tunnelling, which is also a fundamental component of molecular magnet behavior. In this work, we propose a model to describe both the spin-reversal barrier and magnetic tunnelling in Ni(II) trigonal bipyramidal complexes, which could be easily extended to other transitionmetal systems. Based on this model, we show the criteria that lead to the optimal complexes to find molecular magnet behavior. We test our proposal with multi-reference configuration-interaction (MRCI) and ligand-field-density-functional-theory (LF-DFT) first-principles calculations applied over several families of mononuclear Ni(II) complexes. As a salient result, we find that the complex [NiCl3(Hdabco)(2)](+) (dabco is 1,4-diazabicyclo[2.2.2]-octane) displays both a very large magnetic anisotropy energy, 524 cm(-1), and a small tunnelling splitting, 0.2 cm(-1), when compared to other systems containing the same metal. We expect molecular magnet behaviour to be observed when small magnetic fields are employed to disrupt tunnelling. These values are reached due to the choice of ligands that favor a complete destruction of the Jahn-Teller distortions through spin-orbit coupling and an unquenched orbital momentum.
PB  - Royal Soc Chemistry, Cambridge
T2  - Chemical Science
T1  - Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior
VL  - 5
IS  - 4
SP  - 1453
EP  - 1462
DO  - 10.1039/c3sc52984c
ER  - 

@article{
author = "Gruden-Pavlović, Maja and Perić, Marko and Zlatar, Matija and Garcia-Fernandez, Pablo",
year = "2014",
abstract = "Magnetic molecules that present a slow decay of their magnetization (molecular magnets) are very interesting both from a fundamental and applied points of view. While many approaches focus strongly on finding systems with strong magnetic anisotropy giving rise to large spin-reversal barriers, less is known on the behavior of magnetic tunnelling, which is also a fundamental component of molecular magnet behavior. In this work, we propose a model to describe both the spin-reversal barrier and magnetic tunnelling in Ni(II) trigonal bipyramidal complexes, which could be easily extended to other transitionmetal systems. Based on this model, we show the criteria that lead to the optimal complexes to find molecular magnet behavior. We test our proposal with multi-reference configuration-interaction (MRCI) and ligand-field-density-functional-theory (LF-DFT) first-principles calculations applied over several families of mononuclear Ni(II) complexes. As a salient result, we find that the complex [NiCl3(Hdabco)(2)](+) (dabco is 1,4-diazabicyclo[2.2.2]-octane) displays both a very large magnetic anisotropy energy, 524 cm(-1), and a small tunnelling splitting, 0.2 cm(-1), when compared to other systems containing the same metal. We expect molecular magnet behaviour to be observed when small magnetic fields are employed to disrupt tunnelling. These values are reached due to the choice of ligands that favor a complete destruction of the Jahn-Teller distortions through spin-orbit coupling and an unquenched orbital momentum.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Chemical Science",
title = "Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior",
volume = "5",
number = "4",
pages = "1453-1462",
doi = "10.1039/c3sc52984c"
}

Gruden-Pavlović, M., Perić, M., Zlatar, M.,& Garcia-Fernandez, P.. (2014). Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior. in Chemical Science
Royal Soc Chemistry, Cambridge., 5(4), 1453-1462.
https://doi.org/10.1039/c3sc52984c

Gruden-Pavlović M, Perić M, Zlatar M, Garcia-Fernandez P. Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior. in Chemical Science. 2014;5(4):1453-1462.
doi:10.1039/c3sc52984c .

Gruden-Pavlović, Maja, Perić, Marko, Zlatar, Matija, Garcia-Fernandez, Pablo, "Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior" in Chemical Science, 5, no. 4 (2014):1453-1462,
https://doi.org/10.1039/c3sc52984c . .

TY  - JOUR
AU  - Ramanantoanina, Harry
AU  - Zlatar, Matija
AU  - Garcia-Fernandez, Pablo
AU  - Daul, Claude
AU  - Gruden-Pavlović, Maja
PY  - 2013
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/3496
AB  - A general model for the analysis of the Adiabatic Potential Energy Surfaces (APES) of the molecules that are subject to the multimode Jahn-Teller effect is presented. The method utilizes the information obtained by DFT calculations on a distorted stationary point on the APES. The essence of the model is to express the distortion along a model minimal energy path called Intrinsic Distortion Path (IDP), projecting the geometry of the system on the normal modes of the either high-symmetry (HS) or low symmetry (LS) nuclear configuration. This allows us to determine the significance of all of the involved normal modes along a relevant particular path of distortion, and the direct calculation of the vibronic coupling constants. The IDP analysis is illustrated by the discussion of the multimode H circle times (g + 2h) JT effect in fullerene cations (C-60(+)) giving a deep insight into the origin and the mechanism of vibronic coupling in fullerene based molecules.
PB  - Royal Soc Chemistry, Cambridge
T2  - Physical Chemistry Chemical Physics
T1  - General treatment of the multimode Jahn-Teller effect: study of fullerene cations
VL  - 15
IS  - 4
SP  - 1252
EP  - 1259
DO  - 10.1039/c2cp43591h
ER  - 

@article{
author = "Ramanantoanina, Harry and Zlatar, Matija and Garcia-Fernandez, Pablo and Daul, Claude and Gruden-Pavlović, Maja",
year = "2013",
abstract = "A general model for the analysis of the Adiabatic Potential Energy Surfaces (APES) of the molecules that are subject to the multimode Jahn-Teller effect is presented. The method utilizes the information obtained by DFT calculations on a distorted stationary point on the APES. The essence of the model is to express the distortion along a model minimal energy path called Intrinsic Distortion Path (IDP), projecting the geometry of the system on the normal modes of the either high-symmetry (HS) or low symmetry (LS) nuclear configuration. This allows us to determine the significance of all of the involved normal modes along a relevant particular path of distortion, and the direct calculation of the vibronic coupling constants. The IDP analysis is illustrated by the discussion of the multimode H circle times (g + 2h) JT effect in fullerene cations (C-60(+)) giving a deep insight into the origin and the mechanism of vibronic coupling in fullerene based molecules.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Physical Chemistry Chemical Physics",
title = "General treatment of the multimode Jahn-Teller effect: study of fullerene cations",
volume = "15",
number = "4",
pages = "1252-1259",
doi = "10.1039/c2cp43591h"
}

Ramanantoanina, H., Zlatar, M., Garcia-Fernandez, P., Daul, C.,& Gruden-Pavlović, M.. (2013). General treatment of the multimode Jahn-Teller effect: study of fullerene cations. in Physical Chemistry Chemical Physics
Royal Soc Chemistry, Cambridge., 15(4), 1252-1259.
https://doi.org/10.1039/c2cp43591h

Ramanantoanina H, Zlatar M, Garcia-Fernandez P, Daul C, Gruden-Pavlović M. General treatment of the multimode Jahn-Teller effect: study of fullerene cations. in Physical Chemistry Chemical Physics. 2013;15(4):1252-1259.
doi:10.1039/c2cp43591h .

Ramanantoanina, Harry, Zlatar, Matija, Garcia-Fernandez, Pablo, Daul, Claude, Gruden-Pavlović, Maja, "General treatment of the multimode Jahn-Teller effect: study of fullerene cations" in Physical Chemistry Chemical Physics, 15, no. 4 (2013):1252-1259,
https://doi.org/10.1039/c2cp43591h . .

TY  - JOUR
AU  - Garcia-Fernandez, Pablo
AU  - Anđelković, Ljubica
AU  - Zlatar, Matija
AU  - Gruden-Pavlović, Maja
AU  - Dreuw, Andreas
PY  - 2013
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1437
AB  - The interplay of excitonic and vibronic coupling in coupled chromophores determines the efficiency of exciton localization vs delocalization, or in other words, coherent excitation energy transfer vs exciton hopping. For the investigation of exciton localization in large coupled dimers, a model Hamiltonian approach is derived, the ingredients of which can all be obtained from monomer ab initio calculations alone avoiding costly ab initio computation of the full dimer. The accuracy and applicability of this model are exemplified for the benzene dimer by rigorous comparison to ab initio results.
PB  - Amer Inst Physics, Melville
T2  - Journal of Chemical Physics
T1  - A simple monomer-based model-Hamiltonian approach to combine excitonic coupling and Jahn-Teller theory
VL  - 139
IS  - 17
DO  - 10.1063/1.4827398
ER  - 

@article{
author = "Garcia-Fernandez, Pablo and Anđelković, Ljubica and Zlatar, Matija and Gruden-Pavlović, Maja and Dreuw, Andreas",
year = "2013",
abstract = "The interplay of excitonic and vibronic coupling in coupled chromophores determines the efficiency of exciton localization vs delocalization, or in other words, coherent excitation energy transfer vs exciton hopping. For the investigation of exciton localization in large coupled dimers, a model Hamiltonian approach is derived, the ingredients of which can all be obtained from monomer ab initio calculations alone avoiding costly ab initio computation of the full dimer. The accuracy and applicability of this model are exemplified for the benzene dimer by rigorous comparison to ab initio results.",
publisher = "Amer Inst Physics, Melville",
journal = "Journal of Chemical Physics",
title = "A simple monomer-based model-Hamiltonian approach to combine excitonic coupling and Jahn-Teller theory",
volume = "139",
number = "17",
doi = "10.1063/1.4827398"
}

Garcia-Fernandez, P., Anđelković, L., Zlatar, M., Gruden-Pavlović, M.,& Dreuw, A.. (2013). A simple monomer-based model-Hamiltonian approach to combine excitonic coupling and Jahn-Teller theory. in Journal of Chemical Physics
Amer Inst Physics, Melville., 139(17).
https://doi.org/10.1063/1.4827398

Garcia-Fernandez P, Anđelković L, Zlatar M, Gruden-Pavlović M, Dreuw A. A simple monomer-based model-Hamiltonian approach to combine excitonic coupling and Jahn-Teller theory. in Journal of Chemical Physics. 2013;139(17).
doi:10.1063/1.4827398 .

Garcia-Fernandez, Pablo, Anđelković, Ljubica, Zlatar, Matija, Gruden-Pavlović, Maja, Dreuw, Andreas, "A simple monomer-based model-Hamiltonian approach to combine excitonic coupling and Jahn-Teller theory" in Journal of Chemical Physics, 139, no. 17 (2013),
https://doi.org/10.1063/1.4827398 . .

TY  - JOUR
AU  - Ramanantoanina, Harry
AU  - Zlatar, Matija
AU  - Garcia-Fernandez, Pablo
AU  - Daul, Claude
AU  - Gruden-Pavlović, Maja
PY  - 2013
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1562
AB  - A general model for the analysis of the Adiabatic Potential Energy Surfaces (APES) of the molecules that are subject to the multimode Jahn-Teller effect is presented. The method utilizes the information obtained by DFT calculations on a distorted stationary point on the APES. The essence of the model is to express the distortion along a model minimal energy path called Intrinsic Distortion Path (IDP), projecting the geometry of the system on the normal modes of the either high-symmetry (HS) or low symmetry (LS) nuclear configuration. This allows us to determine the significance of all of the involved normal modes along a relevant particular path of distortion, and the direct calculation of the vibronic coupling constants. The IDP analysis is illustrated by the discussion of the multimode H circle times (g + 2h) JT effect in fullerene cations (C-60(+)) giving a deep insight into the origin and the mechanism of vibronic coupling in fullerene based molecules.
PB  - Royal Soc Chemistry, Cambridge
T2  - Physical Chemistry Chemical Physics
T1  - General treatment of the multimode Jahn-Teller effect: study of fullerene cations
VL  - 15
IS  - 4
SP  - 1252
EP  - 1259
DO  - 10.1039/c2cp43591h
ER  - 

@article{
author = "Ramanantoanina, Harry and Zlatar, Matija and Garcia-Fernandez, Pablo and Daul, Claude and Gruden-Pavlović, Maja",
year = "2013",
abstract = "A general model for the analysis of the Adiabatic Potential Energy Surfaces (APES) of the molecules that are subject to the multimode Jahn-Teller effect is presented. The method utilizes the information obtained by DFT calculations on a distorted stationary point on the APES. The essence of the model is to express the distortion along a model minimal energy path called Intrinsic Distortion Path (IDP), projecting the geometry of the system on the normal modes of the either high-symmetry (HS) or low symmetry (LS) nuclear configuration. This allows us to determine the significance of all of the involved normal modes along a relevant particular path of distortion, and the direct calculation of the vibronic coupling constants. The IDP analysis is illustrated by the discussion of the multimode H circle times (g + 2h) JT effect in fullerene cations (C-60(+)) giving a deep insight into the origin and the mechanism of vibronic coupling in fullerene based molecules.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Physical Chemistry Chemical Physics",
title = "General treatment of the multimode Jahn-Teller effect: study of fullerene cations",
volume = "15",
number = "4",
pages = "1252-1259",
doi = "10.1039/c2cp43591h"
}

Ramanantoanina, H., Zlatar, M., Garcia-Fernandez, P., Daul, C.,& Gruden-Pavlović, M.. (2013). General treatment of the multimode Jahn-Teller effect: study of fullerene cations. in Physical Chemistry Chemical Physics
Royal Soc Chemistry, Cambridge., 15(4), 1252-1259.
https://doi.org/10.1039/c2cp43591h

Ramanantoanina H, Zlatar M, Garcia-Fernandez P, Daul C, Gruden-Pavlović M. General treatment of the multimode Jahn-Teller effect: study of fullerene cations. in Physical Chemistry Chemical Physics. 2013;15(4):1252-1259.
doi:10.1039/c2cp43591h .

Ramanantoanina, Harry, Zlatar, Matija, Garcia-Fernandez, Pablo, Daul, Claude, Gruden-Pavlović, Maja, "General treatment of the multimode Jahn-Teller effect: study of fullerene cations" in Physical Chemistry Chemical Physics, 15, no. 4 (2013):1252-1259,
https://doi.org/10.1039/c2cp43591h . .

TY  - JOUR
AU  - Gruden-Pavlović, Maja
AU  - Garcia-Fernandez, Pablo
AU  - Anđelković, Ljubica
AU  - Daul, Claude
AU  - Zlatar, Matija
PY  - 2011
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1202
AB  - The family of the Jahn-Teller (JT) active hydrocarbon rings, CH (n = 5-7), was analyzed by the means of multideterminantal density functional theory (DFT) approach. The multimode problem was addressed using the intrinsic distortion path (IDP) method, in which the JT distortion is expressed as a linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation. Partitioning of the stabilization energy into the various physically meaningful terms arising from Kohn Sham DFT has been performed to get further chemical insight into the coupling of the nuclear movements and the electron distribution.
PB  - Amer Chemical Soc, Washington
T2  - Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Th
T1  - Treatment of the Multimode Jahn-Teller Problem in Small Aromatic Radicals
VL  - 115
IS  - 39
SP  - 10801
EP  - 10813
DO  - 10.1021/jp206083j
ER  - 

@article{
author = "Gruden-Pavlović, Maja and Garcia-Fernandez, Pablo and Anđelković, Ljubica and Daul, Claude and Zlatar, Matija",
year = "2011",
abstract = "The family of the Jahn-Teller (JT) active hydrocarbon rings, CH (n = 5-7), was analyzed by the means of multideterminantal density functional theory (DFT) approach. The multimode problem was addressed using the intrinsic distortion path (IDP) method, in which the JT distortion is expressed as a linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation. Partitioning of the stabilization energy into the various physically meaningful terms arising from Kohn Sham DFT has been performed to get further chemical insight into the coupling of the nuclear movements and the electron distribution.",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Th",
title = "Treatment of the Multimode Jahn-Teller Problem in Small Aromatic Radicals",
volume = "115",
number = "39",
pages = "10801-10813",
doi = "10.1021/jp206083j"
}

Gruden-Pavlović, M., Garcia-Fernandez, P., Anđelković, L., Daul, C.,& Zlatar, M.. (2011). Treatment of the Multimode Jahn-Teller Problem in Small Aromatic Radicals. in Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Th
Amer Chemical Soc, Washington., 115(39), 10801-10813.
https://doi.org/10.1021/jp206083j

Gruden-Pavlović M, Garcia-Fernandez P, Anđelković L, Daul C, Zlatar M. Treatment of the Multimode Jahn-Teller Problem in Small Aromatic Radicals. in Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Th. 2011;115(39):10801-10813.
doi:10.1021/jp206083j .

Gruden-Pavlović, Maja, Garcia-Fernandez, Pablo, Anđelković, Ljubica, Daul, Claude, Zlatar, Matija, "Treatment of the Multimode Jahn-Teller Problem in Small Aromatic Radicals" in Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Th, 115, no. 39 (2011):10801-10813,
https://doi.org/10.1021/jp206083j . .