Research Topics and Interests
My research activity is focused on the theoretical study of the stereochemistry and the electronic structure (and properties) of inorganic solids and co-ordination compounds of transition metals in their ground and lowest excited states (spectroscopy VIS, UV und EPR, papers 1-3, 6-8, 10-11, 13-14, 16, 36-44, 46-48, 62, 63, 68,74,78) and magnetism, papers 9, 15, 21, 27, 32, 35, 70, 71, 76). The emphasis of my theoretical work is the application of a broad variety of methods of quantum chemistry and solid state physics (semi-emprical: ligand field theory, the periodic and cluster Hubbard models and non-empirical DFT and ab-initio, as well as combinations of these) for the interpretation and prediction of interesting properties and in a very tight connection and interactive work with ongoing experimental studies. Examples are my long standing co-operations with inorganic spectroscopists (H.H.Schmidtke, T.Schönherr, Düsseldorf) and solid state chemists (Prof.Dr.D.Reinen, Marburg) and physicists (Prof.Dr.G.Sawatzky, Groningen). In a very fruitful co-operation with the group of C.Daul in Fribourg we developed a new DFT assisted(based) ligand field model (publications 63, 68, 70, 71, 74, 77, 79) which turned out to be extremely powerful not only in interpreting but also in predicting spectroscopic properties (optical, ESR) of transition metals. Recently, the approach has been extended to rare-earth compounds, again in co-operation with spectroscopists (H.U.Güdel, Bern) and theorists (Dr.T.Wesolowski) – papers – 75,76, 78.
In my future work I intend to further extend my DFT based ligand field studies to magnetism and spin-transitions in complexes and the transition metal compounds in the solid state. Presently, we are studying the unique behavior of the CN- as a bridging ligand, in particular the interplay between the magnetic and Jahn-Teller coupling in MnIIICN63- and other Jahn-Teller active TM ions (Fe3+, Ni3+). We further plan to study by means of theory and experiment (in co-operation with the group of P.Comba, Heidelberg) the effect of incapsulation on the magnetic properties of single and bridged TM-cyanide complexes using template synthesis and looking theoretically on the effect of the strain on the magnetic bridging functions of the CN- ligand. Further on, I plan to extend the tools of my studies with the periodic DFT method and supplement it with some effects which are absent in the existing DFT band programs, namely the non-dynamical (long-range) electronic correlation. Our first efforts in that direction, the DFT based ligand field model and its success will help us to extend the approach to periodic structures.
A reasonable extension of my studies is to apply the expertise and knowledge on compounds with opened d-shells to problems of homogeneous catalysis, in particular to the problems of the variable oxidation states of Fe (paper 56) an their activity to bind and activate molecular oxygen for oxidation reactions with organic compounds.
List of publications
(Review articles are given in bold).
1. G.St.Nikolov and M.Atanasov, The electronic spectrum of bis(N,N)-diethyldithiocarbamato
Cu(II), J.Inorg.Nucl.Chem. 43,1201-1206(1981).
2. M.Atanasov and G.St.Nikolov, Electronic spectra of planar chelate nickel(II) complexes,
3.G.St.Nikolov and M.Atanasov, Electronic spectra of planar bis-acetylacetonato copper(II)
complexes, Inorg.Chim.Acta 72,95-101(1983).
4.M.Atanasov and G.St.Nikolov, Geometrical factors affecting the angular overlap parameters of planar copper(II) and nickel(II) bis-(bidentate) complexes, Comm..Dep.Chem.Bulg.Acad.Sci.,16,329-336(1983).
5. M.Atanasov, Structure and spectra of bis-chelate complexes of Ni(II) and Cu(II), PhD Thesis, Bulgarian Academy of Sciences, Sofia, Bulgaria, 1983
6.M.Atanasov and G.St.Nikolov, Intensity of d-d bands in spectra of planar chelate complexes,
I.Electronic Spectrum of nickel(II) diethyldithiophosphate, J.Molec.Struct., 114,65-68(1984).
7.M.Atanasov and G.St.Nikolov, Electronic spectra of pseudotetrahedral bis(bidentate) copper(II) complexes: spectral assignment and effect of ligand asymmetry, Inorg.Chim.Acta 96,29-37(1985).
8.M.Atanasov and G.St.Nikolov, Effect of ligand non-linearity on the spectral parameters of pseudotetrahedral copper(II) complexes, Proc.10th Conference on Coord.Chem.,Smolenice,Bratislava, CSSR,4-7.06.1985,11-16.
9.M.Atanasov,S.Angelov and I.Mayer, Angular dependence of superexchange interactions in s-bonded transition metal clusters,Solid State.Commun.56,743-745(1985).
10.M.Atanasov,T.Schoenherr and H.-H.Schmidtke, The role of p-bonding network for trigonal level splittings of tris-bidendate Cr(acac)3 and Cr(ox)33-, Theor.Chim.Acta,71,59-73(1987).
11.T.Schoenherr,M.Atanasov, and H.-H.Schmidtke, On the coordination sphere geometry of trisacetylacetonato metal (III) complexes of the first transition series rationalized by orbital phase coupling effects, Inorg.Chim.Acta, 141,27-32(1988).
12.M.Atanasov and H.-H.Schmidtke, The angular overlap model for transition metal compounds forming extended structures, Chem.Phys.,124,205-222(1988).
13.D.Reinen,M.Atanasov,G.St.Nikolov and F.Steffens, Local and cooperative Jahn-Teller distortions of Ni2+ and Cu2+ in tetrahedral coordination, Inorg.Chem.,27,1678-1686(1988).
14. N.Trendafilova, M.Atanasov,G.Nikolov,A.Yu.Tsivadze,V.A.Trofimov and I.K.Kireeva,
Soviet J.of Coord.Chem., 14,595-600(1988).
15.M.Atanasov,S.Angelov and I.Mayer, Modelling of angular dependence of superexchange:application to copper(II) dimers, J.Molec.Struct.(Theochem.) 187,23-33(1988).
16.D.Reinen and M.Atanasov, Fluxionality and stereochemistry of 5-coordinate Cu2+ complexes. The potential energy surface and spectroscopic implications, Chem.Phys. 136,27-46(1989).
17.H.-H.Schmidtke and M.Atanasov, An angular overlap model treatment of mixed valence Pt(II)-Pt(IV) haloamine chain complexes, Monatsh. f. Chemie, 120,941-954(1989).
18.M.Atanasov and T.Schoenherr, The role of p-bonding for trigonal level splittings in chelate complexes. 3.The lowest electronic states in Cr(acac)3. Inorg.Chem.29,4545-4550(1990).
19.J.Degen, H.-H.Schmidtke,R.Stoyanova,S.Angelov and M.Atanasov, Emission spectra of CO2- radicals, stabilized in SrCO3 obtained by thermal decomposition of SrC2O4.H2O, Chem.Phys.147,415-420(1990).
20.S.Angelov,E.Zhecheva, R.Stoyanova and M.Atanasov, Bulk defects in Co3O4, pure and slightly doped with lithium, revealed by EPR of the tetrahedral Co2+ ions. J.Phys.Chem.Solids, 51,1157-1161(1990).
21.M.Atanasov and S.Angelov, Angular overlap model parametrization of Andersonïs superexchange theory. I.A quantification of Goodenough-Kanamori rules, Chem.Phys. 150,383-393(1991).
22.D.Reinen and M.Atanasov, The Jahn-Teller effect and vibronic coupling in transition metal chemistry, Magnetic Resonance Review, 15,167-239(1991).
23.D.Reinen and M.Atanasov, Symmetry and vibronic coupling: the stereochemistry and the ground state potential surface of Cu2+ in five-coordination, Chem.Phys.155,157-171(1991).
24.O.Angelova,J.Macicek,M.Atanasov and G.Petrov, Chelating modes of 3-substituted 2,4-pentanediones. crystal and electronic structure of bis(3-cyano-2,4-pentanedionato) cobalt(II), Inorg.Chem., 30,1943-1949(1991).
25.M.Atanasov, J.Reinhold, NDDO-Study of the electronic structure and geometry of CuCl53-, Comp.Rend.Acad.Bulg.Sci.,44,55-57(1991).
26.A.Kutoglu,R.Allmann,J.-V.Folgado,M.Atanasov and D.Reinen, An unusual geometry of five-coordinate copper(II): the structure of Cu(terpy)I2 and spectroscopic investigations of complexes Cu(terpy)X2(X:I,NCS) Z.Naturforsch. 46b,1193-1199(1991).
27.M.Atanasov,S.Angelov and D.Reinen, Local and cooperative magnetic and vibronic interactions in polynuclear transition metal clusters and solids and their parametrization within the extended angular overlap model, Bulg.Chem.Commun.,25,26-38(1992).
28. A.Ahle,B.Neumüller,J.Pebler,M.Atanasov and K.Dehnike, [Na(12-Krone-4)2]2[Ni(Se4)2].DMF; Synthese, Kristallstruktur und magnetisches Verhalten, Z.anorg.allg.Chem., 615,131-136(1992).
29.M.Atanasov,W.Koenig,H.Craubner and D.Reinen, The phase transition of [Co(NH3)6][CuCl5]: A temperature dependent IR study of the square-pyramid to trigonal-bipyramid interconversion. New.J.Chem.,17,115-124(1993).
30.M.Atanasov,U.Kesper,B.L.Ramakrishna and D.Reinen, Electronic factors influencing the local and cooperative Jahn-Teller interactions in spinels with copper(II) and nickel(II), J.Solid St.Chem.,105,1-18(1993).
31.G.Tyuliev,P.Stefanov and M.Atanasov, On the origin of the temperature effects in the photoemission spectra of NiO. J.Electron.Spectrosc. Relat. Phenom.,63,267-281(1993).
and H.Stratemeier, The compressed tetragonal CuF64- complex in KAlCuF6: An angular
overlap treatment of the electronic structure and magnetic exchange coupling, Inorg.Chem.32, 3397-3401(1993).
33.M.Atanasov and M.Hitchman, d-Orbital Energies in b-ketoenolate copper(II) complexes, Inorg.Chem.32,3973-3975(1993).
34. M.Atanasov,N.Zotov,C.Friebel,K.Petrov and D.Reinen, Jahn-Teller distortions and cation distribution in Cu(II)-Me(II) [Me=Mg,Co] hydroxide nitrate solid solutions - a spectroscopic and structural study, J.Solid.St.Chem., 108,37-45(1994).
35. G.-G.Lindner, M.Atanasov and J.Pebler, A single-crystal study of the magnetic behaviour and exchange coupling in Cu2(OH)3NO3,J.Solid.St.Chem., 116,1-7(1995).
36. D.Reinen,U.Kesper,M.Atanasov and J.Roos, Cr4+ in tetrahedral coordination of oxidic solids: a spectroscopic and structural investigation, Inorg.Chem.,34,184-192(1995).
37.M.Atanasov, On the nature of the lowest excited state of Cr4+-doped olivines, Chem.Phys.Lett.234, 313-318(1995).
38.M.Atanasov, Intraconfigurational transitions in tetrahedral d2 ions: on the expediency of the ligand field model for transition metal ions in high-oxidations states, Chem.Phys. 195,49-58(19995).
39.M.Atanasov,K.Petrov,E.Mirtcheva, C.Friebel and D.Reinen, Cation distribution and coordination chemsitry of Cu(II) in Zn(II) hydroxide nitrate solid solutions - a structural and spectroscopic study. J.Solid.St.Chem., 118,303-312(1995).
40.M.Atanasov,R.H.Potze and G.Sawatzky, Electronic structure of tetrahedral iron (III)-sulfur clusters in alkaline thioferrates:An X-ray absorption study, J.Solid.St.Chem., 119,380-393(1995).
41.M.Atanasov, H.Adamsky and D.Reinen, Ligand field analysis of Mn5+ in tetra-oxo coordination, Chem.Phys.,202,155-165(1996).
42.T.Schoenherr,M.Atanasov, and A.Hauser, Role of p-bonding for trigonal level splittings in chromium(III) complexes. 4.Doublet states and Zeeman splittings in [Cr(bpy)3]3+, Inorg.Chem.35,2077-2084(1996).
43.M.F.Hazenkamp,H.U.Guedel,M.Atanasov,U.Kesper and D.Reinen, Optical spectroscopy of Cr4+ doped Ca2GeO4 and Mg2SiO4, Phys.Rev.B,53,2367-2377(1996).
44.D.Reinen,W.Rauw,U.Kesper,M.Atanasov,H.U.Guedel,M.Hazenkamp and U.Oetliker, Colour, luminescence and bonding properties of tetrahedrally coordinated chromium(IV), manganese(V) and iron(VI) in various oxide ceramics, J.Alloys and Compounds, 246, 193-208(1997).
45.M.Atanasov,H.Adamsky and K.Eifert, Valence stabilization, mixed crystal chemistry and electronic transitions in tetrahedral oxo and hydroxo CrIV,MnV and FeVI clusters, J.Solid St.Chem., 128,1-16(1997).
46. M.Atanasov, Jahn-Teller coupling in tetrahedral oxo VIV, CrV and MnVI clusters, an ab-initio study, Z.Phys.Chem.,200,57-68(1997).
47.R.D.Willett, M.Wei and M.Atanasov, Characterization of trigonal bipyramidal [CuCl3(L)2]- anions: evidence for the absence of a pseudo-Jahn-Teller effect, Z.Phys.Chem., 200,31-37(1997).
48.B.L.Ramakrishna, D.Reinen and M.Atanasov, Manifestation of the cooperative Jahn-Teller Effect in the Raman Spectra of Ba2CuxZn1-xWO6 Mixed Crystals, J.Solid.State Chem., 129,117-122(1997).
49.M.Atanasov and D.Reinen, Non-local electronic effects in the core-level photoemission, UV and optical electronic absorption spectra of nickel oxides,
50. M.Atanasov, T.C.Brunold, H.U.Guedel and C.Daul, Charge-Transfer Spectra and Bonding in Tetrahedral MnVI,CrV,VIV and MnVII,CrVI,VV Oxo Anions, Inorg. Chem., 37,4589-4602(1998)
51.D.Reinen, M.Atanasov, Show-Ling Lee, Second-sphere ligand field effects on oxygen ligator atoms and experimental evidence - the transition metal-oxygen bond in oxidic solids, Cooord.Chem.Rev., 175,91-158 (1998)
52. L.Benco, J.-L.Barras, M.Atanasov, C.A.Daul and E.Deiss, First-principles prediction of voltages of lithiated oxides for lithium-ion batteries, Solid State Ionics, 112,255-259 (1998)
53. D.Mehandjiev, M.Atanasov and A.Naydenov, On the mechanism of indeno (1,2,3-c,d) -pyrene ozonation, Monatshefte für Chemie, 129,999-1005(1998)
54. M.Atanasov, C.Daul,J.-L.Barras, L.Benco and E.Deiss, Polarizable continuum model for lithium interface transitions between a liquid electrolyte and an intercalation electrode, Solid State Ionics, 121,165(1999).
55. L.Benco, J.-L.Barras, M.Atanasov, C.Daul, E.Deiss, First principles calculations of electrode materials for lithium intercalation batteries: TiS2 and LiTi2S4 cubic spinel structures, J.Solid State Chem. 145,503-510(1999); invited paper for the celebration volume of P.Day.
56. M.Atanasov, Theoretical Studies on the Higher Oxidation States of Iron, Inorg.Chem. 38,4942-4948(1999).
57. M.Atanasov, J.-L.Barras, L.Benco and C.Daul, Electronic Structure, Chemical Bonding and Vibronic Coupling in MnIV/MnIII Mixed Valent LixMn2O4 Spinels and their Effect on the Dynamics of Intercalated Li: a Cluster Study using DFT, J.Am.Chem.Soc., 2000,122, 4718-4728.
58. M.Atanasov, D.Reinen, Density Functional Studies on the Lone Pair Effect of the Trivalent Group(V) Elements: I. Electronic Structure, Vibronic Coupling, and Chemical Criteria for the Occurrence of Lone Pair Distortions in AX3 Molecules (A=N to Bi; X=H, and F to I). J.Phys.Chem. A 2001, 105, 5450-5467
59. M.Ferbinteanu, H.W.Roesky, F.Cimpoesu, M.Atanasov, S.Köpke, R.Herbst-Irmer, New Synthetic and Structural Aspects in the Chemistry of Alkylaluminium Fluorides. The Mutual Influence of Hard and Soft Ligands and the Hybridization as Rigorous Structural Criterion, Inorg.Chem. 2001, 40, 4947-4955
60. D.Reinen , M.Atanasov, DFT Calculations of the “Lone Pair” Effect – a Tool for the Chemist to predict molecular Distortions?, M.D.Kaplan and G.O.Zimmerman (eds.) “Vibronic Interactions: Jahn-Teller Effect in Crystals and Molecules, p.83-95, Kluwer Academic Publishers, 2001.
61. M.Atanasov, D.Reinen, Predictive Concept for Lone-Pair Distortions – DFT and Vibronic Model Studies of AXn-(n-3) Molecules and Complexes (A=NIII to BiIII; X=F-I to I-I, n=3-6), J.Am.Chem.Soc. 2002, 124, 6693-6705.
62. M.Atanasov and T.Schönherr, The unique spectroscopic behaviour of the Fe(III)-nitroprusside: a DFT study of the vibronic coupling in the ground and in the lowest excited state, Journal of Molecular Structure (Theochem) 2002, 592, 79-93.
63. M.Atanasov, C.A.Daul and C.Rauzy, New insights into the effect of covalency on the ligand field parameters: a DFT study, Chem.Phys.Lett., 2003, 367, 737-746.
64. M.Atanasov and D.Reinen, Outer Sphere Coordination Chemistry, M.Atanasov and D.Reinen, Comprehensive Coordination Chemistry II, From Biology to Nanotechnology, Volume I: Fundamentals, Edited by A.B.P.Lever, Section 1.36, Elsevier, 2003, 669-678.
65. D.Reinen and M.Atanasov, Lone Pair Effects and Stereochemistry, Comprehensive Coordination Chemistry II, From Biology to Nanotechnology, Volume I: Fundamentals, Edited by A.B.P.Lever, Section 1.35, Elsevier, 2003, p.661-667.
66. T.Schönherr, M.Atanasov and H.Adamsky, Angular Overlap Model, Comprehensive Coordination Chemistry II, From Biology to Nanotechnology, Volume I: Fundamentals, Edited by A.B.P.Lever, Section 2.36, Elsevier, 2003, p.443-455.
67. H.Adamsky, M.Atanasov and T.Schönherr, AOMX: Angular Overlap Model Computation, Comprehensive Coordination Chemistry II, From Biology to Nanotechnology, Volume I: Fundamentals, Edited by A.B.P.Lever, Section 2.52, Elsevier, 2003, p.661-664.
68. M.Atanasov, C.Daul and C.Rauzy, A DFT based Ligand Field Theory, Structure and Bonding, Vol.106, 97-125,2004.
69. M.Atanasov and D.Reinen, A DFT based parameterization of the vibronic mixing between two non-degenerate electronic states and the application to s2-lone pairs, Advances in Quantum Chemistry, 44, 355-368
70. M.Atanasov and C.Daul, A DFT based ligand field model for magnetic exchange coupling in transition metal dimer complexes: (i) principles Chem.Phys.Lett. 379,209-215, 2003.
71. M.Atanasov and C.Daul, A DFT based ligand field model for magnetic exchange coupling in transition metal dimer complexes: (ii) application to magnetic systems with more than one unpaired electron per site, Chem. Phys. Lett. 381, 584-591, 2003.
72. D.Reinen and M.Atanasov, The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study, Structure and Bonding, Vol.107, 2004, Springer Verlag.
73. M.Atanasov and D.Reinen, DFT-Based Pseudo-Jahn-Teller Coupling Studies on the Steric and Lone-Pair Effect of Four- and Five-Coordinate Halide Molecules and Complexes with Central Ions from the Fifth, Sixth and Seventh Main Groups, Inorg.Chem. 2004, 43, 1998-2012.
74. M.Atanasov, C.Rauzy, P.Bättig, C.Daul, Calculation of spin-orbit coupling within the LFDFT: applications to [NiX4]2- (X=F-, Cl-, Br-, I-). Int.J.Quantum Chem. 2005,102(2), 119-131.
75. M.Zbiri, M.Atanasov, C.Daul, J.M.Garcia-Lastra and T.Wesolowski, Application of the density functional theory derived orbital-free embedding potential to calculate the splitting energies of lanthanide cations in chloroelpasolite crystals, Chem.Phys.Lett. 2004, 397(4-6), 441-446.
76. Modelling of Anisotropic Exchange Coupling in Rare-Earth-Transition-Metal Pairs:
Applications to Yb3+-Mn2+ and Yb3+-Cr3+ Halide Clusters and Implications to the Light Up-Conversion, M.Atanasov, C.Daul and H.U.Güdel, Computational Chemistry: Reviews of Current Trends, Vol.9, ed. J.Leszczynski (Ed.), World Scientific, Singapore, published june 2005, 981-256-097-1
77. Modelling Magnetic and Photophysical Properties of Coordination Compounds using Density Functional Theory, M.Atanasov and C.A.Daul, Comptes.Rendus, Chimie, Special Issue: “Integrated Experimental, Spectroscopic and Theoretical Aspects in Inorganic Chemistry”, Guest Editor: Dr.C.Mealli, 2005, 8 1421-1433.
78. M.Atanasov, C.Daul, H.U.Güdel, T.Wesolowski and M.Zbiri, Ground States, Excited States and Metal-Ligand Bonding in Rare Earth Hexachloro Complexes: a DFT Based Ligand Field Study, Inorg.Chem. 2005, 44(8), 2954-2963.
79. The Calculation of ESR parameters by Density Functional Theory: the g- and A-tensors of Co(acacen), C.Daul, C.Rauzy, M.Zbiri, P.Baettig, R.Bruyndonckx, E.J.Baerends and M.Atanasov, Chem.Phys.Lett. 2004, 399(4-6),433-439.
80. M.Atanasov and D.Reinen, The Stability and Eventual Lone Pair Distortion of the Hexahalide Complexes and Molecules of the Fifth to Eight Main Group Elements with one Lone Pair, as Isolated Entities and in Oligomeric Clusters – A Vibronic Coupling and DFT Study, Inorganic Chemistry, 2004, 44,5092-5103.……
81. M.Atanasov, C.A.Daul and E. Penka Fowe, Chemical Bonding in Molecules and Complexes Containing d-Elements, Monatshefte für Chemie, 2005, 136, 925-963.
82. M.Atanasov and C.A.Daul, Theoretical Studies on the Electronic Properties and the Chemical Bonding of Transition Metal Complexes using DFT and Ligand Field Theory, Chimia, 2005, 59, 504-510.
83. M.Atanasov, P.Comba, Y.D.Lampeka, G.Linti, T.Malcherek, R.Miletich, A.I.Prikhod’ko and H.Pritzkow, Encapsulation of cyanometalates by a tris-macrocyclic ligand tricopper(II) complex-syntheses, structural variation and magnetic exchange coupling pathways, Chem.Eur.J. 2006, 12, 737.
84. M.Atanasov, C.A.Daul, M.-M. Rohmer and T. Venkatachalam, A DFT based Ligand Field study of the EPR spectra of Co(II) and Cu(II) porphyrins, Chem.Phys.Lett. 2006, 427, 449-454.
85. D. Reinen, M. Atanasov and W. Massa, The Binding Properties of Terminal and Bridging Fluoride and of Aqua Ligands – a Semiempirical Vibronic Coupling and DFT Study of Mixed-Ligand Manganese(III) Complexes (invited review), Z. Anorg.Allg.Chemie, 2006, 632, 1375-1398.
86. M.Atanasov, P.Comba, B.Martin, V.Müller, G.Rajaraman, H.Rohwer, S.Wunderlich, DFT Models for Cu(II) bispidine complexes: structure, stabilities, isomerism, spin distribution and spectroscopy (invited contribution) M.Atanasov, P.Comba, B.Martin, G.Rajaraman, H.Rohwer, J.Comput.Chem. 2006, 27, 1263-1277.
87. M.Atanasov, P.Comba, S.Förster, G.Linti, T.Malcherek, R.Miletich, A.I. Prikhod’ko and H.Wadepohl, Tuning of Inter- versus Intrachain Magnetic Interactions in Cyano-Bridged NiII/MIII(M=Cr,Fe,Co) Chain Complexes, Inorg.Chem. 2006, 45, 7722-7735.
88. M.Atanasov, P.Comba and C.A.Daul, DFT Studies on the Magnetic Exchange Across the Cyanide Bridge, J.Phys.Chem.A, 2006, 110, 13332-13340.