Abstract
We present a two-part systematic density functional theory (DFT) study of the electronic structure of selected transition metal phthalocyanines. We use a semi-local generalized gradient approximation (GGA) functional, as well as several hybrid exchange-correlation functionals, and compare the results to experimental photoemission data. Here, we study the intermediate spin systems MnPc and FePc. We show that DFT calculations of these systems are extremely sensitive to the choice of functional and basis set with respect to the obtained electronic configuration and to symmetry breaking. Interestingly, all simulated spectra are in good agreement with experiment despite the differences in the underlying electronic configurations.
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J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996) [Erratum: Phys. Rev. Lett. 78, 1396 (1997)]
P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch, J. Phys. Chem. 98, 11623 (1994)
J.P. Perdew, M. Ernzerhof, K. Burke, J. Chem. Phys. 105, 9982 (1996)
C. Adamo, V. Barone, J. Chem. Phys. 110, 6158 (1999)
M. Ernzerhof, G.E. Scuseria, J. Chem. Phys. 110, 5029 (1999)
Y. Zhao, D.G. Truhlar, Acc. Chem. Res. 41, 157 (2008)
N. Marom, L. Kronik, Appl. Phys. A (2008). doi:10.1007/s00339-008-5007-z
S. Kümmel, L. Kronik, Rev. Mod. Phys. 80, 3 (2008)
J.P. Perdew, A. Zunger, Phys. Rev. B 23, 5048 (1981)
N. Dori, M. Menon, L. Kilian, M. Sokolowski, L. Kronik, E. Umbach, Phys. Rev. B 73, 195208 (2006)
N. Marom, O. Hod, G.E. Scuseria, L. Kronik, J. Chem. Phys. 128, 164107 (2008)
H. Miyoshi, H. Ohya-Nishiguchi, Y. Deguchi, Bull. Chem. Soc. Jpn. 46, 2724 (1973)
H. Miyoshi, Bull. Chem. Soc. Jpn. 47, 561 (1974)
J.F. Kirner, W. Dow, R. Scheidt, Inorg. Chem. 15, 1685 (1976)
A. Hudson, H.J. Whitfield, Inorg. Chem. 6, 1120 (1967)
T.H. Moss, A.B. Robinson, Inorg. Chem. 7, 1692 (1968)
C.G. Barraclough, R.L. Martin, S. Mitra, R.C. Sherwood, J. Chem. Phys. 53, 1643 (1970)
B.W. Dale, R.J.P. Williams, C.E. Johnson, T.L. Thorp, J. Chem. Phys. 49, 3441 (1968)
B.W. Dale, R.J.P. Williams, P.R. Edwards, C.E. Johnson, J. Chem. Phys. 49, 3445 (1968)
B.W. Dale, Mol. Phys. 28, 503 (1974)
K. Awaga, Y. Maruyama, Phys. Rev. B 44, 2589 (1991)
M. Evangelisti, J. Bartolome, L.J. de Jongh, G. Filoti, Phys. Rev. B 66, 144410 (2002)
G. Filoti, M.D. Kuz’min, J. Bartolome, Phys. Rev. B 74, 134420 (2006)
S. Heutz, C. Mitra, W. Wu, A.J. Fisher, A. Kerridge, M. Stoneham, T.H. Harker, J. Gardener, H.-H. Tseng, T.S. Jones, C. Renner, G. Aeppli, Adv. Mater. 19, 3618 (2007)
A. Calzolari, A. Ferretti, M. Buongiorno Nardelli, Nanotechnologies 18, 424013 (2007)
M.S. Liao, J.D. Watts, M.J. Huang, Inorg. Chem. 44, 1941 (2005)
B. Bialek, I.G. Kim, J.I. Lee, Surf. Sci. 526, 367 (2003)
M.S. Liao, T. Kar, S.M. Gorun, S. Scheiner, Inorg. Chem. 43, 7151 (2004)
M.S. Liao, J.D. Watts, M.J. Huang, J. Phys. Chem. A 109, 7988 (2005)
W. Wu, A. Kerridge, A.H. Harker, A.J. Fisher, Phys. Rev. B 77, 184403 (2008)
Z. Liu, X. Zhang, Y. Zhang, J. Jiang, Spectrochim. Acta A 67, 1232 (2007). Note that, as pointed out in Ref. [32], FePc has been treated in this article as an s=0 system rather than an s=1 system
M. Sumimoto, Y. Kawashima, K. Hori, H. Fujimoto, Spectrochim. Acta A 71, 286 (2008)
J. Åhlund, K. Nilson, J. Schiessling, L. Kjeldgaard, S. Berner, N. Mårtensson, C. Puglia, B. Brena, M. Nyberg, Y. Luo, J. Chem. Phys. 125, 034709 (2006)
E.R. Davidson, W.T. Borden, J. Phys. Chem. 87, 4783 (1983)
C.D. Sherrill, M.S. Lee, M. Head-Gordon, Chem. Phys. Lett. 302, 425 (1999)
R.D. Cohen, C.D. Sherrill, J. Chem. Phys. 114, 8257 (2001)
B.D. Dunietz, M. Head-Gordon, J. Phys. Chem. A 107, 9160 (2003)
N.J. Russ, T.D. Crawford, G.S. Tschumper, J. Chem. Phys. 120, 7298 (2004)
I. Bersuker, The Jahn-Teller Effect (Cambridge University Press, Cambridge, 2006)
P.O. Löwdin, in Rev. Mod. Phys., vol. 35, ed. by P. Lykos, G.W. Pratt (1963), p. 496
A.D. McLean, B.H. Lengsfield, J. Pacansky, Y. Ellinger, J. Chem. Phys. 83, 3567 (1985)
A. Görling, Phys. Rev. A 47, 2783 (1993)
J.P. Perdew, A. Savin, K. Burke, Phys. Rev. A 51, 4531 (1995)
M.J. Frisch et al., Gaussian, Inc., Wallingford, CT (2003), using either Revision C. 01wis2 (2004) or Revision E. 01+MNG (2007)
N.B. Balabanov, K.A. Peterson, J. Chem. Phys. 123, 064107 (2005)
T.H. Dunning Jr., J. Chem. Phys. 90, 1007 (1989)
F. Jensen, J. Chem. Phys. 115, 9113 (2001)
F. Jensen, J. Chem. Phys. 116, 7372 (2002)
M.A. Iron, A.C.B. Lucassen, H. Cohen, M.E. van der Boom, J.M.L. Martin, J. Am. Chem. Soc. 126, 11699 (2004)
B.E. Williamson, T.C. VanCott, M.E. Boyle, G.C. Misener, M.J. Stillman, P.N. Schatz, J. Am. Chem. Soc. 114, 2412 (1992)
S. Nagamatsu, S. Kera, K.K. Okudaira, T. Fujikawa, N. Ueno, in The 4th Conference on Electronic Structure and Processes at Molecular-Based Interfaces, Princeton University, Princeton, NJ, USA, June 2008
P. Coppens, L. Li, N.J. Zhu, J. Am. Chem. Soc. 105, 6173 (1983)
J. Janczak, R. Kubiak, Inorg. Chim. Act. 342, 64 (2003)
N. Papageorgiou, E. Salomon, T. Angot, J.M. Layet, L. Giovanelli, G. Le Lay, Prog. Surf. Sci. 77, 139 (1004)
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Marom, N., Kronik, L. Density functional theory of transition metal phthalocyanines, II: electronic structure of MnPc and FePc—symmetry and symmetry breaking. Appl. Phys. A 95, 165–172 (2009). https://doi.org/10.1007/s00339-008-5005-1
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DOI: https://doi.org/10.1007/s00339-008-5005-1