Ab initio description of photoabsorption and electron transfer in a doubly‐linked porphyrin‐fullerene dyad

Structure, photoabsorption and excited states of two representative conformations obtained from molecular dynamics (MD) simulations of a doubly‐linked porphyrin‐fullerene dyad DHD6ee are studied by using both DFT and wavefunction based methods. Charge transfer from the donor (porphyrin) to the acceptor (fullerene) and the relaxation of the excited state are of special interest. The results obtained with LDA, GGA, and hybrid functionals (SVWN, PBE, and B3LYP, respectively) are analyzed with emphasis on the performance of used functionals as well as from the point of view of their comparison with wavefunction based methods (CCS, CIS(D), and CC2). Characteristics of the MD structures are retained in DFT optimization. The relative orientation of porphyrin and fullerene is significantly influencing the MO energies, the charge transfer (CT) in the ground state of the dyad and the excitation of ground state CT complex (g‐CTC). At the same time, the excitation to the locally excited state of porphyrin is only little influenced by the orientation or cc distance. TD‐DFT underestimates the excitation energy of the CT state, however for some cases (with relatively short donor‐acceptor separations), the use of a hybrid functional like B3LYP alleviates the problem. Wavefunction based methods and CC2 in particular appear to overestimate the CT excitation energies but the inclusion of proper solvation models can significantly improve the results. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009

[1]  Kenneth B. Wiberg,et al.  Solvent effects. 3. Tautomeric equilibria of formamide and 2-pyridone in the gas phase and solution: an ab initio SCRF study , 1992 .

[2]  J. C. Slater.  A Simplification of the Hartree-Fock Method , 1951 .

[3]  Poul Jørgensen,et al.  The second-order approximate coupled cluster singles and doubles model CC2 , 1995 .

[4]  Helge Lemmetyinen,et al.  An Extremely Small Reorganization Energy of Electron Transfer in Porphyrin−Fullerene Dyad , 2001 .

[5]  Fabio Della Sala,et al.  The localized Hartree–Fock method for a self-interaction free Kohn–Sham potential: applications to closed and open-shell molecules , 2007 .

[6]  Dmitrij Rappoport,et al.  Photoinduced intramolecular charge transfer in 4-(dimethyl)aminobenzonitrile--a theoretical perspective. , 2004, Journal of the American Chemical Society.

[7]  Jorge M. Seminario,et al.  Recent developments and applications of modern density functional theory , 1996 .

[8]  Manabu Oumi,et al.  Quasidegenerate second-order perturbation corrections to single-excitation configuration interaction , 1999 .

[9]  Hans W. Horn,et al.  ELECTRONIC STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS: THE PROGRAM SYSTEM TURBOMOLE , 1989 .

[10]  L. Onsager.  Electric Moments of Molecules in Liquids , 1936 .

[11]  Carlo Adamo,et al.  Self-interaction error in density functional theory: a mean-field correction for molecules and large systems , 2005 .

[12]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[13]  Manabu Oumi,et al.  A doubles correction to electronic excited states from configuration interaction in the space of single substitutions , 1994 .

[14]  Christof Hättig,et al.  Analytic gradients for excited states in the coupled-cluster model CC2 employing the resolution-of-the-identity approximation , 2003 .

[15]  Hiroko Yamada,et al.  Exciplex intermediates in photoinduced electron transfer of porphyrin-fullerene dyads. , 2002, Journal of the American Chemical Society.

[16]  Christopher J Cramer,et al.  Quantum Chemical Characterization of the Structural and Energetic Properties of HCN-BF3. , 2005, Journal of chemical theory and computation.

[17]  Dage Sundholm,et al.  Interpretation of the electronic absorption spectrum of free-base porphin using time-dependent density-functional theory , 2000 .

[18]  A. Becke.  A New Mixing of Hartree-Fock and Local Density-Functional Theories , 1993 .

[19]  Hans W. Horn,et al.  Fully optimized contracted Gaussian basis sets for atoms Li to Kr , 1992 .

[20]  Helge Lemmetyinen,et al.  Tuning the ground-state and excited-state interchromophore interactions in porphyrin-fullerene π-stacks , 2004 .

[21]  Stefan Grimme,et al.  Calculation of 0-0 excitation energies of organic molecules by CIS(D) quantum chemical methods , 2004 .

[22]  Yoshiteru Sakata,et al.  Sequential Energy and Electron Transfer in an Artificial Reaction Center: Formation of a Long-Lived Charge-Separated State , 2000 .

[23]  Rudolph A. Marcus,et al.  Chemical and Electrochemical Electron-Transfer Theory , 1964 .

[24]  N V Tkachenko,et al.  Charge-transfer emission of compact porphyrin-fullerene dyad analyzed by Marcus theory of electron-transfer. , 2001, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[25]  Kirsi Tappura,et al.  Computational analysis of the conformations of a doubly linked porphyrin–fullerene dyad , 2006 .

[26]  Marco Häser,et al.  Auxiliary basis sets to approximate Coulomb potentials , 1995 .

[27]  Poul Jørgensen,et al.  Ground and excited state polarizabilities and dipole transition properties of benzene from coupled cluster response theory , 1999 .

[28]  Andreas B. J. Parusel,et al.  A DFT/MRCI study on the excited state charge transfer states of N-pyrrolobenzene, N-pyrrolobenzonitrile and 4-N,N-dimethylaminobenzonitrile , 2000 .

[29]  Helge Lemmetyinen,et al.  TD-DFT description of photoabsorption and electron transfer in a covalently bonded porphyrin-fullerene dyad. , 2006, The journal of physical chemistry. A.

[30]  Helge Lemmetyinen,et al.  The Role of the Exciplex State in Photoinduced Electron Transfer of Phytochlorin−[60]Fullerene Dyads , 2002 .

[31]  Gang Zhang,et al.  Comparison of DFT methods for molecular orbital eigenvalue calculations. , 2007, The journal of physical chemistry. A.

[32]  Chang-Guo Zhan,et al.  Cavity size in reaction field theory , 1998 .

[33]  Helge Lemmetyinen,et al.  Ultrafast Photodynamics of Exciplex Formation and Photoinduced Electron Transfer in Porphyrin−Fullerene Dyads Linked at Close Proximity , 2003 .

[34]  Christof Hättig,et al.  CC2 excitation energy calculations on large molecules using the resolution of the identity approximation , 2000 .

[35]  Alberto Vela,et al.  Charge-Transfer Complexes: Stringent Tests for Widely Used Density Functionals , 1996 .

[36]  Helge Lemmetyinen,et al.  Photoinduced Electron Transfer in Phytochlorin-(60)Fullerene Dyads , 1999 .

[37]  Curtis L. Janssen,et al.  New diagnostics for coupled-cluster and Møller–Plesset perturbation theory , 1998 .

[38]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[39]  Stefan Grimme,et al.  Comparison of multireference Møller-Plesset theory and time-dependent methods for the calculation of vertical excitation energies of molecules , 2002 .

[40]  Helge Lemmetyinen,et al.  Ultrafast charge transfer in phytochlorin-[60]fullerene dyads: influence of the attachment position , 2001 .

[41]  Martin Head-Gordon,et al.  Accurate calculations on excited states: new theories applied to the –OX, –XO, and –XO2 (X=Cl and Br) chromophores and implications for stratospheric bromine chemistry , 1999 .

[42]  Luis Echegoyen,et al.  Design, synthesis, and photophysical studies of a porphyrin-fullerene dyad with parachute topology; charge recombination in the marcus inverted region. , 2004, Journal of the American Chemical Society.

[43]  Angel Rubio,et al.  Electronic structure and excitations in oligoacenes from ab initio calculations. , 2006, The Journal of chemical physics.

[44]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[45]  Filipp Furche,et al.  Adiabatic time-dependent density functional methods for excited state properties , 2002 .

[46]  Hans Lischka,et al.  Excited-state intramolecular proton transfer: a survey of TDDFT and RI-CC2 excited-state potential energy surfaces. , 2005, The journal of physical chemistry. A.

[47]  M. Head‐Gordon,et al.  Long-range charge-transfer excited states in time-dependent density functional theory require non-local exchange , 2003 .