Interpretation of the electronic absorption spectrum of free-base porphin using time-dependent density-functional theory

The electronic absorption spectrum of free-base porphin has been studied at density-functional theory (DFT) level using the time-dependent perturbation theory approach. The optimization of the molecular structure was carried out using the Becke–Perdew functional and split-valence quality basis sets augmented by polarization functions. In the calculation of the electronic excitation energies, the same functional was employed while the basis set was further augmented by diffuse s, p, and d functions. The calculated absorption spectrum agrees with recent ab initio and DFT calculations and with experiment. The B-band must be assigned to the strong 3 1B2u and the 3 1B3u transitions. Two additional weak transitions (2 1B2u and 2 1B3u) are found below the B band. However, these states have not been obtained at CASSCF (CASPT2) and DFT/MRCI levels and might be an artifact of the functional used. The lowest symmetry-allowed triplet–triplet transition is calculated to be 1.58 eV as compared to the experimental value of 1.56–1.58 eV.

[1]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[2]  B. F. Kim,et al.  Site selective optical spectra of free base porphin in anthracene , 1978 .

[3]  Marco Häser,et al.  Auxiliary basis sets to approximate Coulomb potentials (Chem. Phys. Letters 240 (1995) 283-290) , 1995 .

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

[5]  D. Sundholm.  Density functional theory calculations of the visible spectrum of chlorophyll a , 1999 .

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

[7]  Michael J. Frisch,et al.  Toward a systematic molecular orbital theory for excited states , 1992 .

[8]  Theoretical determination of the electronic spectrum of free base porphin , 1994 .

[9]  J. Olsen,et al.  The exactness of the extended Koopmans’ theorem: A numerical study , 1993 .

[10]  Marco Häser,et al.  CALCULATION OF EXCITATION ENERGIES WITHIN TIME-DEPENDENT DENSITY FUNCTIONAL THEORY USING AUXILIARY BASIS SET EXPANSIONS , 1997 .

[11]  Hiroshi Nakatsuji,et al.  Theoretical Study of the Excited States of Chlorin, Bacteriochlorin, Pheophytin a, and Chlorophyll a by the SAC/SAC-CI Method , 1998 .

[12]  R. Ahlrichs,et al.  Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory , 1996 .

[13]  E. Baerends,et al.  Time-dependent density functional calculations on the electronic absorption spectrum of free base porphin , 1999 .

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

[15]  H. Nakatsuji,et al.  SAC-CI Study on the Excited and Ionized States of Free-Base Porphin: Rydberg Excited States and Effect of Polarization and Rydberg Functions , 1998 .

[16]  Nicholas C. Handy,et al.  Improving virtual Kohn-Sham orbitals and eigenvalues: Application to excitation energies and static polarizabilities , 1998 .

[17]  Martin Gouterman,et al.  Study of the Effects of Substitution on the Absorption Spectra of Porphin , 1959 .

[18]  Hiroshi Nakatsuji,et al.  EXCITED AND IONIZED STATES OF FREE BASE PORPHIN STUDIED BY THE SYMMETRY ADAPTED CLUSTER-CONFIGURATION INTERACTION (SAC-CI) METHOD , 1996 .

[19]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[20]  M. Zerner,et al.  Applications of the random phase approximation with the INDO/S Hamiltonian: UVVIS spectra of free base porphin , 1990 .

[21]  L. K. Hanson.  THEORETICAL CALCULATIONS OF PHOTOSYNTHETIC PIGMENTS , 1988 .

[22]  M. Petersilka,et al.  Excitation energies from time-dependent density-functional theory. , 1996 .

[23]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[24]  Martin Gouterman,et al.  Spectra of porphyrins: Part II. Four orbital model , 1963 .

[25]  T. Noro,et al.  Ab initio CI calculations on free-base porphin , 1992 .

[26]  R. C. Morrison.  Comment on ‘‘The exactness of the extended Koopmans’ theorem: A numerical study’’ [J. Chem. Phys. 98, 3999 (1993)] , 1993 .

[27]  C. Mcauliffe,et al.  The status of molecular orbital calculations on porphyrins and their complexes , 1975 .

[28]  R. Ahlrichs,et al.  STABILITY ANALYSIS FOR SOLUTIONS OF THE CLOSED SHELL KOHN-SHAM EQUATION , 1996 .

[29]  Martin Gouterman,et al.  Porphyrin free base phosphorescence , 1974 .

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

[31]  M. Gouterman,et al.  SELF-CONSISTENT MOLECULAR ORBITAL CALCULATIONS OF PORPHYRIN AND RELATED RING SYSTEMS. , 1965 .

[32]  U. Nagashima,et al.  Abinitio SCF‐CI calculation on free base porphin and chlorin; theoretical analysis on intensities of the absorption spectra , 1986 .

[33]  Manuela Merchán,et al.  Interpretation of the electronic absorption spectrum of free base porphin by using multiconfigurational second-order perturbation theory , 1998 .

[34]  Rodney J. Bartlett,et al.  Similarity transformed equation-of-motion coupled-cluster study of ionized, electron attached, and excited states of free base porphin , 1997 .

[35]  Rodney J. Bartlett,et al.  Coupled-cluster calculations of the electronic excitation spectrum of free base porphin in a polarized basis , 1998 .

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

[37]  J. G. Snijders,et al.  Improved density functional theory results for frequency‐dependent polarizabilities, by the use of an exchange‐correlation potential with correct asymptotic behavior , 1996 .

[38]  J. Michl,et al.  Fourier transform fluorescence and phosphorescence of porphine in rare gas matrices , 1991 .

[39]  S. Grimme,et al.  A COMBINATION OF KOHN-SHAM DENSITY FUNCTIONAL THEORY AND MULTI-REFERENCE CONFIGURATION INTERACTION METHODS , 1999 .

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

[41]  David Dolphin,et al.  Porphyrins XVII. Vapor absorption spectra and redox reactions: Tetraphenylporphins and porphin , 1971 .

[42]  Dennis R. Salahub,et al.  Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold , 1998 .

[43]  G. Scuseria,et al.  An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules , 1998 .

[44]  E. Gross,et al.  Density-Functional Theory for Time-Dependent Systems , 1984 .

[45]  O. Kitao,et al.  Theoretical study of the mechanism of electron transfer at photosynthetic reaction centers. I. Singlet excited states of free base porphin , 1999 .

[46]  A. Schäfer,et al.  Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr , 1994 .