Ab initio MRSD-CI calculations of the ground and the two lowest-lying excited states of pyrene

Abstract The ground and the two lowest-lying excited states of pyrene were studied using π-CASSCF and π-MRSD-CI calculations. The results show that the multireference effect is crucial in predicting the correct order of the two lowest-lying singlet excited states, the 1 1 B 2 u ( S 1 ) and the 1 1 B 3 u ( S 2 ) states. The calculated excitation energies from S 0 to S 1 and from S 0 to S 2 are 3.97 and 4.60 eV, respectively, which are about 120% of the experimental values. Various levels of the calculations are presented to analyze the electron correlation effects.

[1]  Kerstin Andersson,et al.  Second-order perturbation theory with a CASSCF reference function , 1990 .

[2]  S. Huzinaga,et al.  A systematic preparation of new contracted Gaussian‐type orbital sets. III. Second‐row atoms from Li through ne , 1980 .

[3]  S. Langhoff.  Theoretical Infrared Spectra for Polycyclic Aromatic Hydrocarbon Neutrals, Cations and Anions , 1996 .

[4]  Rudolph Pariser,et al.  Theory of the Electronic Spectra and Structure of the Polyacenes and of Alternant Hydrocarbons , 1956 .

[5]  B. Roos,et al.  A theoretical study of the electronic spectrum of naphthalene , 1994 .

[6]  M. Baldo,et al.  Dimensional and geometrical effects on the electronic structure of polycyclic hydrocarbons , 1984 .

[7]  D. Talbi,et al.  Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons: effect of ionization. , 1993, The Astrophysical journal.

[8]  B. Gilson,et al.  A comparative study of SCFMO calculations on alternant and nonalternant hydrocarbons , 1967 .

[9]  James F. Harrison,et al.  Ab Initio Study of Polycyclic Aromatic Hydrocarbons in Their Ground and Excited States , 1998 .

[10]  O. Parisel,et al.  Electronic and Vibrational Spectra Of Matrix-Isolated Pyrene Radical Cations: Theoretical and Experimental Aspects , 1994 .

[11]  Kimihiko Hirao,et al.  Multireference Møller—Plesset perturbation theory for high-spin open-shell systems , 1992 .

[12]  F. W. Birss,et al.  Semi-Empirical Configuration Interaction Studies on the π-Electron Spectra of Nonbenzenoid Molecules , 1978 .

[13]  M. Yoshimine,et al.  The alchemy configuration interaction method. I. The symbolic matrix method for determining elements of matrix operators , 1981 .

[14]  Byron H. Lengsfield,et al.  General second order MCSCF theory: A density matrix directed algorithm , 1980 .

[15]  J. K. Dohrmann,et al.  EQUILIBRIA AND RATES OF REDOX REACTIONS INVOLVING THE 2-TERT-BUTYL-1,4-BENZOSEMIQUINONE RADICAL IN AQUEOUS SOLUTION : AN INVESTIGATION BY POTENTIOMETR Y, ESR, AND PULSE RADIOLYSIS , 1995 .

[16]  Bowen Liu,et al.  A second order MCSCF method for large CI expansions , 1981 .

[17]  Yukio Kawashima,et al.  Theoretical study of the valence π → π* excited states of polyacenes: anthracene and naphthacene , 1999 .

[18]  Kimihiko Hirao,et al.  Multireference Møller-Plesset method , 1992 .

[19]  Kimihiko Hirao,et al.  Theoretical study of the valence π→π* excited states of polyacenes: Benzene and naphthalene , 1996 .

[20]  M. Lamotte,et al.  Quasilinear fluorescence of pyrene in a monocrystalline matrix of n-heptane , 1976 .

[21]  E. Castellucci,et al.  The two-photon excitation spectrum of pyrene , 1983 .

[22]  Kimihiko Hirao,et al.  State-specific multireference Møller—Plesset perturbation treatment for singlet and triplet excited states, ionized states and electron attached states of H2O , 1993 .

[23]  Michael R. Topp,et al.  Excited-state dynamics of jet-cooled pyrene and some molecular complexes , 1986 .