TY - JOUR

T1 - Theoretical study on exciton recurrence motion in anthracene dimer using the ab initio MO-CI based quantum master equation approach

AU - Kishi, Ryohei

AU - Nakano, Masayoshi

AU - Minami, Takuya

AU - Fukui, Hitoshi

AU - Nagai, Hiroshi

AU - Yoneda, Kyohei

AU - Takahashi, Hideaki

PY - 2009/5/7

Y1 - 2009/5/7

N2 - We apply the ab initio molecular orbital (MO)-conflguration interaction (CI) based quantum master equation (MOQME) method to the investigation of ultrafast exciton dynamics in an anthracene dimer modeled after anthracenophane, which is experimentally found to exhibit an oscillatory signal of fluorescence anisotropy decay. Two low-lying near-degenerate one-photon allowed excited states with a slight energy difference (42 cm-1) are obtained at the CIS/6-31G**level of approximation using full valence TT-orbitals. The time evolution of reduced exciton density matrices is performed by numerically solving the quantum master equation. After the creation of a superposition state of these near-degenerate states by irradiating a near-resonant laser field, we observe two kinds of oscillatory behaviors of polarizations: field-induced polarizations with faster periods, and amplitude oscillations of x- and z-polarizations, Px and Pz, with a slower period, in which the amplitudes of Px and Pz attain maximum alternately. The latter behavior turns out to be associated with an oscillatory exciton motion between the two monomers, i.e., exciton recurrence motion, using the dynamic exciton expression based on the polarization density. From the analysis of contribution to the exciton distributions, such exciton recurrence motion is found to be characterized by both the difference in eigenfrequencies between the two near-degenerate states excited by the laser field and the relative phases among the frontier MOs primarily contributing to the near-degenerate states.

AB - We apply the ab initio molecular orbital (MO)-conflguration interaction (CI) based quantum master equation (MOQME) method to the investigation of ultrafast exciton dynamics in an anthracene dimer modeled after anthracenophane, which is experimentally found to exhibit an oscillatory signal of fluorescence anisotropy decay. Two low-lying near-degenerate one-photon allowed excited states with a slight energy difference (42 cm-1) are obtained at the CIS/6-31G**level of approximation using full valence TT-orbitals. The time evolution of reduced exciton density matrices is performed by numerically solving the quantum master equation. After the creation of a superposition state of these near-degenerate states by irradiating a near-resonant laser field, we observe two kinds of oscillatory behaviors of polarizations: field-induced polarizations with faster periods, and amplitude oscillations of x- and z-polarizations, Px and Pz, with a slower period, in which the amplitudes of Px and Pz attain maximum alternately. The latter behavior turns out to be associated with an oscillatory exciton motion between the two monomers, i.e., exciton recurrence motion, using the dynamic exciton expression based on the polarization density. From the analysis of contribution to the exciton distributions, such exciton recurrence motion is found to be characterized by both the difference in eigenfrequencies between the two near-degenerate states excited by the laser field and the relative phases among the frontier MOs primarily contributing to the near-degenerate states.

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U2 - 10.1021/jp8111588

DO - 10.1021/jp8111588

M3 - Article

C2 - 19331381

AN - SCOPUS:65649136172

SN - 1089-5639

VL - 113

SP - 5455

EP - 5462

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 18

ER -