title: Excited state structural dynamics and Herzberg-Teller coupling of tetraphenylporphine explored via resonance Raman spectroscopy and density functional theory calculation.
abstract: Resonance Raman spectra of free-base tetraphenylporphine (TPP) were obtained with 397.9, 416, and 435.7nm excitation wavelengths and density functional calculations were done to elucidate the electronic transitions and the resonance Raman spectra (RRs) of TPP. The RRs indicate that the Franck-Condon region photodynamics for S(0)-->S(4) electronic state is predominantly along the C(m)-ph stretch while that for S(0)-->S(3) electronic state is predominantly along the porphin ring C(beta)C(beta) stretch. Non-totally symmetric vibrational modes were regularly presented in resonance Raman spectra: the shorter the excitation wavelengths were, the stronger intensity the modes had, which can be interpreted in terms of electric dipole transition moments caused by Franck-Condon and Herzberg-Teller coupling. Four non-total symmetry vibrational mode upsilon(52,)upsilon(64), upsilon(97) and upsilon(130) in A(2) irreducible representative of TPP were observed in 397.9, 416 and 435.7nm resonance Raman spectrum. With the shorter wavelength laser excitations at 416 or 397.9nm, the A(2) vibrational modes show more enhanced Raman intensity by comparison with those in the TPP spectrum excited at 435.7nm.
authors.affiliation: Department of Chemistry and State Key Laboratory of ATMMT(MOE), Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China.
authors.forename: Jun
authors.initials: J
authors.lastname: Xu
authors.forename: Junmin
authors.initials: J
authors.lastname: Wan
authors.forename: Yanying
authors.initials: Y
authors.lastname: Zhao
authors.forename: Miaoqiang
authors.initials: M
authors.lastname: Lv
authors.forename: Xuming
authors.initials: X
authors.lastname: Zheng
authors.forename: Guodong
authors.initials: G
authors.lastname: Wang
authors.forename: Huigang
authors.initials: H
authors.lastname: Wang
mesh_terms: D004583:Electrons; D008752:Methylene Chloride / Q000737:chemistry; D008956:Models, Chemical; D011166:Porphyrins / Q000737:chemistry*; D012996:Solutions; D012997:Solvents / Q000737:chemistry; D013059:Spectrum Analysis, Raman; D013816:Thermodynamics; D014732:Vibration
chemical_list: D011166:Porphyrins; D012996:Solutions; D012997:Solvents; D008752:Methylene Chloride; C049692:tetraphenylporphine