Photoelectron spectrum and dynamics of the uracil cation. 2015

Mariana Assmann, and Horst Köppel, and Spiridoula Matsika
Department of Chemistry, Temple University , Philadelphia, Pennsylvania 19122, United States.

The photoelectron spectrum of uracil and the molecular dynamics of its radical cation are investigated using the multiconfigurational time-dependent Hartree (MCTDH) method. For this aim, the vibronic coupling model Hamiltonian is used including up to ten important a' modes. Moreover, to account for coupling through conical intersections between states of different symmetry in the system, coupling constants of two a″ modes are taken into account. The parameters used in the model are obtained by fitting to ab inito data obtained with extensive EOM-IP-CCSD calculations. The first four cationic states were investigated, which are either of A″ (hole in a π orbital) or A' (hole in a nO orbital) symmetry. The results of the wavepacket propagations were used to calculate the corresponding photoelectron spectrum and compare to the experimental spectrum. The MCTDH simulations reproduce the experimental spectrum well. The dynamics starting from the D2 and D3 ionic states show a fast relaxation to the cationic ground state often involving direct D2-D0 or D3-D1 transitions.

UI MeSH Term Description Entries
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D002412 Cations Positively charged atoms, radicals or groups of atoms which travel to the cathode or negative pole during electrolysis. Cation
D014498 Uracil One of four nucleotide bases in the nucleic acid RNA.
D056951 Photoelectron Spectroscopy The study of the energy of electrons ejected from matter by the photoelectric effect, i.e., as a direct result of absorption of energy from electromagnetic radiation. As the energies of the electrons are characteristic of a specific element, the measurement of the energy of these electrons is a technique used to determine the chemical composition of surfaces. Photoelectron Spectrometry,Electron Spectroscopy for Chemical Analysis,Photoelectron Emission Spectroscopy,Photoemission Spectroscopy,Ultra-Violet Photoelectron Spectroscopy,Ultraviolet Photoelectron Spectroscopy,X-Ray Photoelectron Spectroscopy,Xray Photoelectron Spectroscopy,Emission Spectroscopies, Photoelectron,Emission Spectroscopy, Photoelectron,Photoelectron Spectroscopy, Ultra-Violet,Photoelectron Spectroscopy, Ultraviolet,Photoelectron Spectroscopy, X-Ray,Photoelectron Spectroscopy, Xray,Spectrometry, Photoelectron,Spectroscopy, Photoelectron,Spectroscopy, Photoelectron Emission,Spectroscopy, Photoemission,Spectroscopy, Ultra-Violet Photoelectron,Spectroscopy, Ultraviolet Photoelectron,Spectroscopy, X-Ray Photoelectron,Spectroscopy, Xray Photoelectron,Ultra Violet Photoelectron Spectroscopy,X Ray Photoelectron Spectroscopy

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