title: First Principles Studies of the Vibrationally Resolved Magnetic Circular Dichroism Spectra of Biphenylene.
abstract: We present density-functional response theory calculations of the one-photon absorption and magnetic circular dichroism spectral bandshapes of biphenylene. The effects from the surrounding solvent environment and molecular vibrations have been included. The solvent is described by the Polarizable Continuum Model (PCM), while the vibrational structures of the spectra have been computed including both Franck-Condon and Herzberg-Teller contributions in the vibronic model. This is the first study of vibronic effects on magnetic circular dichroism spectra including non-Franck-Condon contributions. A detailed comparison with experimental data has been performed, revealing that the B3LYP functional in combination with PCM gives the best agreement with experimental data. Our calculations indicate that nonadiabatic vibronic coupling may play a role, and even small computational inaccuracies might cause significant changes in the calculated HT term, which raises concerns about the inclusion of HT contributions in the calculations of vibronic MCD in systems that have close-lying excited states.
authors.affiliation: State Key Laboratory of Crystal Materials, Shandong University, 250100 Jinan, Shandong, People's Republic of China.|Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
authors.forename: Na
authors.initials: N
authors.lastname: Lin
authors.affiliation: Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
authors.forename: Harald
authors.initials: H
authors.lastname: Solheim
authors.affiliation: State Key Laboratory of Crystal Materials, Shandong University, 250100 Jinan, Shandong, People's Republic of China.
authors.forename: Xian
authors.initials: X
authors.lastname: Zhao
authors.affiliation: Consiglio Nazionale delle Ricerche-CNR, Istituto di Chimica dei Composti Organo Metallici (ICCOM-CNR), UOS di Pisa, Area della Ricerca, Via G. Moruzzi 1, I-56124 Pisa, Italy.
authors.forename: Fabrizio
authors.initials: F
authors.lastname: Santoro
authors.affiliation: Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
authors.forename: Kenneth
authors.initials: K
authors.lastname: Ruud