Article Large Shift and Small Broadening of Br2 Valence Band upon Dimer Formation with H2O: An Ab Initio Study ACS ActiveView PDFHi-Res Print, Annotate, Reference QuickView PDF [1531 KB] PDF w/ Links[906 KB] Full Text HTML Abstract Figures Reference QuickView Citing Articles Add to ACS ChemWorx Ricardo Franklin-Mergarejo , Instituto Superior de Tecnologías y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Quinta de los Molinos, Plaza, Habana 10600, Aptdo. Postal 6163, Ciudad Habana, Cuba Université de Toulouse, UPS, Laboratoire Collisions Agrégats Réactivité, IRSAMC, F-31062 Toulouse, France CNRS, UMR 5589, F-31062 Toulouse, France Jesus Rubayo-Soneira , Instituto Superior de Tecnologías y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Quinta de los Molinos, Plaza, Habana 10600, Aptdo. Postal 6163, Ciudad Habana, Cuba Nadine Halberstadt * , Université de Toulouse, UPS, Laboratoire Collisions Agrégats Réactivité, IRSAMC, F-31062 Toulouse, France CNRS, UMR 5589, F-31062 Toulouse, France Tahra Ayed , Centro de Investigaciones Químicas, UAEM, Cuernavaca, Mor. 62209, México Margarita I. Bernal-Uruchurtu and Ramón Hernández-Lamoneda , Centro de Investigaciones Químicas, UAEM, Cuernavaca, Mor. 62209, México Kenneth C. Janda Department of Chemistry, University of California, Irvine, California 92697-2025, United States J. Phys. Chem. A, 2011, 115 (23), pp 5983-5991 DOI: 10.1021/jp110389z Publication Date (Web): February 1, 2011 Copyright © 2011 American Chemical Society *E-mail: nadine.halberstadt@irsamc.ups-tlse.fr. This article is part of the Victoria Buch Memorial special issue. † Author Present Address Laboratoire de Physique de l′ État Condensé, Université du Maine et CNRS (UMR 6087), Avenue Olivier Messiaen, F-72085 Le Mans cedex, France. CASSection: Optical, Electron, and Mass Spectroscopy and Other Related Properties Abstract Abstract Image Valence electronic excitation spectra are calculated for the H2O***Br2 complex using highly correlated ab initio potentials for both the ground and the valence electronic excited states and a 2-D approximation for vibrational motion. Due to the strong interaction between the O−Br and the Br−Br stretching motions, inclusion of these vibrations is the minimum necessary for the spectrum calculation. A basis set calculation is performed to determine the vibrational wave functions for the ground electronic state and a wave packet simulation is conducted for the nuclear dynamics on the excited state surfaces. The effects of both the spin−orbit interaction and temperature on the spectra are explored. The interaction of Br2 with a single water molecule induces nearly as large a shift in the spectrum as is observed for an aqueous solution. In contrast, complex formation has a remarkably small effect on the T = 0 K width of the valence bands due to the fast dissociation of the dihalogen bond upon excitation. We therefore conclude that the widths of the spectra in aqueous solution are mostly due to inhomogeneous broadening.