Anion photoelectron spectroscopy of B{sub 2}N{sup {minus}}
Abstract
Vibrationally resolved 355 and 266 nm anion photoelectron spectra of B{sub 2}N are presented. Photodetachment to two electronic states of linear B{endash}N{endash}B is observed and, aided by electronic structure calculations, assigned to the {tilde X}&hthinsp;{sup 1}{Sigma}{sub g}{sup +}{r_arrow}{tilde X}&hthinsp;{sup 2}{Sigma}{sub u}{sup +}+e{sup {minus}} and {tilde X}&hthinsp;{sup 1}{Sigma}{sub g}{sup +}{r_arrow}{tilde A}&hthinsp;{sup 2}{Sigma}{sub g}{sup +}+e{sup {minus}} transitions. The electron affinity of B{sub 2}N is 3.098{plus_minus}0.005&hthinsp;eV and the {tilde A}&hthinsp;{sup 2}{Sigma}{sub g}{sup +} term energy T{sub 0} is 0.785{plus_minus}0.005&hthinsp;eV. Observation of excitations involving uneven quanta of the antisymmetric stretching mode (v{sub 3}) indicates a breakdown of the Franck{endash}Condon (FC) approximation and results from Herzberg{endash}Teller vibronic coupling between the {tilde X}&hthinsp;{sup 2}{Sigma}{sub u}{sup +} and {tilde A}&hthinsp;{sup 2}{Sigma}{sub g}{sup +} states involving the v{sub 3} mode. Measurement of the angular dependence of the photodetached electrons serves as a sensitive probe for the identification of these FC forbidden transitions. A linear vibronic coupling model qualitatively reproduces the perturbed v{sub 3} potentials of the {tilde X} and {tilde A} states. Artifactual symmetry breaking along the v{sub 3} coordinate is observed in the {ital ab initio} wave functions for the neutral ground state up to the coupledcluster level of theory, even when Brueckner orbitals are used. Nomore »
 Authors:

 Department of Chemistry, University of California, Berkeley
 Publication Date:
 OSTI Identifier:
 692550
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 111; Journal Issue: 19; Other Information: PBD: Nov 1999
 Country of Publication:
 United States
 Language:
 English
 Subject:
 66 PHYSICS; BORON COMPOUNDS; ANIONS; AFFINITY; PHOTOELECTRON SPECTROSCOPY; BORON NITRIDES; MOLECULAR IONS; ELECTRON DETACHMENT; ELECTRONIC STRUCTURE; VIBRATIONAL STATES; FORBIDDEN TRANSITIONS
Citation Formats
Asmis, K R, Taylor, T R, Neumark, D M, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. Anion photoelectron spectroscopy of B{sub 2}N{sup {minus}}. United States: N. p., 1999.
Web. doi:10.1063/1.480230.
Asmis, K R, Taylor, T R, Neumark, D M, & Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. Anion photoelectron spectroscopy of B{sub 2}N{sup {minus}}. United States. https://doi.org/10.1063/1.480230
Asmis, K R, Taylor, T R, Neumark, D M, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. 1999.
"Anion photoelectron spectroscopy of B{sub 2}N{sup {minus}}". United States. https://doi.org/10.1063/1.480230.
@article{osti_692550,
title = {Anion photoelectron spectroscopy of B{sub 2}N{sup {minus}}},
author = {Asmis, K R and Taylor, T R and Neumark, D M and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720},
abstractNote = {Vibrationally resolved 355 and 266 nm anion photoelectron spectra of B{sub 2}N are presented. Photodetachment to two electronic states of linear B{endash}N{endash}B is observed and, aided by electronic structure calculations, assigned to the {tilde X}&hthinsp;{sup 1}{Sigma}{sub g}{sup +}{r_arrow}{tilde X}&hthinsp;{sup 2}{Sigma}{sub u}{sup +}+e{sup {minus}} and {tilde X}&hthinsp;{sup 1}{Sigma}{sub g}{sup +}{r_arrow}{tilde A}&hthinsp;{sup 2}{Sigma}{sub g}{sup +}+e{sup {minus}} transitions. The electron affinity of B{sub 2}N is 3.098{plus_minus}0.005&hthinsp;eV and the {tilde A}&hthinsp;{sup 2}{Sigma}{sub g}{sup +} term energy T{sub 0} is 0.785{plus_minus}0.005&hthinsp;eV. Observation of excitations involving uneven quanta of the antisymmetric stretching mode (v{sub 3}) indicates a breakdown of the Franck{endash}Condon (FC) approximation and results from Herzberg{endash}Teller vibronic coupling between the {tilde X}&hthinsp;{sup 2}{Sigma}{sub u}{sup +} and {tilde A}&hthinsp;{sup 2}{Sigma}{sub g}{sup +} states involving the v{sub 3} mode. Measurement of the angular dependence of the photodetached electrons serves as a sensitive probe for the identification of these FC forbidden transitions. A linear vibronic coupling model qualitatively reproduces the perturbed v{sub 3} potentials of the {tilde X} and {tilde A} states. Artifactual symmetry breaking along the v{sub 3} coordinate is observed in the {ital ab initio} wave functions for the neutral ground state up to the coupledcluster level of theory, even when Brueckner orbitals are used. No evidence is found for an energetically lowlying cyclic state of B{sub 2}N, which has been invoked in the assignment of the matrix infrared spectrum of B{sub 2}N. However, the matrix infrared data agrees well with the peak spacing observed in the photoelectron spectra and reassigned to the linear {tilde X}&hthinsp;{sup 2}{Sigma}{sub u}{sup +} ground state. {copyright} {ital 1999 American Institute of Physics.}},
doi = {10.1063/1.480230},
url = {https://www.osti.gov/biblio/692550},
journal = {Journal of Chemical Physics},
number = 19,
volume = 111,
place = {United States},
year = {1999},
month = {11}
}