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Title: 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 coupled-cluster level of theory, even when Brueckner orbitals are used. Nomore » evidence is found for an energetically low-lying 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.}« less

Authors:
; ;  [1]
  1. 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 coupled-cluster level of theory, even when Brueckner orbitals are used. No evidence is found for an energetically low-lying 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}
}