An experimental and ab initio study of the electronic spectrum of the jet-cooled F{sub 2}BO free radical

Grimminger, Robert; Sheridan, Phillip M.

doi:10.1063/1.4871010

Title: An experimental and ab initio study of the electronic spectrum of the jet-cooled F{sub 2}BO free radical

Full Record
Other Related Research

Abstract

We have studied the B{sup ~} {sup 2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} laser-induced fluorescence (LIF) spectrum of the jet-cooled F{sub 2}BO radical for the first time. The transition consists of a strong 0{sub 0}{sup 0} band at 446.5 nm and eight weak sequence bands to shorter wavelengths. Single vibronic level emission spectra obtained by laser excitation of individual levels of the B{sup ~} state exhibit two electronic transitions: a very weak, sparse B{sup ~}–X{sup ~} band system in the 450–500 nm region and a stronger, more extensive set of B{sup ~} {sup 2}A{sub 1}–A{sup ~} {sup 2}B{sub 1} bands in the 580–650 nm region. We have also performed a series of high level ab initio calculations to predict the electronic energies, molecular structures, vibrational frequencies, and rotational and spin-rotation constants in the X{sup ~} {sup 2}B{sub 2}, A{sup ~2}B{sub 1} and B{sup ~} {sup 2}A{sub 1} electronic states as an aid to the analysis of the experimental data. The theoretical results have been used as input for simulations of the rotationally resolved B{sup ~} {sup 2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} 0{sub 0}{sup 0} LIF band and Franck-Condon profiles of the LIF and single vibronic level emission spectra. Themore »« less

Authors:

Grimminger, Robert; Sheridan, Phillip M. ^[1]

Department of Chemistry and Biochemistry, Canisius College, Buffalo, New York 14208 (United States)

Publication Date:: Mon Apr 28 00:00:00 EDT 2014

OSTI Identifier:: 22253060

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 140; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; EMISSION SPECTRA; EXCITATION; EXCITED STATES; FLUORESCENCE; LITHIUM FLUORIDES; MOLECULAR STRUCTURE; RADICALS; ROTATION; SIMULATION; WAVELENGTHS

Citation Formats


                    Grimminger, Robert, Clouthier, Dennis J., E-mail: dclaser@uky.edu, and Sheridan, Phillip M. An experimental and ab initio study of the electronic spectrum of the jet-cooled F{sub 2}BO free radical.  United States: N. p., 2014. 
        Web.  doi:10.1063/1.4871010.

Copy to clipboard


                    Grimminger, Robert, Clouthier, Dennis J., E-mail: dclaser@uky.edu, & Sheridan, Phillip M. An experimental and ab initio study of the electronic spectrum of the jet-cooled F{sub 2}BO free radical.  United States.  https://doi.org/10.1063/1.4871010

Copy to clipboard


                    Grimminger, Robert, Clouthier, Dennis J., E-mail: dclaser@uky.edu, and Sheridan, Phillip M. 2014.  
        "An experimental and ab initio study of the electronic spectrum of the jet-cooled F{sub 2}BO free radical".  United States.  https://doi.org/10.1063/1.4871010.

Copy to clipboard


                    
@article{osti_22253060,

  title        = {An experimental and ab initio study of the electronic spectrum of the jet-cooled F{sub 2}BO free radical},

  author       = {Grimminger, Robert and Clouthier, Dennis J., E-mail: dclaser@uky.edu and Sheridan, Phillip M.},

  abstractNote = {We have studied the B{sup ~} {sup 2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} laser-induced fluorescence (LIF) spectrum of the jet-cooled F{sub 2}BO radical for the first time. The transition consists of a strong 0{sub 0}{sup 0} band at 446.5 nm and eight weak sequence bands to shorter wavelengths. Single vibronic level emission spectra obtained by laser excitation of individual levels of the B{sup ~} state exhibit two electronic transitions: a very weak, sparse B{sup ~}–X{sup ~} band system in the 450–500 nm region and a stronger, more extensive set of B{sup ~} {sup 2}A{sub 1}–A{sup ~} {sup 2}B{sub 1} bands in the 580–650 nm region. We have also performed a series of high level ab initio calculations to predict the electronic energies, molecular structures, vibrational frequencies, and rotational and spin-rotation constants in the X{sup ~} {sup 2}B{sub 2}, A{sup ~2}B{sub 1} and B{sup ~} {sup 2}A{sub 1} electronic states as an aid to the analysis of the experimental data. The theoretical results have been used as input for simulations of the rotationally resolved B{sup ~} {sup 2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} 0{sub 0}{sup 0} LIF band and Franck-Condon profiles of the LIF and single vibronic level emission spectra. The agreement between the simulations obtained with purely ab initio parameters and the experimental spectra validates the geometries calculated for the ground and excited states and the conclusion that the radical has C{sub 2v} symmetry in the X{sup ~}, A{sup ~}, and B{sup ~} states. The spectra provide considerable new information about the vibrational energy levels of the X{sup ~} and A{sup ~} states, but very little for the B{sup ~} state, due to the very restrictive Franck-Condon factors in the LIF spectra.},

  doi          = {10.1063/1.4871010},

  url          = {https://www.osti.gov/biblio/22253060},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 16,

  volume       = 140,

  place        = {United States},

  year         = {Mon Apr 28 00:00:00 EDT 2014},

  month        = {Mon Apr 28 00:00:00 EDT 2014}

}

Copy to clipboard

Journal Article:

https://doi.org/10.1063/1.4871010

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

In search of the X{sub 2}BO and X{sub 2}BS (X = H, F) free radicals: Ab initio studies of their spectroscopic signatures

Journal Article

The F{sub 2}BO free radical is a known, although little studied, species but similar X{sub 2}BY (X = H, D, F; Y = O, S) molecules are largely unknown. High level ab initio methods have been used to predict the molecular structures, vibrational frequencies (in cm{sup −1}), and relative energies of the ground and first two excited electronic states of these free radicals, as an aid to their eventual spectroscopic identification. The chosen theoretical methods and basis sets were tested on F{sub 2}BO and found to give good agreement with the known experimental quantities. In particular, complete basis set extrapolationsmore »« less
https://doi.org/10.1063/1.4904290
Communication: A vibrational study of propargyl cation using the vacuum ultraviolet laser velocity-map imaging photoelectron method

Journal Article Hong, Gao; Zhou, Lu; Lei, Yang; ... - Journal of Chemical Physics

By employing the vacuum ultraviolet (VUV) laser velocity-map imaging photoelectron (VUV-VMI-PE) method, we have obtained a vibrationally resolved photoelectron spectrum of gaseous propargyl radical [C{sub 3}H{sub 3}(X{sup 2}B{sub 1})] in the energy range of 0-4600 cm{sup -1} above its ionization energy. The cold C{sub 3}H{sub 3} radicals were produced from a supersonically cooled radical beam source based on 193 nm ArF photodissociation of C{sub 3}H{sub 3}Cl. The VUV-VMI-PE spectrum of C{sub 3}H{sub 3} thus obtained reveals a Franck-Condon factor (FCF) pattern with a highly dominant origin band along with weak vibrational progressions associated with excitations of the C-C {nu}{sub 5}{supmore »« less
https://doi.org/10.1063/1.4764306
Applied quantum chemistry: Spectroscopic detection and characterization of the F{sub 2}BS and Cl{sub 2}BS free radicals in the gas phase

Journal Article Jin, Bing; Sheridan, Phillip - Journal of Chemical Physics

In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X{sub 2}BY (X = H, halogen, Y = O, S) free radicals have been predicted using high level ab initio theory. The theoretical results have been used to calculate the electronic absorption and single vibronic level (SVL) emission spectra of the radicals under typical jet-cooled conditions. Using these diagnostic predictions, the previously unknown F{sub 2}BS and Cl{sub 2}BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF{sub 3}more »« less
https://doi.org/10.1063/1.4915126
Spectroscopic detection and characterization of the FS[sub 2] free radical

Journal Article Zhuo, Q; Karolczak, J; Clouthier, D - Journal of Chemical Physics; (United States)

An extensive vibronic band system of the FS[sub 2] radical in the 700--485 nm region has been observed for the first time by laser-induced fluorescence (LIF) probing of the products of the reaction of F[sub 2] with various sulfur-containing compounds. Jet-cooled spectra were obtained by reacting fluorine with COS, H[sub 2]S, or CS[sub 2] in the body of a continuous supersonic jet, just prior to expansion. Vibrational analysis of the jet spectra gives [nu][sub 1][sup [prime]] = 768, [nu][sub 2][sup [prime]] = 217, [nu][sub 3][sup [prime]] = 495, [nu][sub 1][sup [double prime]] = 705, [nu][sub 2][sup [double prime]] = 293,more »« less
https://doi.org/10.1063/1.467074
Anion photoelectron spectroscopy of B{sub 2}N{sup {minus}}

Journal Article Asmis, K; Taylor, T; Neumark, D - Journal of Chemical Physics

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 frommore »« less
https://doi.org/10.1063/1.480230

Similar Records