Local electronic structure of dicarba-closo-dodecarboranes C 2B10H12

Timothy T. Fister, Fernando D. Vila, Gerald T. Seidler, Lukas Svec, John Linehan, Julie O. Cross

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

We report nonresonant inelastic X-ray scattering (NRIXS) measurement of core-shell excitations from both B 1s and C 1s initial states in all three isomers of the dicarba-closo-dodecarboranes C2B10H 12. First, these data yield an experimental determination of the angular-momentum-projected final local density of states (I-DOS). We find low-energy resonances with distinctive local s- or p-type character, providing a more complete experimental characterization of bond hybridization than is available from dipole-transition limited techniques, such as X-ray absorption spectroscopies. This analysis is supported by independent density functional theory and real-space full multiple scattering calculation of the I-DOS which yield a clear distinction between tangential and radial contributions. Second, we investigate the isomer sensitivity of the NRIXS signal and compare and contrast these results with prior electron energy loss spectroscopy measurements. This work establishes NRIXS as a valuable tool for borane chemistry, not only for the unique spectroscopic capabilities of the technique but also through its compatibility with future studies in solution or in high-pressure environments. In addition, this work also establishes the real-space full multiple scattering approach as a useful alternative to traditional approaches for excited states calculations of aromatic polyhedral boranes and related systems.

Original languageEnglish
Pages (from-to)925-932
Number of pages8
JournalJournal of the American Chemical Society
Volume130
Issue number3
DOIs
Publication statusPublished - Jan 23 2008

Fingerprint

Inelastic scattering
X ray scattering
Boranes
Electronic structure
DOS
Multiple scattering
X-Rays
Isomers
Electron Energy-Loss Spectroscopy
X-Ray Absorption Spectroscopy
X ray absorption spectroscopy
Angular momentum
Electron energy loss spectroscopy
Excited states
Density functional theory
Pressure

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Local electronic structure of dicarba-closo-dodecarboranes C 2B10H12 . / Fister, Timothy T.; Vila, Fernando D.; Seidler, Gerald T.; Svec, Lukas; Linehan, John; Cross, Julie O.

In: Journal of the American Chemical Society, Vol. 130, No. 3, 23.01.2008, p. 925-932.

Research output: Contribution to journalArticle

Fister, Timothy T. ; Vila, Fernando D. ; Seidler, Gerald T. ; Svec, Lukas ; Linehan, John ; Cross, Julie O. / Local electronic structure of dicarba-closo-dodecarboranes C 2B10H12 . In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 3. pp. 925-932.
@article{aa5259d2c2704360a58e58bcf54c2a09,
title = "Local electronic structure of dicarba-closo-dodecarboranes C 2B10H12",
abstract = "We report nonresonant inelastic X-ray scattering (NRIXS) measurement of core-shell excitations from both B 1s and C 1s initial states in all three isomers of the dicarba-closo-dodecarboranes C2B10H 12. First, these data yield an experimental determination of the angular-momentum-projected final local density of states (I-DOS). We find low-energy resonances with distinctive local s- or p-type character, providing a more complete experimental characterization of bond hybridization than is available from dipole-transition limited techniques, such as X-ray absorption spectroscopies. This analysis is supported by independent density functional theory and real-space full multiple scattering calculation of the I-DOS which yield a clear distinction between tangential and radial contributions. Second, we investigate the isomer sensitivity of the NRIXS signal and compare and contrast these results with prior electron energy loss spectroscopy measurements. This work establishes NRIXS as a valuable tool for borane chemistry, not only for the unique spectroscopic capabilities of the technique but also through its compatibility with future studies in solution or in high-pressure environments. In addition, this work also establishes the real-space full multiple scattering approach as a useful alternative to traditional approaches for excited states calculations of aromatic polyhedral boranes and related systems.",
author = "Fister, {Timothy T.} and Vila, {Fernando D.} and Seidler, {Gerald T.} and Lukas Svec and John Linehan and Cross, {Julie O.}",
year = "2008",
month = "1",
day = "23",
doi = "10.1021/ja074794u",
language = "English",
volume = "130",
pages = "925--932",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - Local electronic structure of dicarba-closo-dodecarboranes C 2B10H12

AU - Fister, Timothy T.

AU - Vila, Fernando D.

AU - Seidler, Gerald T.

AU - Svec, Lukas

AU - Linehan, John

AU - Cross, Julie O.

PY - 2008/1/23

Y1 - 2008/1/23

N2 - We report nonresonant inelastic X-ray scattering (NRIXS) measurement of core-shell excitations from both B 1s and C 1s initial states in all three isomers of the dicarba-closo-dodecarboranes C2B10H 12. First, these data yield an experimental determination of the angular-momentum-projected final local density of states (I-DOS). We find low-energy resonances with distinctive local s- or p-type character, providing a more complete experimental characterization of bond hybridization than is available from dipole-transition limited techniques, such as X-ray absorption spectroscopies. This analysis is supported by independent density functional theory and real-space full multiple scattering calculation of the I-DOS which yield a clear distinction between tangential and radial contributions. Second, we investigate the isomer sensitivity of the NRIXS signal and compare and contrast these results with prior electron energy loss spectroscopy measurements. This work establishes NRIXS as a valuable tool for borane chemistry, not only for the unique spectroscopic capabilities of the technique but also through its compatibility with future studies in solution or in high-pressure environments. In addition, this work also establishes the real-space full multiple scattering approach as a useful alternative to traditional approaches for excited states calculations of aromatic polyhedral boranes and related systems.

AB - We report nonresonant inelastic X-ray scattering (NRIXS) measurement of core-shell excitations from both B 1s and C 1s initial states in all three isomers of the dicarba-closo-dodecarboranes C2B10H 12. First, these data yield an experimental determination of the angular-momentum-projected final local density of states (I-DOS). We find low-energy resonances with distinctive local s- or p-type character, providing a more complete experimental characterization of bond hybridization than is available from dipole-transition limited techniques, such as X-ray absorption spectroscopies. This analysis is supported by independent density functional theory and real-space full multiple scattering calculation of the I-DOS which yield a clear distinction between tangential and radial contributions. Second, we investigate the isomer sensitivity of the NRIXS signal and compare and contrast these results with prior electron energy loss spectroscopy measurements. This work establishes NRIXS as a valuable tool for borane chemistry, not only for the unique spectroscopic capabilities of the technique but also through its compatibility with future studies in solution or in high-pressure environments. In addition, this work also establishes the real-space full multiple scattering approach as a useful alternative to traditional approaches for excited states calculations of aromatic polyhedral boranes and related systems.

UR - http://www.scopus.com/inward/record.url?scp=38349149569&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=38349149569&partnerID=8YFLogxK

U2 - 10.1021/ja074794u

DO - 10.1021/ja074794u

M3 - Article

VL - 130

SP - 925

EP - 932

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 3

ER -