Electronic Structure of Naturally Occurring Aromatic Carbon

Pomerantz, Andrew E.; Bostrom, Neil W.; Kleinberg, Robert L.; Crace, Ethan; Weng, Tsu-Chien; Sokaras, Dimosthenis; Nordlund, Dennis

doi:10.1021/acs.energyfuels.8b04366

Title: Electronic Structure of Naturally Occurring Aromatic Carbon

Journal Article · 04 February 2019 · Energy and Fuels

DOI: https://doi.org/10.1021/acs.energyfuels.8b04366 · OSTI ID:1498540

^[1]; Bostrom, Neil W. ^[1]; Kleinberg, Robert L. ^[1]; Crace, Ethan ^[2]; Weng, Tsu-Chien ^[3]; Sokaras, Dimosthenis ^[4]; Nordlund, Dennis ^[4]

Schlumberger-Doll Research, Cambridge, MA (United States)
Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Center for High Pressure Science & Technology Advanced Research, Shanghai (China)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Aromatic carbon in fused-ring systems can be classified into two forms of electronic structure: aromatic sextets, which have large highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gaps and resemble benzene; and isolated double bonds, which have small HOMO–LUMO gaps and resemble olefins. The relative abundance of aromatic sextets versus isolated double bonds in mixtures can be probed by carbon X-ray Raman spectroscopy. Here, we report the carbon X-ray Raman spectra of a wide variety of forms of naturally occurring aromatic carbon: kerogen (insoluble organic carbon in sedimentary rocks, which is the most abundant form of naturally occurring organic carbon in the Earth’s crust) over a range of types and thermal maturities, fresh materials of a variety of forms, and coal and petroleum asphaltenes (toluene soluble and heptane insoluble materials, which represent organic carbon resulting from extensive thermal processing). It is observed that all these materials are dominated by aromatic sextets over isolated double bonds. On the basis of the diversity of materials analyzed, it is concluded that naturally occurring organic carbon is generally dominated by aromatic sextets over isolated double bonds. This conclusion is rationalized in terms of statistical and thermodynamic effects.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1498540

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

Carbon Core Electron Spectra of Polycyclic Aromatic Hydrocarbons Pomerantz, Andrew E.; Crace, Ethan; Weng, Tsu-Chien The Journal of Physical Chemistry A, Vol. 122, Issue 26 https://doi.org/10.1021/acs.jpca.8b04922	journal	June 2018
Assessment of Clar's aromatic π-sextet rule by means of PDI, NICS and HOMA indicators of local aromaticity Portella, Guillem; Poater, Jordi; Solà, Miquel Journal of Physical Organic Chemistry, Vol. 18, Issue 8 https://doi.org/10.1002/poc.938	journal	May 2005
NEXAFS Spectroscopy Stöhr, Joachim Springer Series in Surface Sciences https://doi.org/10.1007/978-3-662-02853-7	book	January 1992
Quantentheoretische Beitr�ge zum Benzolproblem: I. Die Elektronenkonfiguration des Benzols und verwandter Verbindungen H�ckel, Erich Zeitschrift f�r Physik, Vol. 70, Issue 3-4 https://doi.org/10.1007/BF01339530	journal	March 1931
Quanstentheoretische Beitr�ge zum Benzolproblem: II. Quantentheorie der induzierten Polarit�ten H�ckel, Erich Zeitschrift f�r Physik, Vol. 72, Issue 5-6 https://doi.org/10.1007/BF01341953	journal	May 1931
Quantentheoretische Beitr�ge zum Problem der aromatischen und unges�ttigten Verbindungen. III H�ckel, Erich Zeitschrift f�r Physik, Vol. 76, Issue 9-10 https://doi.org/10.1007/bf01341936	journal	September 1932
Direct correlation between aromatization of carbon-rich organic matter and its visible electronic absorption edge Ferralis, Nicola; Liu, Yun; Bake, Kyle D. Carbon, Vol. 88 https://doi.org/10.1016/j.carbon.2015.02.075	journal	July 2015
Changes in optical properties, chemistry, and micropore and mesopore characteristics of bituminous coal at the contact with dikes in the Illinois Basin Mastalerz, M.; Drobniak, A.; Schimmelmann, A. International Journal of Coal Geology, Vol. 77, Issue 3-4 https://doi.org/10.1016/j.coal.2008.05.014	journal	January 2009
Assessing thermal maturity beyond the reaches of vitrinite reflectance and Rock-Eval pyrolysis: A case study from the Silurian Qusaiba formation Cheshire, Stephen; Craddock, Paul R.; Xu, Guangping International Journal of Coal Geology, Vol. 180 https://doi.org/10.1016/j.coal.2017.07.006	journal	July 2017
The neutron scattering length density of kerogen and coal as determined by CH3OH/CD3OH exchange Thomas, Jeffrey J.; Valenza, John J.; Craddock, Paul R. Fuel, Vol. 117 https://doi.org/10.1016/j.fuel.2013.09.075	journal	January 2014
Acid demineralization with critical point drying: A method for kerogen isolation that preserves microstructure Suleimenova, Assiya; Bake, Kyle D.; Ozkan, Aysen Fuel, Vol. 135 https://doi.org/10.1016/j.fuel.2014.07.005	journal	November 2014
Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating Schimmelmann, Arndt; Mastalerz, Maria; Gao, Ling Geochimica et Cosmochimica Acta, Vol. 73, Issue 20 https://doi.org/10.1016/j.gca.2009.07.027	journal	October 2009
Multivariate analysis of ATR-FTIR spectra for assessment of oil shale organic geochemical properties Washburn, Kathryn E.; Birdwell, Justin E. Organic Geochemistry, Vol. 63 https://doi.org/10.1016/j.orggeochem.2013.07.007	journal	October 2013
Kerogen thermal maturity and content of organic-rich mudrocks determined using stochastic linear regression models applied to diffuse reflectance IR Fourier transform spectroscopy (DRIFTS) Craddock, Paul R.; Prange, Michael D.; Pomerantz, Andrew E. Organic Geochemistry, Vol. 110 https://doi.org/10.1016/j.orggeochem.2017.05.005	journal	August 2017
Suppression of vitrinite reflectance by bitumen generated from liptinite during hydrous pyrolysis of artificial source rock Peters, K. E.; Hackley, P. C.; Thomas, J. J. Organic Geochemistry, Vol. 125 https://doi.org/10.1016/j.orggeochem.2018.09.010	journal	November 2018
Carbon K-edge X-ray Raman spectroscopy supports simple, yet powerful description of aromatic hydrocarbons and asphaltenes Bergmann, Uwe; Groenzin, Henning; Mullins, Oliver C. Chemical Physics Letters, Vol. 369, Issue 1-2 https://doi.org/10.1016/s0009-2614(02)02003-1	journal	February 2003
Bulk-sensitive XAS characterization of light elements: from X-ray Raman scattering to X-ray Raman spectroscopy Bergmann, Uwe; Glatzel, Pieter; Cramer, Stephen P. Microchemical Journal, Vol. 71, Issue 2-3 https://doi.org/10.1016/s0026-265x(02)00014-0	journal	April 2002
X-ray Raman Spectroscopy of Carbon in Asphaltene: Light Element Characterization with Bulk Sensitivity Bergmann, Uwe; Mullins, Oliver C.; Cramer, S. P. Analytical Chemistry, Vol. 72, Issue 11 https://doi.org/10.1021/ac990730t	journal	June 2000
Sulfur Species in Source Rock Bitumen before and after Hydrous Pyrolysis Determined by X-ray Absorption Near-Edge Structure Bolin, Trudy B.; Birdwell, Justin E.; Lewan, Michael D. Energy & Fuels, Vol. 30, Issue 8 https://doi.org/10.1021/acs.energyfuels.6b00744	journal	July 2016
Impact of Laboratory-Induced Thermal Maturity on Asphaltene Molecular Structure Pomerantz, Andrew E.; Le Doan, Tuong Van; Craddock, Paul R. Energy & Fuels, Vol. 30, Issue 9 https://doi.org/10.1021/acs.energyfuels.6b01238	journal	August 2016
Heavy Oil Based Mixtures of Different Origins and Treatments Studied by Atomic Force Microscopy Schuler, Bruno; Fatayer, Shadi; Meyer, Gerhard Energy & Fuels, Vol. 31, Issue 7 https://doi.org/10.1021/acs.energyfuels.7b00805	journal	June 2017
Optical Analysis of Pyrolysis Products of Green River Oil Shale Bake, Kyle D.; Pomerantz, Andrew E. Energy & Fuels, Vol. 31, Issue 12 https://doi.org/10.1021/acs.energyfuels.7b01020	journal	November 2017
Nanoaggregates of Diverse Asphaltenes by Mass Spectrometry and Molecular Dynamics Wang, Weiguo; Taylor, Cooper; Hu, Hui Energy & Fuels, Vol. 31, Issue 9 https://doi.org/10.1021/acs.energyfuels.7b01420	journal	September 2017
Chemical, Molecular, and Microstructural Evolution of Kerogen during Thermal Maturation: Case Study from the Woodford Shale of Oklahoma Craddock, Paul R.; Bake, Kyle D.; Pomerantz, Andrew E. Energy & Fuels, Vol. 32, Issue 4 https://doi.org/10.1021/acs.energyfuels.8b00189	journal	March 2018
Toward Molecule-Specific Geochemistry of Heavy Ends: Application to the Upstream Oil Industry Pomerantz, Andrew E. Industrial & Engineering Chemistry Research, Vol. 55, Issue 16 https://doi.org/10.1021/acs.iecr.6b00402	journal	April 2016
Carbon Core Electron Spectra of Polycyclic Aromatic Hydrocarbons Pomerantz, Andrew E.; Crace, Ethan; Weng, Tsu-Chien The Journal of Physical Chemistry A, Vol. 122, Issue 26 https://doi.org/10.1021/acs.jpca.8b04922	journal	June 2018
Aromaticity of Polycyclic Conjugated Hydrocarbons Randić, Milan Chemical Reviews, Vol. 103, Issue 9 https://doi.org/10.1021/cr9903656	journal	September 2003
Carbon-13 solid-state NMR of Argonne-premium coals Solum, Mark S.; Pugmire, Ronald J.; Grant, David M. Energy & Fuels, Vol. 3, Issue 2 https://doi.org/10.1021/ef00014a012	journal	March 1989
Maturity Trends in Raman Spectra from Kerogen and Coal Kelemen, S. R.; Fang, H. L. Energy & Fuels, Vol. 15, Issue 3 https://doi.org/10.1021/ef0002039	journal	March 2001
Pyrite removal from kerogen without altering organic matter: the chromous chloride method Acholla, Francis V.; Orr, Wilson L. Energy & Fuels, Vol. 7, Issue 3 https://doi.org/10.1021/ef00039a012	journal	May 1993
Direct Characterization of Kerogen by X-ray and Solid-State ¹³ C Nuclear Magnetic Resonance Methods Kelemen, S. R.; Afeworki, M.; Gorbaty, M. L. Energy & Fuels, Vol. 21, Issue 3 https://doi.org/10.1021/ef060321h	journal	May 2007
Comparison of Coal-Derived and Petroleum Asphaltenes by ¹³ C Nuclear Magnetic Resonance, DEPT, and XRS Andrews, A. Ballard; Edwards, John C.; Pomerantz, Andrew E. Energy & Fuels, Vol. 25, Issue 7 https://doi.org/10.1021/ef2003443	journal	July 2011
Green River Oil Shale Pyrolysis: Semi-Open Conditions Le Doan, T. V.; Bostrom, N. W.; Burnham, A. K. Energy & Fuels, Vol. 27, Issue 11 https://doi.org/10.1021/ef401162p	journal	October 2013
The Chemical Composition of Bitumen in Pyrolyzed Green River Oil Shale: Characterization by ¹³ C NMR Spectroscopy Feng, Yesu; Le Doan, Tuong Van; Pomerantz, Andrew E. Energy & Fuels, Vol. 27, Issue 12 https://doi.org/10.1021/ef4016685	journal	November 2013
Characterization of Macromolecular Structure Elements from a Green River Oil Shale, I. Extracts Solum, Mark S.; Mayne, Charles L.; Orendt, Anita M. Energy & Fuels, Vol. 28, Issue 1 https://doi.org/10.1021/ef401918u	journal	December 2013
Evolution of Kerogen and Bitumen during Thermal Maturation via Semi-Open Pyrolysis Investigated by Infrared Spectroscopy Craddock, Paul R.; Le Doan, Tuong Van; Bake, Kyle Energy & Fuels, Vol. 29, Issue 4 https://doi.org/10.1021/ef5027532	journal	March 2015
Unraveling the Molecular Structures of Asphaltenes by Atomic Force Microscopy Schuler, Bruno; Meyer, Gerhard; Peña, Diego Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b04056	journal	July 2015
Heptacene: Characterization in Solution, in the Solid State, and in Films Einholz, Ralf; Fang, Treliant; Berger, Robert Journal of the American Chemical Society, Vol. 139, Issue 12 https://doi.org/10.1021/jacs.6b13212	journal	March 2017
Inner-Shell Excitation Spectroscopy of Fused-Ring Aromatic Molecules by Electron Energy Loss and X-ray Raman Techniques Gordon, Michelle L.; Tulumello, David; Cooper, Glyn The Journal of Physical Chemistry A, Vol. 107, Issue 41 https://doi.org/10.1021/jp035607r	journal	October 2003
The Agreement between Clar Structures and Nucleus-Independent Chemical Shift Values in Pericondensed Benzenoid Polycyclic Aromatic Hydrocarbons: An Application of the Y-Rule Ruiz-Morales, Yosadara The Journal of Physical Chemistry A, Vol. 108, Issue 49 https://doi.org/10.1021/jp040179q	journal	November 2004
Extended Y-Rule Method for the Characterization of the Aromatic Sextets in Cata-Condensed Polycyclic Aromatic Hydrocarbons Oña-Ruales, Jorge O.; Ruiz-Morales, Yosadara The Journal of Physical Chemistry A, Vol. 118, Issue 51 https://doi.org/10.1021/jp510180j	journal	December 2014
Reduced HOMO−LUMO Gap as an Index of Kinetic Stability for Polycyclic Aromatic Hydrocarbons Aihara, Jun-ichi The Journal of Physical Chemistry A, Vol. 103, Issue 37 https://doi.org/10.1021/jp990092i	journal	September 1999
Thermal alteration of Cretaceous black shale by basaltic intrusions in the Eastern Atlantic Simoneit, Bernd R. T.; Brenner, Shmuel; Peters, K. E. Nature, Vol. 273, Issue 5663 https://doi.org/10.1038/273501a0	journal	June 1978
Pictorial representation and validation of Clar's aromatic sextet theory using molecular electrostatic potentials Vijayalakshmi, Kunduchi Periya; Suresh, Cherumuttathu H. New Journal of Chemistry, Vol. 34, Issue 10 https://doi.org/10.1039/c0nj00177e	journal	January 2010
A high resolution and large solid angle x-ray Raman spectroscopy end-station at the Stanford Synchrotron Radiation Lightsource Sokaras, D.; Nordlund, D.; Weng, T. -C. Review of Scientific Instruments, Vol. 83, Issue 4 https://doi.org/10.1063/1.4704458	journal	April 2012
X-Ray Raman Spectroscopy—A New Tool to Study Local Structure of Aromatic Hydrocarbons and Asphaltenes Bergmann, Uwe; Groenzin, Henning; Mullins, Oliver C. Petroleum Science and Technology, Vol. 22, Issue 7-8 https://doi.org/10.1081/lft-120038722	journal	January 2004
Three common source rock evaluation errors made by geologists during prospect or play appraisals Dembicki, Harry AAPG Bulletin, Vol. 93, Issue 3 https://doi.org/10.1306/10230808076	journal	March 2009
The Electronic Absorption Edge of Petroleum Mullins, Oliver C.; Mitra-Kirtley, Sudipa; Zhu, Yifu Applied Spectroscopy, Vol. 46, Issue 9 https://doi.org/10.1366/0003702924123737	journal	September 1992
Forty years of Clar's aromatic π-sextet rule Solà, Miquel Frontiers in Chemistry, Vol. 1 https://doi.org/10.3389/fchem.2013.00022	journal	January 2013

Similar Records

Aromaticity-induced changes in the electronic properties of size-expanded DNA bases: Case of xC.

Journal Article · 2005 · International Journal of Quantum Chemistry · OSTI ID:1003411

Fuentes-Cabrera, Miguel A; Lipkowski, Pawel; Huertas, Oscar; +5 more

First-principles investigation on the electronic efficiency and binding energy of the contacts formed by graphene and poly-aromatic hydrocarbon anchoring groups

Journal Article · 2015 · Journal of Chemical Physics · OSTI ID:22415718

Li, Yang; Tu, Xingchen; Wang, Hao; +2 more

UV resonance Raman analysis of trishomocubane and diamondoid dimers

Journal Article · 2014 · Journal of Chemical Physics · OSTI ID:22255267

Meinke, Reinhard; Thomsen, Christian; Maultzsch, Janina; +6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Electronic Structure of Naturally Occurring Aromatic Carbon

Citation Formats

References (49)

Similar Records

Related Subjects