Carbon Core Electron Spectra of Polycyclic Aromatic Hydrocarbons

Pomerantz, Andrew E.; Crace, Ethan; Weng, Tsu -Chien; Sokaras, Dimosthenis; Nordlund, Dennis

doi:10.1021/acs.jpca.8b04922

Carbon Core Electron Spectra of Polycyclic Aromatic Hydrocarbons

Journal Article · Wed Jun 13 00:00:00 EDT 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b04922· OSTI ID:1469708

^[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)

Aromaticity profoundly affects molecular orbitals in polycyclic aromatic hydrocarbons. X-ray core electron spectroscopy has observed that carbon 1s–π* transitions can be broadened or even split in some polycyclic systems, although the origin of the effect has remained obscure. The π electrons in polycyclic systems are typically classified in the Clar model as belonging to either true aromatic sextets (similar to benzene) or isolated double bonds (similar to olefins). Here, bulk-sensitive carbon core excitation spectra are presented for a series of polycyclic systems and show that the magnitude of the 1s–π* splitting is determined primarily by the ratio of true aromatic sextets to isolated double bonds. The observed splitting can be rationalized in terms of ground state energetics as described by Hückel, driven by the π electron structure described by Clar. In conclusion, this simple model including only ground state energetics is shown to explain the basics physics behind the spectral evolution for a broad set of polycyclic aromatic hydrocarbons, although some residual deviations between this model and experiment can likely be improved by including a more detailed electronic structure and the core hole effect.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1469708

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 26 Vol. 122; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (23)

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
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
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
Near-edge core photoabsorption in polyacenes: model molecules for graphite Ågren, Hans; Vahtras, Olav; Carravetta, Vincenzo Chemical Physics, Vol. 196, Issue 1-2 https://doi.org/10.1016/0301-0104(95)00091-2	journal	June 1995
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
Isotope effects in high-resolution NEXAFS spectra of naphthalene Hübner, D.; Holch, F.; Rocco, M. L. M. Chemical Physics Letters, Vol. 415, Issue 1-3 https://doi.org/10.1016/j.cplett.2005.09.018	journal	October 2005
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
Aromaticity of Polycyclic Conjugated Hydrocarbons Randić, Milan Chemical Reviews, Vol. 103, Issue 9 https://doi.org/10.1021/cr9903656	journal	September 2003
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
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
Detailed study of pyridine at the C 1 s and N 1 s ionization thresholds: The influence of the vibrational fine structure Kolczewski, C.; Püttner, R.; Plashkevych, O. The Journal of Chemical Physics, Vol. 115, Issue 14 https://doi.org/10.1063/1.1397797	journal	October 2001
Extended Hückel Theory. III. Compounds of Boron and Nitrogen Hoffmann, Roald The Journal of Chemical Physics, Vol. 40, Issue 9 https://doi.org/10.1063/1.1725550	journal	May 1964
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
Core hole effect in NEXAFS spectroscopy of polycyclic aromatic hydrocarbons: Benzene, chrysene, perylene, and coronene Oji, Hiroshi; Mitsumoto, Ryuichi; Ito, Eisuke The Journal of Chemical Physics, Vol. 109, Issue 23 https://doi.org/10.1063/1.477696	journal	December 1998
Analysis of the near-edge X-ray-absorption fine-structure of anthracene: A combined theoretical and experimental study Klues, Michael; Hermann, Klaus; Witte, Gregor The Journal of Chemical Physics, Vol. 140, Issue 1 https://doi.org/10.1063/1.4855215	journal	January 2014
X-ray absorption spectra of poly-p-phenylenes and polyacenes: localization of π orbitals Yokoyama, Toshihiko; Seki, Kazuhiko; Morisada, Ikuo Physica Scripta, Vol. 41, Issue 1 https://doi.org/10.1088/0031-8949/41/1/046	journal	January 1990
Theory of X-Ray Raman Scattering Mizuno, Yukio; Ohmura, Yoshihiro Journal of the Physical Society of Japan, Vol. 22, Issue 2 https://doi.org/10.1143/JPSJ.22.445	journal	February 1967

Cited By (1)

Electronic Structure of Naturally Occurring Aromatic Carbon Pomerantz, Andrew E.; Bostrom, Neil W.; Kleinberg, Robert L. Energy & Fuels, Vol. 33, Issue 3 https://doi.org/10.1021/acs.energyfuels.8b04366	journal	February 2019