Diabatic Valence-Hole Concept

Jiang, Jun

doi:10.1021/acs.jpca.4c00289

Diabatic Valence-Hole Concept

Journal Article · Mon Apr 22 00:00:00 EDT 2024 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.4c00289· OSTI ID:2427464

^[1]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

A global diabatization scheme, based on the “valence-hole” concept, has been previously applied to model webs of avoided crossings that exist in four electronic-state symmetry manifolds of C₂ (¹Π_g, ³Π_g, ¹Σ_u⁺, and ³Σ_u⁺). Here, this model is extended to the electronically excited states of four more molecules: CN (²Σ⁺), N₂ (³Π_u), SiC (³Π), and Si₂ (³Π_g). Many strangenesses in the spectroscopic observations (e.g., energy level structure, predissociation linewidths, and radiative lifetimes) for all four electronic state systems discussed here are accounted for by this unified model. The key concept of the model is valence-hole electron configurations: 3σ²4σ¹1π⁴5σ² in CN (²Σ⁺), 2σ_g²2σ_u¹1π_u⁴3σ_g²1π_g¹ in N₂ (³Π_u), 5σ²6σ¹7σ²2π³ in SiC (³Π), and 4σ_g²4σ_u¹5σ_g²2π_u³ in Si₂ (³Π_g), all of which have a triply occupied “valence-core” (i.e., 2σ_g²2σ_u¹ or the equivalent). These valence-hole configurations have a nominal bond order of three or higher and correlate with high-energy separated-atom limits with an np ← ns (n = 2, 3) promotion in one of the atomic constituents. On its way to dissociation, the strongly bound diabatic valence-hole state crosses multiple weakly bound or repulsive states, which belong to electron configurations with a completely filled valence-core. These curve crossings between diabatic potentials result in a network of many avoided crossings among multiple electronic states, analogous to the well-studied electronic structure landscape of ionic-covalent crossings in strongly ionic molecules. In conclusion, considering the unique role of valence-hole states in shaping the global electronic structure, the valence-hole concept should be added to our intuitive framework of chemical bonding.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2427464

Report Number(s):: LLNL--JRNL-858990; 1089693

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: 17 Vol. 128; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Femtochemistry: Atomic-Scale Dynamics of the Chemical Bond Using Ultrafast Lasers (Nobel Lecture) Zewail, Ahmed H. Angewandte Chemie International Edition, Vol. 39, Issue 15, p. 2586-2631 https://doi.org/10.1002/1521-3773(20000804)39:15<2586::AID-ANIE2586>3.0.CO;2-O	journal	August 2000
Über die Struktur der zweiten positiven Stickstoffgruppe und die Prädissoziation des N₂‐Moleküls Büttenbender, G.; Herzberg, G. Annalen der Physik, Vol. 413, Issue 6 https://doi.org/10.1002/andp.19344130606	journal	January 1934
Estimating local bonding/antibonding character of canonical molecular orbitals from their energy derivatives. The case of coordinating lone pair orbitals Chaquin, Patrick; Canac, Yves; Lepetit, Christine International Journal of Quantum Chemistry, Vol. 116, Issue 17 https://doi.org/10.1002/qua.25174	journal	June 2016
High-Resolution Fourier Spectrometry of 14N2 Violet Emission Spectrum: Extensive Analysis of the C3Πu → B3Πg System Roux, F.; Michaud, F.; Vervloet, M. Journal of Molecular Spectroscopy, Vol. 158, Issue 2 https://doi.org/10.1006/jmsp.1993.1071	journal	April 1993
�ber dieTriplett-Bandentermformel f�r den allgemeinen intermedi�ren Fall und Anwendung derselben auf dieB 3?-,C 3?-Terme des N2-Molek�ls Bud�, A. Zeitschrift f�r Physik, Vol. 96, Issue 3-4 https://doi.org/10.1007/BF01341523	journal	March 1935
Zur Theorie nicht adiabatisch verlaufender chemischer Prozesse London, F. Zeitschrift f�r Physik, Vol. 74, Issue 3-4 https://doi.org/10.1007/BF01342370	journal	March 1932
Intramolecular perturbations and the quenching of luminescence in small molecules Gelbart, William M.; Freed, Karl F. Chemical Physics Letters, Vol. 18, Issue 4 https://doi.org/10.1016/0009-2614(73)80445-2	journal	February 1973
Abundances of the elements: Meteoritic and solar Anders, Edward; Grevesse, Nicolas Geochimica et Cosmochimica Acta, Vol. 53, Issue 1 https://doi.org/10.1016/0016-7037(89)90286-X	journal	January 1989
Molecular constants of the B3Π and A3Σ states of N2 Bullock, L. E.; Hause, C. D. Journal of Molecular Spectroscopy, Vol. 39, Issue 3 https://doi.org/10.1016/0022-2852(71)90222-0	journal	September 1971
Interaction of the C′ and C states in 14N2, 14N15N, and 15N2 Ledbetter, John W.; Dressler, K. Journal of Molecular Spectroscopy, Vol. 63, Issue 3 https://doi.org/10.1016/0022-2852(76)90303-9	journal	December 1976
Potential energy curves and transition moments for the low-lying electronic states of the Si2 molecule Peyerimhoff, Sigrid D.; Buenker, Robert J. Chemical Physics, Vol. 72, Issue 1-2 https://doi.org/10.1016/0301-0104(82)87071-7	journal	November 1982
Charge-transfer production of predissociated N2 states. I. The n = 3 Rydberg state region (12.8–14 eV) Barbara van der Kamp, A.; Cosby, P. C.; van der Zande, Wim J. Chemical Physics, Vol. 184, Issue 1-3 https://doi.org/10.1016/0301-0104(94)00105-7	journal	June 1994
A predissociative triplet Rydberg state of the nitrogen molecule studied by near-infrared diode laser kinetic spectroscopy Hashimoto, Tatsuya; Kanamori, Hideto Journal of Molecular Spectroscopy, Vol. 235, Issue 1 https://doi.org/10.1016/j.jms.2005.10.008	journal	January 2006
Fourier transform emission spectroscopy of the B2Σ+–X2Σ+ system of CN Ram, R. S.; Davis, S. P.; Wallace, L. Journal of Molecular Spectroscopy, Vol. 237, Issue 2 https://doi.org/10.1016/j.jms.2006.03.016	journal	June 2006
On the complexity of the absorption spectrum of molecular nitrogen Vieitez, M. O.; Ivanov, T. I.; Ubachs, W. Journal of Molecular Liquids, Vol. 141, Issue 3 https://doi.org/10.1016/j.molliq.2008.01.014	journal	June 2008
Diabatic Valence-Hole States in the C₂ Molecule: “Putting Humpty Dumpty Together Again” Jiang, Jun; Ye, Hong-Zhou; Nauta, Klaas The Journal of Physical Chemistry A, Vol. 126, Issue 20 https://doi.org/10.1021/acs.jpca.2c00495	journal	May 2022
Extreme ultraviolet laser excitation of isotopic molecular nitrogen: The dipole-allowed spectrum of 15N2 and 14N15N Sprengers, J. P.; Ubachs, W.; Baldwin, K. G. H. The Journal of Chemical Physics, Vol. 119, Issue 6 https://doi.org/10.1063/1.1589478	journal	August 2003
Electronic Structures and Potential Energy Curves for the Low‐Lying States of the CN Radical Schaefer, Henry F.; Heil, Timothy G. The Journal of Chemical Physics, Vol. 54, Issue 6 https://doi.org/10.1063/1.1675214	journal	March 1971
3Π Levels and Predissociations of N2 near the 12.135-eV Dissociation Limit Carroll, P. K.; Mulliken, R. S. The Journal of Chemical Physics, Vol. 43, Issue 7 https://doi.org/10.1063/1.1697107	journal	October 1965
Theoretical Analysis of the Effects of Hydrogenation in Hydrocarbons: Accurate SCF MO Wavefunctions for C2H2, C2H4, and C2H6 Buenker, Robert J.; Peyerimhoff, Sigrid D.; Whitten, Jerry L. The Journal of Chemical Physics, Vol. 46, Issue 6 https://doi.org/10.1063/1.1840998	journal	March 1967
Predissociation mechanism for the lowest Πu1 states of N2 Lewis, B. R.; Gibson, S. T.; Zhang, W. The Journal of Chemical Physics, Vol. 122, Issue 14 https://doi.org/10.1063/1.1869986	journal	April 2005
Rotational effects in the band oscillator strengths and predissociation linewidths for the lowest Πu1–XΣg+1 transitions of N2 Haverd, V. E.; Lewis, B. R.; Gibson, S. T. The Journal of Chemical Physics, Vol. 123, Issue 21 https://doi.org/10.1063/1.2134704	journal	December 2005
Optical observation of the C, 3sσgF3, and 3pπuG3 Π3u states of N2 Lewis, B. R.; Baldwin, K. G. H.; Sprengers, J. P. The Journal of Chemical Physics, Vol. 129, Issue 16 https://doi.org/10.1063/1.2990655	journal	October 2008
A coupled-channel model of the Π3u states of N2: Structure and interactions of the 3sσgF3 Π3u and 3pπuG3 Π3u Rydberg states Lewis, B. R.; Heays, A. N.; Gibson, S. T. The Journal of Chemical Physics, Vol. 129, Issue 16 https://doi.org/10.1063/1.2990656	journal	October 2008
Sign reversal of the spin-orbit constant for the C Π3u state of N2 Ndome, H.; Hochlaf, M.; Lewis, B. R. The Journal of Chemical Physics, Vol. 129, Issue 16 https://doi.org/10.1063/1.2990658	journal	October 2008
A new band of N2 and identification of the lower vibronic level of the C′, v=1 and the C, v=5 3Πu state interaction Ledbetter, John W. The Journal of Chemical Physics, Vol. 67, Issue 7 https://doi.org/10.1063/1.435293	journal	October 1977
Theoretical prediction of the potential curves for the lowest‐lying states of the isovalent diatomics CN ⁺ , Si ₂ , SiC, CP ⁺ , and SiN ⁺ using the a b i n i t i o MRD‐CI method Bruna, Pablo J.; Peyerimhoff, Sigrid D.; Buenker, Robert J. The Journal of Chemical Physics, Vol. 72, Issue 10 https://doi.org/10.1063/1.439012	journal	May 1980
The C 3Π–X 3Π band system of the SiC radical Butenhoff, Thomas J.; Rohlfing, Eric A. The Journal of Chemical Physics, Vol. 95, Issue 6 https://doi.org/10.1063/1.460800	journal	September 1991
The C 3Π(v′=0–6)–X 3Π(v″=0) transition in SiC Ebben, Maarten; Drabbels, Marcel; ter Meulen, J. J. The Journal of Chemical Physics, Vol. 95, Issue 4 https://doi.org/10.1063/1.460988	journal	August 1991
A novel discrete variable representation for quantum mechanical reactive scattering via the S ‐matrix Kohn method Colbert, Daniel T.; Miller, William H. The Journal of Chemical Physics, Vol. 96, Issue 3 https://doi.org/10.1063/1.462100	journal	February 1992
Emission spectrum of the CN( B ² Σ ⁺ – X ² Σ ⁺ ) tail band system: B ² Σ ⁺ ∼ ⁴ Π perturbations in the v _B =9, 12, and 17 levels Ito, Haruhiko; Ozaki, Yasushi; Suzuki, Kaoru The Journal of Chemical Physics, Vol. 96, Issue 6 https://doi.org/10.1063/1.462838	journal	March 1992
Equivalence of the Wei potential model and Tietz potential model for diatomic molecules Jia, Chun-Sheng; Diao, Yong-Feng; Liu, Xiang-Jun The Journal of Chemical Physics, Vol. 137, Issue 1 https://doi.org/10.1063/1.4731340	journal	July 2012
First observation of the 3Πg3 state of C ₂ : Born-Oppenheimer breakdown Krechkivska, O.; Welsh, B. A.; Bacskay, G. B. The Journal of Chemical Physics, Vol. 146, Issue 13 https://doi.org/10.1063/1.4979293	journal	April 2017
The e Πg3 state of C ₂ : A pathway to dissociation Welsh, B. A.; Krechkivska, O.; Nauta, K. The Journal of Chemical Physics, Vol. 147, Issue 2 https://doi.org/10.1063/1.4985882	journal	July 2017
The spin-forbidden vacuum-ultraviolet absorption spectrum of 14N15N Heays, A. N.; Lewis, B. R.; de Oliveira, N. The Journal of Chemical Physics, Vol. 151, Issue 22 https://doi.org/10.1063/1.5130206	journal	December 2019
The spectrum of molecular nitrogen Lofthus, Alf; Krupenie, Paul H. Journal of Physical and Chemical Reference Data, Vol. 6, Issue 1 https://doi.org/10.1063/1.555546	journal	January 1977
The ORCA quantum chemistry program package Neese, Frank; Wennmohs, Frank; Becker, Ute The Journal of Chemical Physics, Vol. 152, Issue 22 https://doi.org/10.1063/5.0004608	journal	June 2020
The Molpro quantum chemistry package Werner, Hans-Joachim; Knowles, Peter J.; Manby, Frederick R. The Journal of Chemical Physics, Vol. 152, Issue 14 https://doi.org/10.1063/5.0005081	journal	April 2020
Photodissociation of dicarbon: How nature breaks an unusual multiple bond Borsovszky, Jasmin; Nauta, Klaas; Jiang, Jun Proceedings of the National Academy of Sciences, Vol. 118, Issue 52 https://doi.org/10.1073/pnas.2113315118	journal	December 2021
The Structure of the Third Cyanogen Band and the Associated Tails Uhler, H. S.; Patterson, R. A. The Astrophysical Journal, Vol. 42 https://doi.org/10.1086/142222	journal	December 1915
An Extension of the Phillips System of C_{2} and a Survey of C_{2} States. Ballik, E. A.; Ramsay, D. A. The Astrophysical Journal, Vol. 137 https://doi.org/10.1086/147486	journal	January 1963
The High-Resolution Absorption Spectrum of Mitrogen from 1060 TO 1520 Å. V. The C^{3}Π_{u} <- Χ^{1}Σ_{g}^{+} System. Tilford, S. G.; Wilkinson, P. G. The Astrophysical Journal, Vol. 142 https://doi.org/10.1086/148390	journal	October 1965
The Spectrum of the CN Molecule. Douglas, A. E.; Routly, P. M. The Astrophysical Journal Supplement Series, Vol. 1 https://doi.org/10.1086/190010	journal	February 1955
Solar System Abundances and Condensation Temperatures of the Elements Lodders, Katharina The Astrophysical Journal, Vol. 591, Issue 2 https://doi.org/10.1086/375492	journal	July 2003
An ab initio study of singlet and triplet Rydberg states of N ₂ Little, Duncan A.; Tennyson, Jonathan Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 46, Issue 14 https://doi.org/10.1088/0953-4075/46/14/145102	journal	June 2013
Experimental energy levels of 12C14N through marvel analysis Syme, Anna-Maree; McKemmish, Laura K. Monthly Notices of the Royal Astronomical Society, Vol. 499, Issue 1 https://doi.org/10.1093/mnras/staa2791	journal	September 2020
Mass Ratio of the Carbon Isotopes from the Spectrum of CN Jenkins, F. A.; Wooldridge, Dean E. Physical Review, Vol. 53, Issue 2 https://doi.org/10.1103/PhysRev.53.137	journal	January 1938
Theoretical Predictions and Experimental Detection of the SiC Molecule Bernath, P. F.; Rogers, S. A.; O'Brien, L. C. Physical Review Letters, Vol. 60, Issue 3 https://doi.org/10.1103/PhysRevLett.60.197	journal	January 1988
THE SPECTRUM OF THE Si₂ MOLECULE Douglas, A. E. Canadian Journal of Physics, Vol. 33, Issue 12 https://doi.org/10.1139/p55-096	journal	December 1955
The Spectrum of cn in the Vacuum Ultraviolet Carroll, P. K. Canadian Journal of Physics, Vol. 34, Issue 1 https://doi.org/10.1139/p56-010	journal	January 1956
Spectrum of the CN molecule. I. Absorption in the vacuum ultraviolet Lutz, Barry L. Canadian Journal of Physics, Vol. 48, Issue 10 https://doi.org/10.1139/p70-150	journal	May 1970
High-resolution Fourier spectrometry of ¹⁴N₂: analysis of the (0–0), (0–1), (0–2), (0–3) bands of the C³Π_u – B³Π_g system Roux, F.; Michaud, F.; Vervloet, M. Canadian Journal of Physics, Vol. 67, Issue 2-3 https://doi.org/10.1139/p89-023	journal	February 1989
A New Method for Producing the Auroral Afterglow of Nitrogen and Its Spectrum Tanaka, Y.; Jursa, A. S. Journal of the Optical Society of America, Vol. 51, Issue 11 https://doi.org/10.1364/JOSA.51.001239	journal	November 1961
Theoretical Study of the C³II-X³II Transition in CSi Trinder, W.; Reinsch, E. A.; Rosmus, P. Zeitschrift für Naturforschung A, Vol. 48, Issue 8-9 https://doi.org/10.1515/zna-1993-8-910	journal	September 1993

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