X-ray transient absorption reveals the 1Au (nπ*) state of pyrazine in electronic relaxation

Scutelnic, Valeriu; Tsuru, Shota; Pápai, Mátyás; Yang, Zheyue; Epshtein, Michael; Xue, Tian; Haugen, Eric; Kobayashi, Yuki; Krylov, Anna I.; Møller, Klaus B.; Coriani, Sonia; Leone, Stephen R.

doi:10.1038/s41467-021-25045-0

X-ray transient absorption reveals the 1Au (nπ*) state of pyrazine in electronic relaxation

Journal Article · Wed Aug 18 00:00:00 EDT 2021 · Nature Communications

DOI:https://doi.org/10.1038/s41467-021-25045-0· OSTI ID:1813873

; ; ; Yang, Zheyue; Epshtein, Michael; Xue, Tian; ; Kobayashi, Yuki; ; ; ;

Abstract

Electronic relaxation in organic chromophores often proceeds via states not directly accessible by photoexcitation. We report on the photoinduced dynamics of pyrazine that involves such states, excited by a 267 nm laser and probed with X-ray transient absorption spectroscopy in a table-top setup. In addition to the previously characterized ¹ B _2u (ππ*) (S ₂ ) and ¹ B _3u (nπ*) (S ₁ ) states, the participation of the optically dark ¹ A _u (nπ*) state is assigned by a combination of experimental X-ray core-to-valence spectroscopy, electronic structure calculations, nonadiabatic dynamics simulations, and X-ray spectral computations. Despite ¹ A _u (nπ*) and ¹ B _3u (nπ*) states having similar energies at relaxed geometry, their X-ray absorption spectra differ largely in transition energy and oscillator strength. The ¹ A _u (nπ*) state is populated in 200 ± 50 femtoseconds after electronic excitation and plays a key role in the relaxation of pyrazine to the ground state.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1813873

Alternate ID(s):: OSTI ID: 1819703

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 12; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (51)

Software update: the ORCA program system, version 4.0: Software update Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1 https://doi.org/10.1002/wcms.1327	journal	July 2017
NEXAFS Spectroscopy Stöhr, Joachim Springer Series in Surface Sciences https://doi.org/10.1007/978-3-662-02853-7	book	January 1992
Internal conversion funnel in benzene and pyrazine: adiabatic and diabatic representation Domcke, W.; Sobolewski, A. L.; Woywod, C. Chemical Physics Letters, Vol. 203, Issue 2-3 https://doi.org/10.1016/0009-2614(93)85391-Z	journal	February 1993
Nonadiabatic dynamics within the time dependent density functional theory: Ultrafast photodynamics in pyrazine Werner, Ute; Mitrić, Roland; Suzuki, Toshinori Chemical Physics, Vol. 349, Issue 1-3 https://doi.org/10.1016/j.chemphys.2008.02.061	journal	June 2008
Ultrafast nonradiative transition pathways in photo-excited pyrazine: Ab initio analysis of time-resolved vacuum ultraviolet photoelectron spectrum Mignolet, Benoît; Kanno, Manabu; Shimakura, Noriyuki Chemical Physics, Vol. 515 https://doi.org/10.1016/j.chemphys.2018.07.015	journal	November 2018
Using singular value decomposition for a compact presentation and improved interpretation of the CIS wave functions Mayer, I. Chemical Physics Letters, Vol. 437, Issue 4-6 https://doi.org/10.1016/j.cplett.2007.02.038	journal	April 2007
Quantum Mechanical Studies on the Photophysics and the Photochemistry of Nucleic Acids and Nucleobases Improta, Roberto; Santoro, Fabrizio; Blancafort, Lluís Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00444	journal	March 2016
Photoinduced Chemistry in Fluorescent Proteins: Curse or Blessing? Acharya, Atanu; Bogdanov, Alexey M.; Grigorenko, Bella L. Chemical Reviews, Vol. 117, Issue 2 https://doi.org/10.1021/acs.chemrev.6b00238	journal	March 2016
First-Principles Simulations of X-ray Transient Absorption for Probing Attosecond Electron Dynamics Chen, Min; Lopata, Kenneth Journal of Chemical Theory and Computation, Vol. 16, Issue 7 https://doi.org/10.1021/acs.jctc.0c00122	journal	May 2020
Table-Top X-ray Spectroscopy of Benzene Radical Cation Epshtein, Michael; Scutelnic, Valeriu; Yang, Zheyue The Journal of Physical Chemistry A, Vol. 124, Issue 46 https://doi.org/10.1021/acs.jpca.0c08736	journal	October 2020
New Insights into the Photophysics of DNA Nucleobases Prokhorenko, Valentyn I.; Picchiotti, Alessandra; Pola, Martina The Journal of Physical Chemistry Letters, Vol. 7, Issue 22 https://doi.org/10.1021/acs.jpclett.6b02085	journal	October 2016
Transient X-ray Absorption Spectral Fingerprints of the S ₁ Dark State in Uracil Hua, Weijie; Mukamel, Shaul; Luo, Yi The Journal of Physical Chemistry Letters, Vol. 10, Issue 22 https://doi.org/10.1021/acs.jpclett.9b02692	journal	October 2019
Femtosecond spectroscopy of ultrafast nonadiabatic excited-state dynamics on the basis of ab initio potential-energy surfaces: the S2 state of pyrazine Stock, Gerhard; Domcke, Wolfgang The Journal of Physical Chemistry, Vol. 97, Issue 48 https://doi.org/10.1021/j100150a004	journal	December 1993
Efficient Excited-State Deactivation of the Gly-Phe-Ala Tripeptide via an Electron-Driven Proton-Transfer Process Shemesh, Dorit; Sobolewski, Andrzej L.; Domcke, Wolfgang Journal of the American Chemical Society, Vol. 131, Issue 4 https://doi.org/10.1021/ja808485b	journal	January 2009
Probing Ultrafast Internal Conversion through Conical Intersection via Time-Energy Map of Photoelectron Angular Anisotropy Horio, Takuya; Fuji, Takao; Suzuki, Yoshi-Ichi Journal of the American Chemical Society, Vol. 131, Issue 30 https://doi.org/10.1021/ja904780b	journal	August 2009
Ultrafast Intersystem Crossing in Acetylacetone via Femtosecond X-ray Transient Absorption at the Carbon K-Edge Bhattacherjee, Aditi; Pemmaraju, Chaitanya Das; Schnorr, Kirsten Journal of the American Chemical Society, Vol. 139, Issue 46 https://doi.org/10.1021/jacs.7b07532	journal	November 2017
Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy Bhattacherjee, Aditi; Schnorr, Kirsten; Oesterling, Sven Journal of the American Chemical Society, Vol. 140, Issue 39 https://doi.org/10.1021/jacs.8b07155	journal	September 2018
Electron-Withdrawing Effects in the Photodissociation of CH ₂ ICl To Form CH ₂ Cl Radical, Simultaneously Viewed Through the Carbon K and Chlorine L _2,3 X-ray Edges Yang, Zheyue; Schnorr, Kirsten; Bhattacherjee, Aditi Journal of the American Chemical Society, Vol. 140, Issue 41 https://doi.org/10.1021/jacs.8b08303	journal	September 2018
Self-Consistent Field Calculations of Excited States Using the Maximum Overlap Method (MOM) ^† Gilbert, Andrew T. B.; Besley, Nicholas A.; Gill, Peter M. W. The Journal of Physical Chemistry A, Vol. 112, Issue 50 https://doi.org/10.1021/jp801738f	journal	December 2008
Conical intersection dynamics of the primary photoisomerization event in vision Polli, Dario; Altoè, Piero; Weingart, Oliver Nature, Vol. 467, Issue 7314 https://doi.org/10.1038/nature09346	journal	September 2010
Probing ultrafast ππ/nπ internal conversion in organic chromophores via K-edge resonant absorption Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00069-7	journal	June 2017
The soft X-ray absorption spectrum of the allyl free radical Alagia, M.; Bodo, E.; Decleva, P. Phys. Chem. Chem. Phys., Vol. 15, Issue 4 https://doi.org/10.1039/C2CP43466K	journal	January 2013
The role of the low-lying dark nπ* states in the photophysics of pyrazine: a quantum dynamics study Sala, Matthieu; Lasorne, Benjamin; Gatti, Fabien Physical Chemistry Chemical Physics, Vol. 16, Issue 30 https://doi.org/10.1039/C4CP02165G	journal	January 2014
Ab initio quantum dynamical analysis of ultrafast nonradiative transitions via conical intersections in pyrazine Kanno, Manabu; Ito, Yuta; Shimakura, Noriyuki Physical Chemistry Chemical Physics, Vol. 17, Issue 3 https://doi.org/10.1039/C4CP04807E	journal	January 2015
Quantum dynamics of the photostability of pyrazine Sala, Matthieu; Guérin, Stéphane; Gatti, Fabien Physical Chemistry Chemical Physics, Vol. 17, Issue 44 https://doi.org/10.1039/C5CP04605J	journal	January 2015
Ultrafast nonadiabatic dynamics probed by nitrogen K-edge absorption spectroscopy Northey, T.; Norell, J.; Fouda, A. E. A. Physical Chemistry Chemical Physics, Vol. 22, Issue 5 https://doi.org/10.1039/C9CP03019K	journal	January 2020
Time-dependent density functional theory calculations of the spectroscopy of core electrons Besley, Nicholas A.; Asmuruf, Frans A. Physical Chemistry Chemical Physics, Vol. 12, Issue 38 https://doi.org/10.1039/c002207a	journal	January 2010
Molecular mechanisms involved in plant photoprotection Pinnola, Alberta; Bassi, Roberto Biochemical Society Transactions, Vol. 46, Issue 2 https://doi.org/10.1042/BST20170307	journal	April 2018
Natural transition orbitals Martin, Richard L. The Journal of Chemical Physics, Vol. 118, Issue 11 https://doi.org/10.1063/1.1558471	journal	March 2003
Efficient and accurate approximations to the molecular spin-orbit coupling operator and their use in molecular g-tensor calculations Neese, Frank The Journal of Chemical Physics, Vol. 122, Issue 3 https://doi.org/10.1063/1.1829047	journal	January 2005
The C 1s and N 1s near edge x-ray absorption fine structure spectra of five azabenzenes in the gas phase Vall-llosera, G.; Gao, B.; Kivimäki, A. The Journal of Chemical Physics, Vol. 128, Issue 4 https://doi.org/10.1063/1.2822985	journal	January 2008
Time-resolved photoelectron imaging of ultrafast S2→S1 internal conversion through conical intersection in pyrazine Suzuki, Yoshi-Ichi; Fuji, Takao; Horio, Takuya The Journal of Chemical Physics, Vol. 132, Issue 17 https://doi.org/10.1063/1.3395206	journal	May 2010
Including quantum decoherence in surface hopping Granucci, Giovanni; Persico, Maurizio; Zoccante, Alberto The Journal of Chemical Physics, Vol. 133, Issue 13 https://doi.org/10.1063/1.3489004	journal	October 2010
The Morse oscillator in position space, momentum space, and phase space Dahl, Jens Peder; Springborg, Michael The Journal of Chemical Physics, Vol. 88, Issue 7 https://doi.org/10.1063/1.453761	journal	April 1988
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Characterization of the S ₁ – S ₂ conical intersection in pyrazine using ab initio multiconfiguration self‐consistent‐field and multireference configuration‐interaction methods Woywod, Clemens; Domcke, Wolfgang; Sobolewski, Andrzej L. The Journal of Chemical Physics, Vol. 100, Issue 2 https://doi.org/10.1063/1.466618	journal	January 1994
Surface hopping dynamics using a locally diabatic formalism: Charge transfer in the ethylene dimer cation and excited state dynamics in the 2-pyridone dimer Plasser, Felix; Granucci, Giovanni; Pittner, Jiri The Journal of Chemical Physics, Vol. 137, Issue 22 https://doi.org/10.1063/1.4738960	journal	December 2012
Electron configuration changes in excited pyrazine molecules analyzed by femtosecond time-resolved photoelectron spectroscopy Stert, V.; Farmanara, P.; Radloff, W. The Journal of Chemical Physics, Vol. 112, Issue 10 https://doi.org/10.1063/1.481008	journal	March 2000
Full observation of ultrafast cascaded radiationless transitions from S ₂ (ππ ^∗ ) state of pyrazine using vacuum ultraviolet photoelectron imaging Horio, Takuya; Spesyvtsev, Roman; Nagashima, Kazuki The Journal of Chemical Physics, Vol. 145, Issue 4 https://doi.org/10.1063/1.4955296	journal	July 2016
Assessing the performance of trajectory surface hopping methods: Ultrafast internal conversion in pyrazine Xie, Weiwei; Sapunar, Marin; Došlić, Nađa The Journal of Chemical Physics, Vol. 150, Issue 15 https://doi.org/10.1063/1.5084961	journal	April 2019
Time-resolved near-edge X-ray absorption fine structure of pyrazine from electronic structure and nuclear wave packet dynamics simulations Tsuru, Shota; Vidal, Marta L.; Pápai, Mátyás The Journal of Chemical Physics, Vol. 151, Issue 12 https://doi.org/10.1063/1.5115154	journal	September 2019
Multi-faceted spectroscopic mapping of ultrafast nonadiabatic dynamics near conical intersections: A computational study Sun, Kewei; Xie, Weiwei; Chen, Lipeng The Journal of Chemical Physics, Vol. 153, Issue 17 https://doi.org/10.1063/5.0024148	journal	November 2020
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
High-resolution pre-edge structure in the inner-shell ionization threshold region of rare gases Xe, Kr, and Ar Sairanen, O. -P.; Kivimäki, A.; Nõmmiste, E. Physical Review A, Vol. 54, Issue 4 https://doi.org/10.1103/PhysRevA.54.2834	journal	October 1996
Time-resolved x-ray absorption spectroscopy with a water window high-harmonic source Pertot, Yoann; Schmidt, Cédric; Matthews, Mary Science, Vol. 355, Issue 6322 https://doi.org/10.1126/science.aah6114	journal	January 2017
Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction Attar, Andrew R.; Bhattacherjee, Aditi; Pemmaraju, C. D. Science, Vol. 356, Issue 6333 https://doi.org/10.1126/science.aaj2198	journal	April 2017
Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy Kobayashi, Yuki; Chang, Kristina F.; Zeng, Tao Science, Vol. 365, Issue 6448 https://doi.org/10.1126/science.aax0076	journal	July 2019
Early Events of DNA Photodamage Schreier, Wolfgang J.; Gilch, Peter; Zinth, Wolfgang Annual Review of Physical Chemistry, Vol. 66, Issue 1 https://doi.org/10.1146/annurev-physchem-040214-121821	journal	April 2015
Femtosecond Time-Resolved Photoelectron Imaging Suzuki, Toshinori Annual Review of Physical Chemistry, Vol. 57, Issue 1 https://doi.org/10.1146/annurev.physchem.57.032905.104601	journal	May 2006

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