Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory

Zhang, Yu; Bergmann, Uwe; Schoenlein, Robert; Khalil, Munira; Govind, Niranjan

doi:10.1063/1.5111141

Title: Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory

Abstract

With the help of newly developed X-ray free-electron laser (XFEL) sources, creating double core holes (DCHs) simultaneously at the same or different atomic sites in a molecule has now become possible. DCH X-ray emission is a new form of X-ray nonlinear spectroscopy that can be studied with a XFEL. Here in this paper, we computationally explore the metal K-edge valence-to-core (VtC) X-ray emission spectroscopy (XES) of metal/metal and metal/ligand DCH states in a series of transition metal complexes with time-dependent density functional theory. The simulated DCH VtC-XES signals are compared with conventional single core hole (SCH) XES signals. The energy shifts and intensity changes of the DCH emission lines with respect to the corresponding SCH-XES features are fingerprints of the coupling between the second core hole and the occupied orbitals around the DCHs that contain important chemical bonding information of the complex. The difference between delocalized/localized core hole models on DCH VtC-XES is also briefly discussed. We theoretically demonstrate that DCH XES provides subtle information on the local electronic structure around metal centers in transition metal complexes beyond conventional linear XES. In conclusion, our predicted changes from calculations between SCH-XES and DCH-XES features should be detectable with modern XFEL sources.

Authors:

^[1];

^[2]; Schoenlein, Robert ^[3];

^[4];

^[5]

SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford PULSE Inst.
SLAC National Accelerator Lab., Menlo Park, CA (United States). LCLS and Stanford PULSE Inst.
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of Washington, Seattle, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Publication Date:: Fri Oct 11 00:00:00 EDT 2019

Research Org.:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Laboratory Directed Research and Development (LDRD) Program

OSTI Identifier:: 1591640

Alternate Identifier(s):: OSTI ID: 1570073; OSTI ID: 1608543

Report Number(s):: PNNL-SA-143614
Journal ID: ISSN 0021-9606; TRN: US2102049

Grant/Contract Number:: KC030105172685; SC0019277; AC05-76RL1830; AC02-76SF00515; AC02-05CH11231; AC05-76RL01830

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 151; Journal Issue: 14; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Zhang, Yu, Bergmann, Uwe, Schoenlein, Robert, Khalil, Munira, and Govind, Niranjan. Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory.  United States: N. p., 2019. 
Web.  doi:10.1063/1.5111141.

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                    Zhang, Yu, Bergmann, Uwe, Schoenlein, Robert, Khalil, Munira, & Govind, Niranjan. Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory.  United States.  https://doi.org/10.1063/1.5111141

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                    Zhang, Yu, Bergmann, Uwe, Schoenlein, Robert, Khalil, Munira, and Govind, Niranjan. Fri .  
"Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory".  United States.  https://doi.org/10.1063/1.5111141.  https://www.osti.gov/servlets/purl/1591640.

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@article{osti_1591640,

  title        = {Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory},

  author       = {Zhang, Yu and Bergmann, Uwe and Schoenlein, Robert and Khalil, Munira and Govind, Niranjan},

  abstractNote = {With the help of newly developed X-ray free-electron laser (XFEL) sources, creating double core holes (DCHs) simultaneously at the same or different atomic sites in a molecule has now become possible. DCH X-ray emission is a new form of X-ray nonlinear spectroscopy that can be studied with a XFEL. Here in this paper, we computationally explore the metal K-edge valence-to-core (VtC) X-ray emission spectroscopy (XES) of metal/metal and metal/ligand DCH states in a series of transition metal complexes with time-dependent density functional theory. The simulated DCH VtC-XES signals are compared with conventional single core hole (SCH) XES signals. The energy shifts and intensity changes of the DCH emission lines with respect to the corresponding SCH-XES features are fingerprints of the coupling between the second core hole and the occupied orbitals around the DCHs that contain important chemical bonding information of the complex. The difference between delocalized/localized core hole models on DCH VtC-XES is also briefly discussed. We theoretically demonstrate that DCH XES provides subtle information on the local electronic structure around metal centers in transition metal complexes beyond conventional linear XES. In conclusion, our predicted changes from calculations between SCH-XES and DCH-XES features should be detectable with modern XFEL sources.},

  doi          = {10.1063/1.5111141},

  journal      = {Journal of Chemical Physics},

  number       = 14,

  volume       = 151,

  place        = {United States},

  year         = {Fri Oct 11 00:00:00 EDT 2019},

  month        = {Fri Oct 11 00:00:00 EDT 2019}

}

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Figures / Tables:

Fig. 1: Calculated SCH and DCH Fe1s VtC-XES signals of Cp₂Fe(μ-C0)₂ (Fe-cplx, Cp = cyclopentadienyl). All calculated spectra have not been shifted and have been Lorentzian broadened by 1.3 eV. SCH and DCH spectra are scaled differently for the convenience of plotting. Stick heights in different panels are not calibrated.more »

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Theoretical spectroscopy on K–2, K–1L–1, and L–2 double core hole states of SiX4 (X=H, F, Cl, and CH3) molecules
journal, June 2011

Takahashi, Osamu; Tashiro, Motomichi; Ehara, Masahiro
Chemical Physics, Vol. 384, Issue 1-3
DOI: 10.1016/j.chemphys.2011.04.015

Double-core-hole states in CH ₃ CN: Pre-edge structures and chemical-shift contributions
journal, October 2018

Koulentianos, D.; Carniato, S.; Püttner, R.
The Journal of Chemical Physics, Vol. 149, Issue 13
DOI: 10.1063/1.5047854

Molecular-Photoelectron Angular Distributions as a Probe of Dynamic Symmetry Breaking
journal, October 1978

Dill, Dan; Wallace, Scott; Siegel, Jon
Physical Review Letters, Vol. 41, Issue 18
DOI: 10.1103/physrevlett.41.1230

Structure sensitivity of double inner-shell holes in sulfur-containing molecules
journal, February 2011

Linusson, P.; Takahashi, O.; Ueda, K.
Physical Review A, Vol. 83, Issue 2
DOI: 10.1103/physreva.83.022506

Wave and Reaction Operators in the Quantum Theory of Many-Particle Systems
journal, July 1963

Löwdin, Per-Olov
Reviews of Modern Physics, Vol. 35, Issue 3
DOI: 10.1103/revmodphys.35.702

Configuration interaction calculations of satellite structure in photoelectron spectra of H2O
journal, January 1982

Arneberg, Reidar; Müller, Jiri; Manne, Rolf
Chemical Physics, Vol. 64, Issue 2
DOI: 10.1016/0301-0104(82)87091-2

Inner-shell single and double ionization potentials of aminophenol isomers
journal, August 2011

Kryzhevoi, Nikolai V.; Santra, Robin; Cederbaum, Lorenz S.
The Journal of Chemical Physics, Vol. 135, Issue 8
DOI: 10.1063/1.3624393

Molecular double core hole electron spectroscopy for chemical analysis
journal, May 2010

Tashiro, Motomichi; Ehara, Masahiro; Fukuzawa, Hironobu
The Journal of Chemical Physics, Vol. 132, Issue 18
DOI: 10.1063/1.3408251

Atomic inner-shell laser at 1.5-ångström wavelength pumped by an X-ray free-electron laser
journal, August 2015

Yoneda, Hitoki; Inubushi, Yuichi; Nagamine, Kazunori
Nature, Vol. 524, Issue 7566
DOI: 10.1038/nature14894

Compact effective potentials and efficient shared‐exponent basis sets for the first‐ and second‐row atoms
journal, December 1984

Stevens, Walter J.; Basch, Harold; Krauss, Morris
The Journal of Chemical Physics, Vol. 81, Issue 12
DOI: 10.1063/1.447604

Double-core excitations in formamide can be probed by X-ray double-quantum-coherence spectroscopy
journal, April 2013

Zhang, Yu; Healion, Daniel; Biggs, Jason D.
The Journal of Chemical Physics, Vol. 138, Issue 14
DOI: 10.1063/1.4798635

Theoretical Molecular Double-Core-Hole Spectroscopy of Nucleobases
journal, November 2011

Takahashi, Osamu; Tashiro, Motomichi; Ehara, Masahiro
The Journal of Physical Chemistry A, Vol. 115, Issue 44
DOI: 10.1021/jp205923m

Theoretical double-core-hole spectroscopy of cytosine tautomers
journal, February 2018

Takahashi, Osamu
Journal of Electron Spectroscopy and Related Phenomena, Vol. 223
DOI: 10.1016/j.elspec.2018.01.001

Double vacancies in the cores of silane and tetrafluorosilane
journal, July 1991

Ohrendorf, E. M. -L.; Cederbaum, L. S.; Tarantelli, F.
Physical Review A, Vol. 44, Issue 1
DOI: 10.1103/physreva.44.205

Auger Electron Angular Distribution of Double Core-Hole States in the Molecular Reference Frame
journal, August 2010

Cryan, James P.; Glownia, J. M.; Andreasson, J.
Physical Review Letters, Vol. 105, Issue 8
DOI: 10.1103/physrevlett.105.083004

Double Core-Hole Production in $N_{2}$ : Beating the Auger Clock
journal, August 2010

Fang, L.; Hoener, M.; Gessner, O.
Physical Review Letters, Vol. 105, Issue 8
DOI: 10.1103/physrevlett.105.083005

Valence to Core X-ray Emission Spectroscopy
journal, May 2014

Gallo, Erik; Glatzel, Pieter
Advanced Materials, Vol. 26, Issue 46
DOI: 10.1002/adma.201304994

Evidence of Single-Photon Two-Site Core Double Ionization of $C_{2} H_{2}$ Molecules
journal, November 2011

Lablanquie, P.; Grozdanov, T. P.; Žitnik, M.
Physical Review Letters, Vol. 107, Issue 19
DOI: 10.1103/physrevlett.107.193004

On double vacancies in the core
journal, December 1986

Cederbaum, L. S.; Tarantelli, F.; Sgamellotti, A.
The Journal of Chemical Physics, Vol. 85, Issue 11
DOI: 10.1063/1.451432

Role of localization in the prediction of core ESCA lineshapes of N2, O2 and NO
journal, May 1979

Müller, Jiri; Ågren, Hans; Goscinski, Osvaldo
Chemical Physics, Vol. 38, Issue 3
DOI: 10.1016/0301-0104(79)89009-6

Chemical analysis: Double core-hole spectroscopy with free-electron lasers
journal, October 2015

Berrah, N.; Fang, L.
Journal of Electron Spectroscopy and Related Phenomena, Vol. 204
DOI: 10.1016/j.elspec.2015.05.020

Correlated, relativistic, and basis set limit molecular polarizability calculations to evaluate an augmented effective core potential basis set
journal, January 2006

Labello, Nicholas P.; Ferreira, Antonio M.; Kurtz, Henry A.
International Journal of Quantum Chemistry, Vol. 106, Issue 15
DOI: 10.1002/qua.21129

Single photon simultaneous K-shell ionization and K-shell excitation. I. Theoretical model applied to the interpretation of experimental results on H ₂ O
journal, January 2015

Carniato, S.; Selles, P.; Andric, L.
The Journal of Chemical Physics, Vol. 142, Issue 1
DOI: 10.1063/1.4904273

Covariance mapping of two-photon double core hole states in C ₂ H ₂ and C ₂ H ₆ produced by an x-ray free electron laser
journal, July 2015

Mucke, M.; Zhaunerchyk, V.; Frasinski, L. J.
New Journal of Physics, Vol. 17, Issue 7
DOI: 10.1088/1367-2630/17/7/073002

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

Valiev, M.; Bylaska, E. J.; Govind, N.
Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
DOI: 10.1016/j.cpc.2010.04.018

Experimental Verification of the Chemical Sensitivity of Two-Site Double Core-Hole States Formed by an X-Ray Free-Electron Laser
journal, April 2012

Salén, P.; van der Meulen, P.; Schmidt, H. T.
Physical Review Letters, Vol. 108, Issue 15
DOI: 10.1103/physrevlett.108.153003

Localized and Delocalized 1 s Hole States of the O 2 + Molecular Ion
journal, January 1972

Bagus, Paul S.; Schaefer, Henry F.
The Journal of Chemical Physics, Vol. 56, Issue 1
DOI: 10.1063/1.1676850

Molecular double core–hole electron spectroscopy of large molecules for probing molecular size: A series of bridged trihalosilyl–trimethylsilyl molecules
journal, December 2011

Takahashi, Osamu; Yamasaki, Katsuyoshi; Nagaoka, Shin-ichi
Chemical Physics Letters, Vol. 518
DOI: 10.1016/j.cplett.2011.11.006

Extracting chemical information of free molecules from K-shell double core-hole spectroscopy
journal, September 2012

Ueda, Kiyoshi; Takahashi, Osamu
Journal of Electron Spectroscopy and Related Phenomena, Vol. 185, Issue 8-9
DOI: 10.1016/j.elspec.2012.04.003

Double core hole spectroscopy with synchrotron radiation
journal, October 2015

Penent, F.; Nakano, M.; Tashiro, M.
Journal of Electron Spectroscopy and Related Phenomena, Vol. 204
DOI: 10.1016/j.elspec.2015.06.015

K-shell double core-hole spectroscopy in molecules
journal, October 2013

Piancastelli, M. N.
The European Physical Journal Special Topics, Vol. 222, Issue 9
DOI: 10.1140/epjst/e2013-01985-9

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

Weigend, Florian; Ahlrichs, Reinhart
Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
DOI: 10.1039/b508541a

Double core–hole correlation satellite spectra of N2 and CO molecules
journal, January 2012

Tashiro, Motomichi; Ueda, Kiyoshi; Ehara, Masahiro
Chemical Physics Letters, Vol. 521
DOI: 10.1016/j.cplett.2011.11.062

Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q)
journal, February 2012

Noro, Takeshi; Sekiya, Masahiro; Koga, Toshikatsu
Theoretical Chemistry Accounts, Vol. 131, Issue 2
DOI: 10.1007/s00214-012-1124-z

Hole localization and broken symmetry: A theoretical study of core electron ionization in the Li2 molecule
journal, March 1987

Bacskay, George B.; Bryant, Glenn; Hush, Noel S.
International Journal of Quantum Chemistry, Vol. 31, Issue 3
DOI: 10.1002/qua.560310319

Study of double core hole excitations in molecules by X-ray double-quantum-coherence signals: a multi-configuration simulation
journal, January 2016

Hua, Weijie; Bennett, Kochise; Zhang, Yu
Chemical Science, Vol. 7, Issue 9
DOI: 10.1039/c6sc01571a

Auger decay of molecular double core-hole and its satellite states: Comparison of experiment and calculation
journal, December 2012

Penent, Francis; Andric, Lidija; Palaudoux, Jérôme
The Journal of Chemical Physics, Vol. 137, Issue 22
DOI: 10.1063/1.4769777

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc
journal, December 2018

Duncan Lyngdoh, Richard H.; Schaefer, Henry F.; King, R. Bruce
Chemical Reviews, Vol. 118, Issue 24
DOI: 10.1021/acs.chemrev.8b00297

Ab initio Hartree-Fock calculations of molecular X-ray intensities. Validity of one-center approximations
journal, January 1981

�gren, Hans; Nordgren, Joseph
Theoretica Chimica Acta, Vol. 58, Issue 2
DOI: 10.1007/BF00550423

Single and Double Core-Hole Ionization Energies in Molecules
journal, April 2012

Thomas, T. Darrah
The Journal of Physical Chemistry A, Vol. 116, Issue 15
DOI: 10.1021/jp211741e

Double Core Hole Creation and Subsequent Auger Decay in ${NH}_{3}$ and ${CH}_{4}$ Molecules
journal, November 2010

Eland, J. H. D.; Tashiro, M.; Linusson, P.
Physical Review Letters, Vol. 105, Issue 21
DOI: 10.1103/physrevlett.105.213005

Femtosecond electronic response of atoms to ultra-intense X-rays
journal, July 2010

Young, L.; Kanter, E. P.; Krässig, B.
Nature, Vol. 466, Issue 7302
DOI: 10.1038/nature09177

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

Adamo, Carlo; Barone, Vincenzo
The Journal of Chemical Physics, Vol. 110, Issue 13
DOI: 10.1063/1.478522

Probing chemical environment with molecular double core-hole electron spectroscopy
journal, October 2015

Takahashi, Osamu; Kryzhevoi, Nikolai V.; Ueda, Kiyoshi
Journal of Electron Spectroscopy and Related Phenomena, Vol. 204
DOI: 10.1016/j.elspec.2015.08.015

Localized and delocalized core holes and their interrelation
journal, June 1977

Cederbaum, L. S.; Domcke, W.
The Journal of Chemical Physics, Vol. 66, Issue 11
DOI: 10.1063/1.433763

Properties of Hollow Molecules Probed by Single-Photon Double Ionization
journal, February 2011

Lablanquie, P.; Penent, F.; Palaudoux, J.
Physical Review Letters, Vol. 106, Issue 6
DOI: 10.1103/physrevlett.106.063003

Localized and delocalized 1s core-holes in DFT calculations
journal, June 2007

Chong, Delano P.
Journal of Electron Spectroscopy and Related Phenomena, Vol. 159, Issue 1-3
DOI: 10.1016/j.elspec.2007.01.005

X-Ray Two-Photon Photoelectron Spectroscopy: A Theoretical Study of Inner-Shell Spectra of the Organic Para-Aminophenol Molecule
journal, July 2009

Santra, Robin; Kryzhevoi, Nikolai V.; Cederbaum, Lorenz S.
Physical Review Letters, Vol. 103, Issue 1
DOI: 10.1103/physrevlett.103.013002

Disentangling formation of multiple-core holes in aminophenol molecules exposed to bright X-FEL radiation
journal, October 2015

Zhaunerchyk, V.; Kamińska, M.; Mucke, M.
Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 48, Issue 24
DOI: 10.1088/0953-4075/48/24/244003

Atomic inner-shell X-ray laser at 1.46 nanometres pumped by an X-ray free-electron laser
journal, January 2012

Rohringer, Nina; Ryan, Duncan; London, Richard A.
Nature, Vol. 481, Issue 7382
DOI: 10.1038/nature10721

Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions
journal, September 2011

Beckwith, Martha A.; Roemelt, Michael; Collomb, Marie-Noëlle
Inorganic Chemistry, Vol. 50, Issue 17
DOI: 10.1021/ic200970t

Multiple Bonds Between Metal Atoms
book, January 2005

Cotton, F. Albert; Murillo, Carlos A.; Walton, Richard A.
DOI: 10.1007/b136230

Ultrafast Probing of Core Hole Localization in N2
journal, May 2008

Schoffler, M. S.; Titze, J.; Petridis, N.
Science, Vol. 320, Issue 5878
DOI: 10.1126/science.1154989

Double-core-hole spectroscopy for chemical analysis with an intense X-ray femtosecond laser
journal, October 2011

Berrah, N.; Fang, L.; Murphy, B.
Proceedings of the National Academy of Sciences, Vol. 108, Issue 41
DOI: 10.1073/pnas.1111380108

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
DOI: 10.1063/1.472933

Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory
journal, November 2015

Zhang, Yu; Mukamel, Shaul; Khalil, Munira
Journal of Chemical Theory and Computation, Vol. 11, Issue 12
DOI: 10.1021/acs.jctc.5b00763

Double core-hole formation in small molecules at the LCLS free electron laser
journal, August 2013

Larsson, M.; Salén, P.; van der Meulen, P.
Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 46, Issue 16
DOI: 10.1088/0953-4075/46/16/164030

Unsaturation in Binuclear Cyclopentadienyliron Carbonyls
journal, April 2006

Wang, Hongyan; Xie, Yaoming; King, R. Bruce
Inorganic Chemistry, Vol. 45, Issue 8
DOI: 10.1021/ic051613l

Metal–Metal Bonds: From Fundamentals to Applications
journal, June 2017

Berry, John F.; Lu, Connie C.
Inorganic Chemistry, Vol. 56, Issue 14
DOI: 10.1021/acs.inorgchem.7b01330

Molecular double core-hole electron spectroscopy for probing chemical bonds: C60 and chain molecules revisited
journal, August 2014

Takahashi, Osamu; Ueda, Kiyoshi
Chemical Physics, Vol. 440
DOI: 10.1016/j.chemphys.2014.06.007

Open chains versus closed rings: Comparison of binuclear butadiene cobalt carbonyls with cyclic hydrocarbon analogs
journal, June 2012

Fan, Qunchao; Feng, Hao; Sun, Weiguo
Inorganica Chimica Acta, Vol. 388
DOI: 10.1016/j.ica.2012.03.018

Selecting core-hole localization or delocalization in CS2 by photofragmentation dynamics
journal, January 2015

Guillemin, R.; Decleva, P.; Stener, M.
Nature Communications, Vol. 6, Issue 1
DOI: 10.1038/ncomms7166

Double core–hole electron spectroscopy for open-shell molecules: Theoretical perspective
journal, August 2010

Tashiro, Motomichi; Ehara, Masahiro; Ueda, Kiyoshi
Chemical Physics Letters, Vol. 496, Issue 1-3
DOI: 10.1016/j.cplett.2010.07.046

Symmetry Breaking and Hole Localization in Multiple Core Electron Ionization
journal, July 2013

Carravetta, V.; Ågren, H.
The Journal of Physical Chemistry A, Vol. 117, Issue 31
DOI: 10.1021/jp406602y

Molecular-Photoelectron Angular Distributions as a Probe of Dynamic Symmetry Breaking.
journal, February 1979

Dill, Dan; Wallace, Scott; Siegel, Jon
Physical Review Letters, Vol. 42, Issue 6
DOI: 10.1103/physrevlett.42.411

Stimulated X-Ray Emission Spectroscopy in Transition Metal Complexes
text, January 2018

Kroll, Thomas; Weninger, Clemens; Alonso-Mori, Roberto
Deutsches Elektronen-Synchrotron, DESY, Hamburg
DOI: 10.3204/pubdb-2019-00874

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays
journal, May 2020

Smolentsev, Grigory; Milne, Christopher J.; Guda, Alexander
Nature Communications, Vol. 11, Issue 1
DOI: 10.1038/s41467-020-15998-z

Multiple Bonds Between Metal Atoms
journal, November 1993

Lappert, M. F.
Journal of Organometallic Chemistry, Vol. 461, Issue 1-2
DOI: 10.1016/0022-328x(93)83301-b

Auger Electron Angular Distribution of Double Core-Hole States in the Molecular Reference Frame
text, January 2010

Cryan, J. P.; Glownia, J. M.; Andreasson, J.
Deutsches Elektronen-Synchrotron, DESY, Hamburg
DOI: 10.3204/phppubdb-14448

X-ray two-photon photoelectron sectroscopy: a theoretical study of inner-shell spectra of the organic para-aminophenol molecule
text, January 2009

Santra, Robin; Kryzhevoi, N.; Cederbaum, L.
Deutsches Elektronen-Synchrotron, DESY, Hamburg
DOI: 10.3204/phppubdb-22207

Double core-hole electron spectroscopy for open-shell molecules: theoretical perspective
text, January 2010

Tashiro, Motomichi; Ehara, Masahiro; Ueda, Kiyoshi
arXiv
DOI: 10.48550/arxiv.1007.0530

Double-core Excitations in Formamide Can Be Probed by X-ray Double-quantum-coherence Spectroscopy
text, January 2013

Zhang, Yu; Healion, Daniel; Biggs, Jason D.
arXiv
DOI: 10.48550/arxiv.1303.4721

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We probe the dynamics of valence electrons in photoexcited [Fe(terpy)2]2+ in solution to gain deeper insight into the Fe-ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete 1s X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitals directly involved inmore »« less
Cited by 19
https://doi.org/10.1021/acs.jpcc.6b12940
Valence-to-core X-ray emission spectroscopy to resolve the size-dependent valence electronic structure of Pt nanoparticles

Journal Article Dean, David P. ; Deshmukh, Gaurav S. ; Russell, Christopher K. ; ... - Catalysis Science and Technology

X-ray characterization of catalyst materials using synchrotron radiation has become more widely available to the scientific community in recent decades. Techniques such as X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) have enabled in-situ and in-operando studies of dilute catalyst sites for heterogeneous catalyst materials in order to obtain information about local geometric and electronic structure and how it impacts chemical transformations. Non-resonant or valence-to-core X-ray emission spectroscopy (NR-XES or VtC-XES) is an emerging technique used to probe changes to the d-electron density of states (d-DOS) for various factors such as ligand environment or alloy formation. In thismore »« less
https://doi.org/10.1039/D3CY01554H
Valence-to-core X-ray emission spectroscopy of titanium compounds using energy dispersive detectors

Journal Article Miaja‐Avila, Luis ; O'Neil, Galen C. ; Joe, Young Il ; ... - X-Ray Spectrometry, XRS

X-ray emission spectroscopy (XES) of transition metal compounds is a powerful tool for investigating the spin and oxidation state of the metal centers. Valence-to-core (vtc) XES is of special interest, as it contains information on the ligand nature, hybridization, and protonation. To date, most vtc-XES studies have been performed with high-brightness sources, such as synchrotrons, due to the weak fluorescence lines from vtc transitions. Here, we present a systematic study of the vtc-XES for different titanium compounds in a laboratory setting using an X-ray tube source and energy dispersive microcalorimeter sensors. With a full-width at half-maximum energy resolution of approximatelymore »« less
Cited by 8
https://doi.org/10.1002/xrs.3183

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Title: Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory

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Theoretical spectroscopy on K–2, K–1L–1, and L–2 double core hole states of SiX4 (X=H, F, Cl, and CH3) molecules journal, June 2011

Double-core-hole states in CH 3 CN: Pre-edge structures and chemical-shift contributions journal, October 2018

Molecular-Photoelectron Angular Distributions as a Probe of Dynamic Symmetry Breaking journal, October 1978

Structure sensitivity of double inner-shell holes in sulfur-containing molecules journal, February 2011

Wave and Reaction Operators in the Quantum Theory of Many-Particle Systems journal, July 1963

Configuration interaction calculations of satellite structure in photoelectron spectra of H2O journal, January 1982

Inner-shell single and double ionization potentials of aminophenol isomers journal, August 2011

Molecular double core hole electron spectroscopy for chemical analysis journal, May 2010

Atomic inner-shell laser at 1.5-ångström wavelength pumped by an X-ray free-electron laser journal, August 2015

Compact effective potentials and efficient shared‐exponent basis sets for the first‐ and second‐row atoms journal, December 1984

Double-core excitations in formamide can be probed by X-ray double-quantum-coherence spectroscopy journal, April 2013

Theoretical Molecular Double-Core-Hole Spectroscopy of Nucleobases journal, November 2011

Theoretical double-core-hole spectroscopy of cytosine tautomers journal, February 2018

Double vacancies in the cores of silane and tetrafluorosilane journal, July 1991

Auger Electron Angular Distribution of Double Core-Hole States in the Molecular Reference Frame journal, August 2010

Double Core-Hole Production in N 2 : Beating the Auger Clock journal, August 2010

Valence to Core X-ray Emission Spectroscopy journal, May 2014

Evidence of Single-Photon Two-Site Core Double Ionization of C 2 H 2 Molecules journal, November 2011

On double vacancies in the core journal, December 1986

Role of localization in the prediction of core ESCA lineshapes of N2, O2 and NO journal, May 1979

Chemical analysis: Double core-hole spectroscopy with free-electron lasers journal, October 2015

Correlated, relativistic, and basis set limit molecular polarizability calculations to evaluate an augmented effective core potential basis set journal, January 2006

Single photon simultaneous K-shell ionization and K-shell excitation. I. Theoretical model applied to the interpretation of experimental results on H 2 O journal, January 2015

Covariance mapping of two-photon double core hole states in C 2 H 2 and C 2 H 6 produced by an x-ray free electron laser journal, July 2015

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal, September 2010

Experimental Verification of the Chemical Sensitivity of Two-Site Double Core-Hole States Formed by an X-Ray Free-Electron Laser journal, April 2012

Localized and Delocalized 1 s Hole States of the O 2 + Molecular Ion journal, January 1972

Molecular double core–hole electron spectroscopy of large molecules for probing molecular size: A series of bridged trihalosilyl–trimethylsilyl molecules journal, December 2011

Extracting chemical information of free molecules from K-shell double core-hole spectroscopy journal, September 2012

Double core hole spectroscopy with synchrotron radiation journal, October 2015

K-shell double core-hole spectroscopy in molecules journal, October 2013

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal, January 2005

Double core–hole correlation satellite spectra of N2 and CO molecules journal, January 2012

Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q) journal, February 2012

Hole localization and broken symmetry: A theoretical study of core electron ionization in the Li2 molecule journal, March 1987

Study of double core hole excitations in molecules by X-ray double-quantum-coherence signals: a multi-configuration simulation journal, January 2016

Auger decay of molecular double core-hole and its satellite states: Comparison of experiment and calculation journal, December 2012

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc journal, December 2018

Ab initio Hartree-Fock calculations of molecular X-ray intensities. Validity of one-center approximations journal, January 1981

Single and Double Core-Hole Ionization Energies in Molecules journal, April 2012

Double Core Hole Creation and Subsequent Auger Decay in NH 3 and CH 4 Molecules journal, November 2010

Femtosecond electronic response of atoms to ultra-intense X-rays journal, July 2010

Toward reliable density functional methods without adjustable parameters: The PBE0 model journal, April 1999

Probing chemical environment with molecular double core-hole electron spectroscopy journal, October 2015

Localized and delocalized core holes and their interrelation journal, June 1977

Properties of Hollow Molecules Probed by Single-Photon Double Ionization journal, February 2011

Localized and delocalized 1s core-holes in DFT calculations journal, June 2007

X-Ray Two-Photon Photoelectron Spectroscopy: A Theoretical Study of Inner-Shell Spectra of the Organic Para-Aminophenol Molecule journal, July 2009

Disentangling formation of multiple-core holes in aminophenol molecules exposed to bright X-FEL radiation journal, October 2015

Atomic inner-shell X-ray laser at 1.46 nanometres pumped by an X-ray free-electron laser journal, January 2012

Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions journal, September 2011

Multiple Bonds Between Metal Atoms book, January 2005

Ultrafast Probing of Core Hole Localization in N2 journal, May 2008

Double-core-hole spectroscopy for chemical analysis with an intense X-ray femtosecond laser journal, October 2011

Rationale for mixing exact exchange with density functional approximations journal, December 1996

Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory journal, November 2015

Double core-hole formation in small molecules at the LCLS free electron laser journal, August 2013

Unsaturation in Binuclear Cyclopentadienyliron Carbonyls journal, April 2006

Metal–Metal Bonds: From Fundamentals to Applications journal, June 2017

Molecular double core-hole electron spectroscopy for probing chemical bonds: C60 and chain molecules revisited journal, August 2014

Open chains versus closed rings: Comparison of binuclear butadiene cobalt carbonyls with cyclic hydrocarbon analogs journal, June 2012

Selecting core-hole localization or delocalization in CS2 by photofragmentation dynamics journal, January 2015

Double core–hole electron spectroscopy for open-shell molecules: Theoretical perspective journal, August 2010

Symmetry Breaking and Hole Localization in Multiple Core Electron Ionization journal, July 2013

Molecular-Photoelectron Angular Distributions as a Probe of Dynamic Symmetry Breaking. journal, February 1979

Stimulated X-Ray Emission Spectroscopy in Transition Metal Complexes text, January 2018

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays journal, May 2020

Multiple Bonds Between Metal Atoms journal, November 1993

Auger Electron Angular Distribution of Double Core-Hole States in the Molecular Reference Frame text, January 2010

X-ray two-photon photoelectron sectroscopy: a theoretical study of inner-shell spectra of the organic para-aminophenol molecule text, January 2009

Double core-hole electron spectroscopy for open-shell molecules: theoretical perspective text, January 2010

Double-core Excitations in Formamide Can Be Probed by X-ray Double-quantum-coherence Spectroscopy text, January 2013

Theoretical spectroscopy on K–2, K–1L–1, and L–2 double core hole states of SiX4 (X=H, F, Cl, and CH3) molecules
journal, June 2011

Double-core-hole states in CH ₃ CN: Pre-edge structures and chemical-shift contributions
journal, October 2018

Molecular-Photoelectron Angular Distributions as a Probe of Dynamic Symmetry Breaking
journal, October 1978

Structure sensitivity of double inner-shell holes in sulfur-containing molecules
journal, February 2011

Wave and Reaction Operators in the Quantum Theory of Many-Particle Systems
journal, July 1963

Configuration interaction calculations of satellite structure in photoelectron spectra of H2O
journal, January 1982

Inner-shell single and double ionization potentials of aminophenol isomers
journal, August 2011

Molecular double core hole electron spectroscopy for chemical analysis
journal, May 2010

Atomic inner-shell laser at 1.5-ångström wavelength pumped by an X-ray free-electron laser
journal, August 2015

Compact effective potentials and efficient shared‐exponent basis sets for the first‐ and second‐row atoms
journal, December 1984

Double-core excitations in formamide can be probed by X-ray double-quantum-coherence spectroscopy
journal, April 2013

Theoretical Molecular Double-Core-Hole Spectroscopy of Nucleobases
journal, November 2011

Theoretical double-core-hole spectroscopy of cytosine tautomers
journal, February 2018

Double vacancies in the cores of silane and tetrafluorosilane
journal, July 1991

Auger Electron Angular Distribution of Double Core-Hole States in the Molecular Reference Frame
journal, August 2010

Double Core-Hole Production in $N_{2}$ : Beating the Auger Clock
journal, August 2010

Valence to Core X-ray Emission Spectroscopy
journal, May 2014

Evidence of Single-Photon Two-Site Core Double Ionization of $C_{2} H_{2}$ Molecules
journal, November 2011

On double vacancies in the core
journal, December 1986

Role of localization in the prediction of core ESCA lineshapes of N2, O2 and NO
journal, May 1979

Chemical analysis: Double core-hole spectroscopy with free-electron lasers
journal, October 2015

Correlated, relativistic, and basis set limit molecular polarizability calculations to evaluate an augmented effective core potential basis set
journal, January 2006

Single photon simultaneous K-shell ionization and K-shell excitation. I. Theoretical model applied to the interpretation of experimental results on H ₂ O
journal, January 2015

Covariance mapping of two-photon double core hole states in C ₂ H ₂ and C ₂ H ₆ produced by an x-ray free electron laser
journal, July 2015

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

Experimental Verification of the Chemical Sensitivity of Two-Site Double Core-Hole States Formed by an X-Ray Free-Electron Laser
journal, April 2012

Localized and Delocalized 1 s Hole States of the O 2 + Molecular Ion
journal, January 1972

Molecular double core–hole electron spectroscopy of large molecules for probing molecular size: A series of bridged trihalosilyl–trimethylsilyl molecules
journal, December 2011

Extracting chemical information of free molecules from K-shell double core-hole spectroscopy
journal, September 2012

Double core hole spectroscopy with synchrotron radiation
journal, October 2015

K-shell double core-hole spectroscopy in molecules
journal, October 2013

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

Double core–hole correlation satellite spectra of N2 and CO molecules
journal, January 2012

Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q)
journal, February 2012

Hole localization and broken symmetry: A theoretical study of core electron ionization in the Li2 molecule
journal, March 1987

Study of double core hole excitations in molecules by X-ray double-quantum-coherence signals: a multi-configuration simulation
journal, January 2016

Auger decay of molecular double core-hole and its satellite states: Comparison of experiment and calculation
journal, December 2012

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc
journal, December 2018

Ab initio Hartree-Fock calculations of molecular X-ray intensities. Validity of one-center approximations
journal, January 1981

Single and Double Core-Hole Ionization Energies in Molecules
journal, April 2012

Double Core Hole Creation and Subsequent Auger Decay in ${NH}_{3}$ and ${CH}_{4}$ Molecules
journal, November 2010

Femtosecond electronic response of atoms to ultra-intense X-rays
journal, July 2010

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

Probing chemical environment with molecular double core-hole electron spectroscopy
journal, October 2015

Localized and delocalized core holes and their interrelation
journal, June 1977

Properties of Hollow Molecules Probed by Single-Photon Double Ionization
journal, February 2011

Localized and delocalized 1s core-holes in DFT calculations
journal, June 2007

X-Ray Two-Photon Photoelectron Spectroscopy: A Theoretical Study of Inner-Shell Spectra of the Organic Para-Aminophenol Molecule
journal, July 2009

Disentangling formation of multiple-core holes in aminophenol molecules exposed to bright X-FEL radiation
journal, October 2015

Atomic inner-shell X-ray laser at 1.46 nanometres pumped by an X-ray free-electron laser
journal, January 2012

Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions
journal, September 2011

Multiple Bonds Between Metal Atoms
book, January 2005

Ultrafast Probing of Core Hole Localization in N2
journal, May 2008

Double-core-hole spectroscopy for chemical analysis with an intense X-ray femtosecond laser
journal, October 2011

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory
journal, November 2015

Double core-hole formation in small molecules at the LCLS free electron laser
journal, August 2013

Unsaturation in Binuclear Cyclopentadienyliron Carbonyls
journal, April 2006

Metal–Metal Bonds: From Fundamentals to Applications
journal, June 2017

Molecular double core-hole electron spectroscopy for probing chemical bonds: C60 and chain molecules revisited
journal, August 2014

Open chains versus closed rings: Comparison of binuclear butadiene cobalt carbonyls with cyclic hydrocarbon analogs
journal, June 2012

Selecting core-hole localization or delocalization in CS2 by photofragmentation dynamics
journal, January 2015

Double core–hole electron spectroscopy for open-shell molecules: Theoretical perspective
journal, August 2010

Symmetry Breaking and Hole Localization in Multiple Core Electron Ionization
journal, July 2013

Molecular-Photoelectron Angular Distributions as a Probe of Dynamic Symmetry Breaking.
journal, February 1979

Stimulated X-Ray Emission Spectroscopy in Transition Metal Complexes
text, January 2018

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays
journal, May 2020

Multiple Bonds Between Metal Atoms
journal, November 1993

Auger Electron Angular Distribution of Double Core-Hole States in the Molecular Reference Frame
text, January 2010

X-ray two-photon photoelectron sectroscopy: a theoretical study of inner-shell spectra of the organic para-aminophenol molecule
text, January 2009

Double core-hole electron spectroscopy for open-shell molecules: theoretical perspective
text, January 2010

Double-core Excitations in Formamide Can Be Probed by X-ray Double-quantum-coherence Spectroscopy
text, January 2013