The nitrogen and sulfur K-edge X-ray absorption spectra of aqueous 2-thiopyridone, a model system for excited-state proton transfer in several recent time-resolved measurements, have been simulated from ab initio molecular dynamics. Spectral signatures of the local intra- and inter-molecular structure are identified and rationalized, which facilitates experimental interpretation and optimization. In particular, comparison of aqueous and gas phase spectrum simulations assesses the previously unquantified solvatization effects, where hydrogen bonding is found to yield solvatochromatic shifts up to nearly 1 eV of the main peak positions. Thereby, while each K-edge can still decisively determine the local protonation of its core-excited site, only their combined, complementary fingerprints allow separating all of the three relevant molecular forms, giving a complete picture of the proton transfer.
REFERENCES
1.
P. M.
Kraus
, M.
Zurch
, S. K.
Cushing
, D. M.
Neumark
, and S. R.
Leone
, “The ultrafast X-ray spectroscopic revolution in chemical dynamics
,” Nat. Rev. Chem.
2
, 82
(2018
).2.
L. X.
Chen
, X.
Zhang
, and M.
Shelby
, “Recent advances on ultrafast x-ray spectroscopy in the chemical sciences
,” Chem. Sci.
5
, 4136
–4152
(2014
).3.
B.
Winter
and M.
Faubel
, “Photoemission from liquid aqueous solutions
,” Chem. Rev.
106
, 1176
–1211
(2006
).4.
O.
Gessner
and M.
Guhr
, “Monitoring ultrafast chemical dynamics by time-domain x-ray photo-and Auger-electron spectroscopy
,” Acc. Chem. Res.
49
, 138
–145
(2015
).5.
J. W.
Smith
and R. J.
Saykally
, “Soft x-ray absorption spectroscopy of liquids and solutions
,” Chem. Rev.
117
, 13909
–13934
(2017
).6.
F.
De Groot
, “High-resolution x-ray emission and x-ray absorption spectroscopy
,” Chem. Rev.
101
, 1779
–1808
(2001
).7.
C.
Bressler
and M.
Chergui
, “Ultrafast x-ray absorption spectroscopy
,” Chem. Rev.
104
, 1781
–1812
(2004
).8.
M.
Blum
, M.
Odelius
, L.
Weinhardt
, S.
Pookpanratana
, M.
Bär
, Y.
Zhang
, O.
Fuchs
, W.
Yang
, E.
Umbach
, and C.
Heske
, “Ultra-fast proton dynamics in aqueous amino acid solutions studied by resonant inelastic soft x-ray scattering
,” J. Phys. Chem. B
116
, 13757
–13764
(2012
).9.
M.
Ekimova
, W.
Quevedo
, Ł.
Szyc
, M.
Iannuzzi
, P.
Wernet
, M.
Odelius
, and E. T. J.
Nibbering
, “Aqueous solvation of ammonia and ammonium: Probing hydrogen bond motifs with FT-IR and soft x-ray spectroscopy
,” J. Am. Chem. Soc.
139
, 12773
–12783
(2017
).10.
S.
Eckert
, J.
Niskanen
, R. M.
Jay
, P. S.
Miedema
, M.
Fondell
, B.
Kennedy
, W.
Quevedo
, M.
Iannuzzi
, and A.
Föhlisch
, “Valence orbitals and local bond dynamics around N atoms of histidine under X-ray irradiation
,” Phys. Chem. Chem. Phys.
19
, 32091
–32098
(2017
).11.
F.
Meyer
, M.
Blum
, A.
Benkert
, D.
Hauschild
, Y. L.
Jeyachandran
, R. G.
Wilks
, W.
Yang
, M.
Bär
, F.
Reinert
, C.
Heske
, M.
Zharnikov
, and L.
Weinhardt
, “Site-specific electronic structure of imidazole and imidazolium in aqueous solutions
,” Phys. Chem. Chem. Phys.
20
, 8302
–8310
(2018
).12.
S.
Melandri
, L.
Evangelisti
, A.
Maris
, W.
Caminati
, B. M.
Giuliano
, V.
Feyer
, K. C.
Prince
, and M.
Coreno
, “Rotational and core level spectroscopies as complementary techniques in tautomeric/conformational studies: The case of 2-mercaptopyridine
,” J. Am. Chem. Soc.
132
, 10269
–10271
(2010
).13.
S.
Eckert
, P.
Miedema
, W.
Quevedo
, B.
O’Cinneide
, M.
Fondell
, M.
Beye
, A.
Pietzsch
, M.
Ross
, M.
Khalil
, and A.
Föhlisch
, “Molecular structures and protonation state of 2-Mercaptopyridine in aqueous solution
,” Chem. Phys. Lett.
647
, 103
–106
(2016
).14.
S.
Eckert
, J.
Norell
, P. S.
Miedema
, M.
Beye
, M.
Fondell
, W.
Quevedo
, B.
Kennedy
, M.
Hantschmann
, A.
Pietzsch
, B. E.
VanKuiken
, M.
Ross
, M. P.
Minitti
, S. P.
Moeller
, W. F.
Schlotter
, M.
Khalil
, M.
Odelius
, and A.
Föhlisch
, “Ultrafast independent N-H and N-C bond deformation investigated with resonant inelastic x-ray scattering
,” Angew. Chem., Int. Ed.
56
, 6088
–6092
(2017
).15.
B. E.
Van Kuiken
, M. R.
Ross
, M. L.
Strader
, A. A.
Cordones
, H.
Cho
, J. H.
Lee
, R. W.
Schoenlein
, and M.
Khalil
, “Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer
,” Struct. Dyn.
4
, 044021
(2017
).16.
S.
Eckert
, J.
Norell
, R. M.
Jay
, M.
Fondell
, R.
Mitzner
, M.
Odelius
, and A.
Föhlisch
, “T1 population as the driver of excited-state proton-transfer in 2-thiopyridone
,” Chem. - Eur. J.
25
, 1733
–1739
(2019
).17.
T.
Tokushima
, Y.
Horikawa
, Y.
Harada
, O.
Takahashi
, A.
Hiraya
, and S.
Shin
, “Selective observation of the two oxygen atoms at different sites in the carboxyl group (–COOH) of liquid acetic acid
,” Phys. Chem. Chem. Phys.
11
, 1679
–1682
(2009
).18.
E.
Spinner
, “250. The infrared spectra of some N-heteroaromatic mercaptocompounds and of their N-methyl and S-methyl derivatives
,” J. Chem. Soc. (Resumed)
1960
, 1237
–1242
.19.
R.
Du
, C.
Liu
, Y.
Zhao
, K.-M.
Pei
, H.-G.
Wang
, X.
Zheng
, M.
Li
, J.-D.
Xue
, and D. L.
Phillips
, “Resonance Raman spectroscopic and theoretical investigation of the excited state proton transfer reaction dynamics of 2-thiopyridone
,” J. Phys. Chem.
115
, 8266
–8277
(2011
).20.
R.
Jones
and A.
Katritzky
, “721. Tautomeric pyridines. Part I. Pyrid-2-and-4-thione
,” J. Chem. Soc. (Resumed)
1958
, 3610
–3613
.21.
P.
Beak
, F. S.
Fry
, Jr., J.
Lee
, and F.
Steele
, “Equilibration studies. Protomeric equilibria of 2-and 4-hydroxypyridines, 2- and 4-hydroxypyrimidines, 2- and 4-mercaptopyridines, and structurally related compounds in the gas phase
,” J. Am. Chem. Soc.
98
, 171
–179
(1976
).22.
S.
Stoyanov
, I.
Petkov
, L.
Antonov
, T.
Stoyanova
, P.
Karagiannidis
, and P.
Aslanidis
, “Thione-thiol tautomerism and stability of 2- and 4-mercaptopyridines and 2-mercaptopyrimidines
,” Can. J. Chem.
68
, 1482
–1489
(1990
).23.
G.
Vall-llosera
, B.
Gao
, A.
Kivimäki
, M.
Coreno
, J.
Álvarez Ruiz
, M.
de Simone
, H.
Ågren
, and E.
Rachlew
, “The C 1s and N 1s near edge x-ray absorption fine structure spectra of five azabenzenes in the gas phase
,” J. Chem. Phys.
128
, 044316
(2008
).24.
C.
Kolczewski
, R.
Püttner
, O.
Plashkevych
, H.
Ågren
, V.
Staemmler
, M.
Martins
, G.
Snell
, A. S.
Schlachter
, M.
Sant’Anna
, G.
Kaindl
, and L. G. M.
Pettersson
, “Detailed study of pyridine at the C1s and N1s ionization thresholds: The influence of the vibrational fine structure
,” J. Chem. Phys.
115
, 6426
–6437
(2001
).25.
M.
Nagasaka
, H.
Yuzawa
, and N.
Kosugi
, “Intermolecular interactions of pyridine in liquid phase and aqueous solution studied by soft x-ray absorption spectroscopy
,” Z. Phys. Chem.
232
, 705
–722
(2018
).26.
N.
Agmon
, “Elementary steps in excited-state proton transfer
,” J. Phys. Chem. A
109
, 13
–35
(2005
).27.
H.
Kagel
, M.
Frohme
, and J.
Glökler
, “Photoacids in biochemical applications
,” J. Cell. Biotechnol.
4
, 23
–30
(2018
).28.
J.
Norell
, A.
Ljungdahl
, and M.
Odelius
, “Interdependent electronic structure, protonation and solvatization of aqueous 2-thiopyridone
,” J. Phys. Chem. B
123
(26
), 5555
–5567
(2019
).29.
B. G.
Lippert
, J.
Hutter
, and M.
Parrinello
, “A hybrid Gaussian and plane wave density functional scheme
,” Mol. Phys.
92
, 477
–488
(1997
).30.
J.
Hutter
, M.
Iannuzzi
, F.
Schiffmann
, and J.
VandeVondele
, “CP2K: Atomistic simulations of condensed matter systems
,” Wiley Interdiscip. Rev.: Comput. Mol. Sci.
4
, 15
–25
(2014
).31.
CP2K, the CP2K developers group, http://www.cp2k.org (
2018
).32.
J.
VandeVondele
, M.
Krack
, F.
Mohamed
, M.
Parrinello
, T.
Chassaing
, and J.
Hutter
, “Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
,” Comput. Phys. Commun.
167
, 103
–128
(2005
).33.
G.
Lippert
, J.
Hutter
, and M.
Parrinello
, “The Gaussian and augmented-plane-wave density functional method for ab initio molecular dynamics simulations
,” Theor. Chem. Acc.
103
, 124
–140
(1999
).34.
M.
Iannuzzi
and J.
Hutter
, “Inner-shell spectroscopy by the Gaussian and augmented plane wave method
,” Phys. Chem. Chem. Phys.
9
, 1599
–1610
(2007
).35.
A. D.
Becke
, “Density-functional exchange-energy approximation with correct asymptotic behavior
,” Phys. Rev. A
38
, 3098
–3100
(1988
).36.
C.
Lee
, W.
Yang
, and R. G.
Parr
, “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
,” Phys. Rev. B
37
, 785
–789
(1988
).37.
S.
Grimme
, S.
Ehrlich
, and L.
Goerigk
, “Effect of the damping function in dispersion corrected density functional theory
,” J. Comput. Chem.
32
, 1456
–1465
(2011
).38.
S.
Grimme
, J.
Antony
, S.
Ehrlich
, and H.
Krieg
, “A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
,” J. Chem. Phys.
132
, 154104
(2010
).39.
L.
Triguero
, L.
Pettersson
, and H.
Ågren
, “Calculations of near-edge x-ray-absorption spectra of gas-phase and chemisorbed molecules by means of density-functional and transition-potential theory
,” Phys. Rev. B
58
, 8097
(1998
).40.
D.
Prendergast
and G.
Galli
, “X-ray absorption spectra of water from first principles calculations
,” Phys. Rev. Lett.
96
, 215502
(2006
).41.
J. S.
Binkley
, J. A.
Pople
, and W. J.
Hehre
, “Self-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elements
,” J. Am. Chem. Soc.
102
, 939
–947
(1980
).42.
M. M.
Francl
, W. J.
Pietro
, W. J.
Hehre
, J. S.
Binkley
, M. S.
Gordon
, D. J.
DeFrees
, and J. A.
Pople
, “Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for second-row elements
,” J. Chem. Phys.
77
, 3654
–3665
(1982
).43.
T.
Clark
, J.
Chandrasekhar
, G. W.
Spitznagel
, and P. V. R.
Schleyer
, “Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+ g basis set for first-row elements, Li–F
,” J. Comput. Chem.
4
, 294
–301
(1983
).44.
P. C.
Hariharan
and J. A.
Pople
, “The influence of polarization functions on molecular orbital hydrogenation energies
,” Theor. Chim. Acta
28
, 213
–222
(1973
).45.
M.
Krack
, “Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals
,” Theor. Chem. Acc.
114
, 145
–152
(2005
).46.
C.
Hartwigsen
, S.
Goedecker
, and J.
Hutter
, “Relativistic separable dual-space Gaussian pseudopotentials from H to Rn
,” Phys. Rev. B
58
, 3641
–3662
(1998
).47.
S.
Goedecker
, M.
Teter
, and J.
Hutter
, “Separable dual-space Gaussian pseudopotentials
,” Phys. Rev. B
54
, 1703
–1710
(1996
).48.
J.
VandeVondele
and J.
Hutter
, “Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
,” J. Chem. Phys.
127
, 114105
(2007
).49.
G. J.
Martyna
and M. E.
Tuckerman
, “A reciprocal space based method for treating long range interactions in ab initio and force-field based calculations in clusters
,” J. Chem. Phys.
110
, 2810
–2821
(1999
).50.
F.
Aquilante
, J.
Autschbach
, R. K.
Carlson
, L. F.
Chibotaru
, M. G.
Delcey
, L.
De Vico
, I. F.
Galván
, N.
Ferré
, L. M.
Frutos
, L.
Gagliardi
, M.
Garavelli
, A.
Giussani
, C. E.
Hoyer
, G.
Li Manni
, H.
Lischka
, D.
Ma
, P.-Å.
Malmqvist
, T.
Müller
, A.
Nenov
, M.
Olivucci
, T. B.
Pedersen
, D.
Peng
, F.
Plasser
, B.
Pritchard
, M.
Reiher
, I.
Rivalta
, I.
Schapiro
, J.
Segarra-Martí
, M.
Stenrup
, D. G.
Truhlar
, L.
Ungur
, A.
Valentini
, S.
Vancoillie
, V.
Veryazov
, V. P.
Vysotskiy
, O.
Weingart
, F.
Zapata
, and R.
Lindh
, “Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table
,” J. Comput. Chem.
37
, 506
–541
(2016
).51.
The OpenMolcas developer team, Openmolcas.
52.
E.
Runge
and E. K.
Gross
, “Density-functional theory for time-dependent systems
,” Phys. Rev. Lett.
52
, 997
(1984
).53.
K.
Burke
, J.
Werschnik
, and E.
Gross
, “Time-dependent density functional theory: Past, present, and future
,” J. Chem. Phys.
123
, 062206
(2005
).54.
E. L.
Shirley
, “Ab initio inclusion of electron-hole attraction: Application to x-ray absorption and resonant inelastic x-ray scattering
,” Phys. Rev. Lett.
80
, 794
(1998
).55.
J. C.
Slater
, Statistical Exchange-Correlation in the Self-Consistent Field
(Academic Press
, 1972
), pp. 1
–92
.56.
J. C.
Slater
and K. H.
Johnson
, “Self-consistent-field xα cluster method for polyatomic molecules and solids
,” Phys. Rev. B
5
, 844
–853
(1972
).57.
J.
Janak
, “Proof that ∂E/∂ni = ε in density-functional theory
,” Phys. Rev. B
18
, 7165
(1978
).58.
L. X.
Chen
, “Probing transient molecular structures in photochemical processes using laser-initiated time-resolved x-ray absorption spectroscopy
,” Annu. Rev. Phys. Chem.
56
, 221
–254
(2005
).59.
M.
Ekimova
, M.
Kubin
, M.
Ochmann
, J.
Ludwig
, N.
Huse
, P.
Wernet
, M.
Odelius
, and E. T. J.
Nibbering
, “Soft-x-ray spectroscopy of the amine group: Hydrogen bond motifs in alkylamine/alkylammonium acid-base pairs
,” J. Phys. Chem. B
122
, 7737
–7746
(2018
).60.
M.
Prémont-Schwarz
, S.
Schreck
, M.
Iannuzzi
, E. T. J.
Nibbering
, M.
Odelius
, and P.
Wernet
, “Correlating infrared and x-ray absorption energies for molecular-level insight into hydrogen bond making and breaking in solution
,” J. Phys. Chem. B
119
, 8115
–8124
(2015
).© 2019 Author(s).
2019
Author(s)
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