We have observed details of the internal motion and dissociation channels in photoexcited carbon disulfide (CS2) using time-resolved x-ray scattering (TRXS). Photoexcitation of gas-phase CS2 with a 200 nm laser pulse launches oscillatory bending and stretching motion, leading to dissociation of atomic sulfur in under a picosecond. During the first 300 fs following excitation, we observe significant changes in the vibrational frequency as well as some dissociation of the C–S bond, leading to atomic sulfur in the both 1D and 3P states. Beyond 1400 fs, the dissociation is consistent with primarily 3P atomic sulfur dissociation. This channel-resolved measurement of the dissociation time is based on our analysis of the time-windowed dissociation radial velocity distribution, which is measured using the temporal Fourier transform of the TRXS data aided by a Hough transform that extracts the slopes of linear features in an image. The relative strength of the two dissociation channels reflects both their branching ratio and differences in the spread of their dissociation times. Measuring the time-resolved dissociation radial velocity distribution aids the resolution of discrepancies between models for dissociation proposed by prior photoelectron spectroscopy work.
REFERENCES
1.
M. S.
Schuurman
and A.
Stolow
, “Dynamics at conical intersections
,” Annu. Rev. Phys. Chem.
69
, 427
–450
(2018
).2.
W.
Siebrand
and M. Z.
Zgierski
, “Matrix elements for intersystem crossing
,” Chem. Phys. Lett.
35
, 151
–155
(1975
).3.
S.
Mai
, P.
Marquetand
, and L.
González
, “A general method to describe intersystem crossing dynamics in trajectory surface hopping
,” Int. J. Quantum Chem.
115
, 1215
–1231
(2015
).4.
S.
Mai
, P.
Marquetand
, and L.
González
, “Nonadiabatic dynamics: The SHARC approach
,” WIREs Comput. Mol. Sci.
8
, e1370
(2018
).5.
M. E.
Corrales
, V.
Loriot
, G.
Balerdi
, J.
González-Vázquez
, R.
de Nalda
, L.
Bañares
, and A. H.
Zewail
, “Structural dynamics effects on the ultrafast chemical bond cleavage of a photodissociation reaction
,” Phys. Chem. Chem. Phys.
16
, 8812
–8818
(2014
).6.
K. F.
Chang
, H.
Wang
, S. M.
Poullain
, D.
Prendergast
, D. M.
Neumark
, and S. R.
Leone
, “Mapping wave packet bifurcation at a conical intersection in CH3I by attosecond XUV transient absorption spectroscopy
,” J. Chem. Phys.
154
, 234301
(2021
).7.
K. F.
Chang
, M.
Reduzzi
, H.
Wang
, S. M.
Poullain
, Y.
Kobayashi
, L.
Barreau
, D.
Prendergast
, D. M.
Neumark
, and S. R.
Leone
, “Revealing electronic state-switching at conical intersections in alkyl iodides by ultrafast XUV transient absorption spectroscopy
,” Nat. Commun.
11
, 4042
(2020
) bandiera_abtest: a Cc_license_type: cc_by Cg_type: Nature Research Journals Number: 1 Primary_atype: Research Publisher: Nature Publishing Group Subject_term: Chemistry;Physics Subject_term_id: chemistry;physics.8.
S.
Matsika
, “Radiationless decay of excited states of uracil through conical intersections
,” J. Phys. Chem. A
108
, 7584
–7590
(2004
).9.
S.
Perun
, A. L.
Sobolewski
, and W.
Domcke
, “Conical intersections in thymine
,” J. Phys. Chem. A
110
, 13238
–13244
(2006
).10.
C.
Starrs
, M. N.
Jego
, A.
Mank
, and J. W.
Hepburn
, “Mode specific photodissociation of the 1B2 state of carbon disulfide
,” J. Phys. Chem. A
96
, 6526
–6529
(1992
).11.
A. D.
Smith
, E. M.
Warne
, D.
Bellshaw
, D. A.
Horke
, M.
Tudorovskya
, E.
Springate
, A. J. H.
Jones
, C.
Cacho
, R. T.
Chapman
, A.
Kirrander
, and R. S.
Minns
, “Mapping the complete reaction path of a complex photochemical reaction
,” Phys. Rev. Lett.
120
, 183003
(2018
).12.
C. Z.
Bisgaard
, O. J.
Clarkin
, G.
Wu
, A. M. D.
Lee
, O.
Geßner
, C. C.
Hayden
, and A.
Stolow
, “Time-resolved molecular frame dynamics of fixed-in-space CS2 molecules
,” Science
323
, 1464
–1468
(2009
).13.
P.
Hockett
, C. Z.
Bisgaard
, O. J.
Clarkin
, and A.
Stolow
, “Time-resolved imaging of purely valence-electron dynamics during a chemical reaction
,” Nat. Phys.
7
, 612
–615
(2011
).14.
D.
Townsend
, H.
Satzger
, T.
Ejdrup
, A. M. D.
Lee
, H.
Stapelfeldt
, and A.
Stolow
, “1B2(1Σu+) excited state decay dynamics in CS2
,” J. Chem. Phys.
125
, 234302
(2006
).15.
P.
Farmanara
, O.
Steinkellner
, M. T.
Wick
, M.
Wittmann
, G.
Korn
, V.
Stert
, and W.
Radloff
, “Ultrafast internal conversion and photodissociation of molecules excited by femtosecond 155 nm laser pulses
,” J. Chem. Phys.
111
, 6264
–6270
(1999
).16.
P.
Farmanara
, V.
Stert
, and W.
Radloff
, “Ultrafast predissociation and coherent phenomena in CS2 excited by femtosecond laser pulses at 194–207 nm
,” J. Chem. Phys.
111
, 5338
–5343
(1999
).17.
D.
Bellshaw
, D. A.
Horke
, A. D.
Smith
, H. M.
Watts
, E.
Jager
, E.
Springate
, O.
Alexander
, C.
Cacho
, R. T.
Chapman
, A.
Kirrander
, and R. S.
Minns
, “Ab-initio surface hopping and multiphoton ionisation study of the photodissociation dynamics of CS2
,” Chem. Phys. Lett.
683
, 383
–388
(2017
) Commemoration Issue of Chemical Physics Letters Ahmed Zewail (1946-2016).18.
S.
Karashima
, Y.-I.
Suzuki
, and T.
Suzuki
, “Ultrafast extreme ultraviolet photoelectron spectroscopy of nonadiabatic photodissociation of CS2 from 1B2 (1Σu+) state: Product formation via an intermediate electronic state
,” J. Phys. Chem. Lett.
12
, 3755
–3761
(2021
).19.
E. M.
Warne
, A. D.
Smith
, D. A.
Horke
, E.
Springate
, A. J. H.
Jones
, C.
Cacho
, R. T.
Chapman
, and R. S.
Minns
, “Time resolved detection of the S(1D) product of the UV induced dissociation of CS2
,” J. Chem. Phys.
154
, 034302
(2021
).20.
R.
Spesyvtsev
, T.
Horio
, Y.-I.
Suzuki
, and T.
Suzuki
, “Observation of the wavepacket dynamics on the 1B2(1Σu+) state of CS2 by sub-20 fs photoelectron imaging using 159 nm probe pulses
,” J. Chem. Phys.
142
, 074308
(2015
).21.
T.
Horio
, R.
Spesyvtsev
, Y.
Furumido
, and T.
Suzuki
, “Real-time detection of S(1D2) photofragments produced from the 1B2(1Σu+) state of CS2 by vacuum ultraviolet photoelectron imaging using 133 nm probe pulses
,” J. Chem. Phys.
147
, 013932
(2017
).22.
E.
Campbell
, “Atomic polarisation in molecular photodissociation
,” Ph.D. thesis, University of Oxford
, 2016
.23.
M.
Brouard
, E. K.
Campbell
, R.
Cireasa
, A. J.
Johnsen
, and W.-H.
Yuen
, “The ultraviolet photodissociation of CS2: The S(1D2) channel
,” J. Chem. Phys.
136
, 044310
(2012
).24.
M.
Stefanou
, K.
Saita
, D. V.
Shalashilin
, and A.
Kirrander
, “Comparison of ultrafast electron and X-ray diffraction—A computational study
,” Chem. Phys. Lett.
683
, 300
–305
(2017
) Ahmed Zewail Commemoration Issue of Chemical Physics Letters.25.
W. O.
Razmus
, K.
Acheson
, P.
Bucksbaum
, M.
Centurion
, E.
Champenois
, I.
Gabalski
, M. C.
Hoffman
, A.
Howard
, M.-F.
Lin
, Y.
Liu
, P.
Nunes
, S.
Saha
, X.
Shen
, M.
Ware
, E. M.
Warne
, T.
Weinacht
, K.
Wilkin
, J.
Yang
, T. J. A.
Wolf
, A.
Kirrander
, R. S.
Minns
, and R.
Forbes
, “Multichannel photodissociation dynamics in CS2 studied by ultrafast electron diffraction
,” Phys. Chem. Chem. Phys.
24
, 15416
(2022
).26.
M. R.
Ware
, J. M.
Glownia
, N.
Al-Sayyad
, J. T.
O’Neal
, and P. H.
Bucksbaum
, “Characterizing dissociative motion in time-resolved x-ray scattering from gas-phase diatomic molecules
,” Phys. Rev. A
100
, 033413
(2019
).27.
M. R.
Ware
, “From time-resolved to frequency-resolved X-ray scattering
,” Ph.D. thesis, Stanford University
, 2019
.28.
B.
Stankus
, H.
Yong
, N.
Zotev
, J. M.
Ruddock
, D.
Bellshaw
, T. J.
Lane
, M.
Liang
, S.
Boutet
, S.
Carbajo
, J. S.
Robinson
, W.
Du
, N.
Goff
, Y.
Chang
, J. E.
Koglin
, M. P.
Minitti
, A.
Kirrander
, and P. M.
Weber
, “Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation
,” Nat. Chem.
11
, 716
–721
(2019
) bandiera_abtest: a Cg_type: Nature Research Journals Number: 8 Primary_atype: Research Publisher: Nature Publishing Group Subject_term: Chemical physics;Excited states;Reaction kinetics and dynamics Subject_term_id: chemical-physics;excited-states;kinetics-and-dynamics.29.
B.
Stankus
, H.
Yong
, J.
Ruddock
, L.
Ma
, A. M.
Carrascosa
, N.
Goff
, S.
Boutet
, X.
Xu
, N.
Zotev
, A.
Kirrander
, M. P.
Minitti
, and P. M.
Weber
, “Advances in ultrafast gas-phase x-ray scattering
,” J. Phys. B: At., Mol. Opt. Phys.
53
, 234004
(2020
).30.
M. P.
Minitti
, J. M.
Budarz
, A.
Kirrander
, J. S.
Robinson
, D.
Ratner
, T. J.
Lane
, D.
Zhu
, J. M.
Glownia
, M.
Kozina
, H. T.
Lemke
, M.
Sikorski
, Y.
Feng
, S.
Nelson
, K.
Saita
, B.
Stankus
, T.
Northey
, J. B.
Hastings
, and P. M.
Weber
, “Imaging molecular motion: Femtosecond X-ray scattering of an electrocyclic chemical reaction
,” Phys. Rev. Lett.
114
, 255501
(2015
).31.
J. M.
Budarz
, M. P.
Minitti
, D. V.
Cofer-Shabica
, B.
Stankus
, A.
Kirrander
, J. B.
Hastings
, and P. M.
Weber
, “Observation of femtosecond molecular dynamics via pump–probe gas phase x-ray scattering
,” J. Phys. B: At., Mol. Opt. Phys.
49
, 034001
(2016
).32.
I.
Gabalski
, M. R.
Ware
, and P. H.
Bucksbaum
, “X-ray scattering signatures of early-time accelerations in iodine dissociation
,” J. Phys. B: At., Mol. Opt. Phys.
53
, 244002
(2020
).33.
H.
Yong
, A.
Moreno Carrascosa
, L.
Ma
, B.
Stankus
, M. P.
Minitti
, A.
Kirrander
, and P. M.
Weber
, “Determination of excited state molecular structures from time-resolved gas-phase X-ray scattering
,” Faraday Discuss.
228
, 104
–122
(2021
).34.
H.
Yong
, X.
Xu
, J. M.
Ruddock
, B.
Stankus
, A. M.
Carrascosa
, N.
Zotev
, D.
Bellshaw
, W.
Du
, N.
Goff
, Y.
Chang
, S.
Boutet
, S.
Carbajo
, J. E.
Koglin
, M.
Liang
, J. S.
Robinson
, A.
Kirrander
, M. P.
Minitti
, and P. M.
Weber
, “Ultrafast X-ray scattering offers a structural view of excited-state charge transfer
,” Proc. Natl. Acad. Sci. U. S. A.
118
, e2021714118
(2021
).35.
G.
Dixit
, O.
Vendrell
, and R.
Santra
, “Imaging electronic quantum motion with light
,” Proc. Natl. Acad. Sci. U. S. A.
109
, 11636
–11640
(2012
).36.
G.
Dixit
, J. M.
Slowik
, and R.
Santra
, “Theory of time-resolved nonresonant x-ray scattering for imaging ultrafast coherent electron motion
,” Phys. Rev. A
89
, 043409
(2014
).37.
G.
Dixit
and R.
Santra
, “Time-resolved ultrafast x-ray scattering from an incoherent electronic mixture
,” Phys. Rev. A
96
, 053413
(2017
).38.
T.
Bredtmann
, M.
Ivanov
, and G.
Dixit
, “X-ray imaging of chemically active valence electrons during a pericyclic reaction
,” Nat. Commun.
5
, 5589
(2014
).39.
H.
Yong
, N.
Zotev
, J. M.
Ruddock
, B.
Stankus
, M.
Simmermacher
, A. M.
Carrascosa
, W.
Du
, N.
Goff
, Y.
Chang
, D.
Bellshaw
, M.
Liang
, S.
Carbajo
, J. E.
Koglin
, J. S.
Robinson
, S.
Boutet
, M. P.
Minitti
, A.
Kirrander
, and P. M.
Weber
, “Observation of the molecular response to light upon photoexcitation
,” Nat. Commun.
11
, 2157
(2020
) bandiera_abtest: a Cc_license_type: cc_by Cg_type: Nature Research Journals Number: 1 Primary_atype: Research Publisher: Nature Publishing Group Subject_term: Chemical physics;Excited states;Imaging techniques;Quantum chemistry Subject_term_id: chemical-physics;excited-states;imaging-techniques;quantum-chemistry.40.
M. R.
Ware
, J. M.
Glownia
, A.
Natan
, J. P.
Cryan
, and P. H.
Bucksbaum
, “On the limits of observing motion in time-resolved X-ray scattering
,” Philos. Trans. R. Soc., A
377
, 20170477
(2019
).41.
P. H.
Bucksbaum
, M. R.
Ware
, A.
Natan
, J. P.
Cryan
, and J. M.
Glownia
, “Characterizing multiphoton excitation using time-resolved X-ray scattering
,” Phys. Rev. X
10
, 011065
(2020
).42.
S.
Boutet
and G.
J Williams
, “The coherent X-ray imaging (CXI) instrument at the Linac coherent light source (LCLS)
,” New J. Phys.
12
, 035024
(2010
).43.
M.
Harmand
, R.
Coffee
, M. R.
Bionta
, M.
Chollet
, D.
French
, D.
Zhu
, D. M.
Fritz
, H. T.
Lemke
, N.
Medvedev
, B.
Ziaja
, S.
Toleikis
, and M.
Cammarata
, “Achieving few-femtosecond time-sorting at hard X-ray free-electron lasers
,” Nat. Photonics
7
, 215
–218
(2013
).44.
R. R.
Sadeghi
, S. R.
Gwaltney
, J. L.
Krause
, R. T.
Skodje
, and P. M.
Weber
, “Structure and dynamics of the S3 state of CS2
,” J. Chem. Phys.
107
, 6570
–6576
(1997
).45.
D.
Bellshaw
, R. S.
Minns
, and A.
Kirrander
, “Correspondence between electronic structure calculations and simulations: Nonadiabatic dynamics in CS2
,” Phys. Chem. Chem. Phys.
21
, 14226
–14237
(2019
).46.
M.
Richter
, P.
Marquetand
, J.
González-Vázquez
, I.
Sola
, and L.
González
, “SHARC: Ab initio molecular dynamics with surface hopping in the adiabatic representation including arbitrary couplings
,” J. Chem. Theory Comput.
7
, 1253
–1258
(2011
).47.
H.-J.
Werner
, P. J.
Knowles
, G.
Knizia
, F. R.
Manby
, and M.
Schütz
, “Molpro: A general-purpose quantum chemistry program package
,” WIREs Comput. Mol. Sci.
2
, 242
–253
(2012
).48.
S.
Mai
, M.
Richter
, M.
Heindl
, M. F. S. J.
Menger
, A.
Atkins
, M.
Ruckenbauer
, F.
Plasser
, L. M.
Ibele
, S.
Kropf
, M.
Oppel
, P.
Marquetand
, and L.
González
, “SHARC2.1: Surface hopping including arbitrary couplings—Program package for non-adiabatic dynamics
,” 2019
, published: sharc-md.org.49.
M. D.
Hack
, A. M.
Wensmann
, D. G.
Truhlar
, M.
Ben-Nun
, and T. J.
Martínez
, “Comparison of full multiple spawning, trajectory surface hopping, and converged quantum mechanics for electronically nonadiabatic dynamics
,” J. Chem. Phys.
115
, 1172
–1186
(2001
).50.
A.
Kirrander
, K.
Saita
, and D. V.
Shalashilin
, “Ultrafast X-ray scattering from molecules
,” J. Chem. Theory Comput.
12
, 957
–967
(2016
).51.
A.
Moreno Carrascosa
, H.
Yong
, D. L.
Crittenden
, P. M.
Weber
, and A.
Kirrander
, “Ab initio calculation of total X-ray scattering from molecules
,” J. Chem. Theory Comput.
15
, 2836
–2846
(2019
).52.
B.
Efron
and R.
Tibshirani
, “The bootstrap method for assessing statistical accuracy
,” Behaviormetrika
12
, 1
–35
(1985
).53.
R. O.
Duda
and P. E.
Hart
, “Use of the Hough transformation to detect lines and curves in pictures
,” Commun. ACM
15
, 11
–15
(1972
).54.
P. E.
Hart
, “How the Hough transform was invented [DSP History]
,” IEEE Signal Process. Mag.
26
, 18
–22
(2009
) conference Name: IEEE Signal Processing Magazine.© 2022 Author(s). Published under an exclusive license by AIP Publishing.
2022
Author(s)
You do not currently have access to this content.
