To simulate a 200 nm photoexcitation in cyclobutanone to the n-3s Rydberg state, classical trajectories were excited from a Wigner distribution to the singlet state manifold based on excitation energies and oscillator strengths. Twelve singlet and 12 triplet states are treated using TD-B3LYP-D3/6-31+G** for the electronic structure, and the nuclei are propagated with the Tully surface hopping method. Using time-dependent density functional theory, we are able to predict the bond cleavage that takes place on the S1 surface as well as the ultrafast deactivation from the Rydberg n-3s state to the nπ*. After showing that triplet states and higher-lying singlet states do not play any crucial role during the early dynamics (i.e., the first 300 fs), the SA(6)-CASSCF(8,11)/aug-cc-pVDZ method is used as an electronic structure and the outcome of the non-adiabatic dynamic simulations is recomputed. Gas-phase ultrafast electron diffraction spectra are computed for both electronic structure methods, showing significantly different results.
REFERENCES
1.
W.
Domcke
and D. R.
Yarkony
, “Role of conical intersections in molecular spectroscopy and photoinduced chemical dynamics
,” Annu. Rev. Phys. Chem.
63
, 325
–352
(2012
).2.
R. C.
Evans
, P.
Douglas
, and H. D.
Burrow
, Applied Photochemistry
(Springer
, 2013
), Vol. 36
.3.
S.
Mai
and L.
Gonzalez
, “Molecular photochemistry: Recent developments in theory
,” Angew. Chem., Int. Ed.
59
, 16832
–16846
(2020
).4.
T. R.
Nelson
, A. J.
White
, J. A.
Bjorgaard
, A. E.
Sifain
, Y.
Zhang
, B.
Nebgen
, S.
Fernandez-Alberti
, D.
Mozyrsky
, A. E.
Roitberg
, and S.
Tretiak
, “Non-adiabatic excited-state molecular dynamics: Theory and applications for modeling photophysics in extended molecular materials
,” Chem. Rev.
120
, 2215
–2287
(2020
).5.
D. R.
Morton
, E.
Lee-Ruff
, R. M.
Southam
, and N. J.
Turro
, “Molecular photochemistry. XXVII. Photochemical ring expansion of cyclobutanone, substituted cyclobutanones, and related cyclic ketones
,” J. Am. Chem. Soc.
92
, 4349
–4357
(1970
).6.
G.
Umbricht
, M. D.
Hellman
, and L. S.
Hegedus
, “Photochemical ring expansion of α-alkoxycyclobutanones to 2-acetoxy-5-alkoxytetrahydrofurans: Nucleophilic reactions at the 2-position
,” J. Org. Chem.
63
, 5173
–5178
(1998
).7.
B. T.
Hue
, J.
Dijkink
, S.
Kuiper
, K. K.
Larson
, F. S.
Guziec Jr
, K.
Goubitz
, J.
Fraanje
, H.
Schenk
, J. H.
van Maarseveen
, and H.
Hiemstra
, “Synthesis of the cyclobutanone core of solanoeclepin a via intramolecular allene butenolide photocycloaddition
,” Org. Biomol. Chem.
1
, 4364
–4366
(2003
).8.
M. D.
Kärkäs
, J. A. J.
Porco
, and C. R. J.
Stephenson
, “Photochemical approaches to complex chemotypes: Applications in natural product synthesis
,” Chem. Rev.
116
, 9683
–9747
(2016
).9.
M.
Zanini
, A.
Cataffo
, and A. M.
Echavarren
, “Synthesis of cyclobutanones by gold(I)-catalyzed [2 + 2] cycloaddition of ynol ethers with alkenes
,” Org. Lett.
23
, 8989
–8993
(2021
).10.
T. I.
Solling
, “Nonstatistical photoinduced processes in gaseous organic molecules
,” ACS Omega
6
, 29325
–29344
(2021
).11.
N. J.
Turro
, J. C.
Dalton
, K.
Dawes
, G.
Farrington
, R.
Hautala
, D.
Morton
, M.
Niemczyk
, and N.
Schore
, “Molecular photochemistry. L. Molecular photochemistry of alkanones in solution: α-cleavage, hydrogen abstraction, cycloaddition, and sensitization reactions
,” Acc. Chem. Res.
5
, 92
–101
(1972
).12.
E. K.
Lee
, “Laser photochemistry of selected vibronic and rotational states
,” Acc. Chem. Res.
10
, 319
–326
(1977
).13.
S.
Benson
and G.
Kistiakowsky
, “The photochemical decomposition of cyclic ketones
,” J. Am. Chem. Soc.
64
, 80
–86
(1942
).14.
R. F.
Whitlock
and A. B. F.
Duncan
, “Electronic spectrum of cyclobutanone
,” J. Chem. Phys.
55
, 218
(1971
).15.
E. K.
Lee
, R. G.
Shortridge
, Jr., and C. F.
Rusbult
, “Fluorescence excitation study of cyclobutanone, cyclopentanone, and cyclohexanone in the gas phase
,” J. Am. Chem. Soc.
93
, 1863
–1867
(1971
).16.
J. C.
Hemminger
and E. K. C.
Lee
, “Fluorescence excitation and photodecomposition of the first excited singlet cyclobutanone (1A2): A study of predissociation of and collisional energy transfer from the vibronically selected species
,” J. Chem. Phys.
56
, 5284
(1972
).17.
C.
Drury-Lessard
and D.
Moule
, “Ring puckering in the 1B2 (n,3s) Rydberg electronic state of cyclobutanone
,” J. Chem. Phys.
68
, 5392
–5395
(1978
).18.
M.
Baba
and I.
Hanazaki
, “The S1(n,π*) states of cyclopentanone and cyclobutanone in a supersonic nozzle beam
,” J. Chem. Phys.
81
, 5426
–5433
(1984
).19.
L.
O’Toole
, P.
Brint
, C.
Kosmidis
, G.
Boulakis
, and P.
Tsekeris
, “Vacuum-ultraviolet absorption spectra of propanone, butanone and the cyclic ketones CnH2n−2O (n= 4, 5, 6, 7)
,” J. Chem. Soc., Faraday Trans.
87
, 3343
–3351
(1991
).20.
E. W.-G.
Diau
, C.
Kötting
, and A. H.
Zewail
, “Femtochemistry of Norrish type-I reactions: II. The anomalous predissociation dynamics of cyclobutanone on the S1 surface
,” ChemPhysChem
2
, 294
–309
(2001
).21.
T. S.
Kuhlman
, S.
Sauer
, T. I.
Sølling
, and K. B.
Møller
, “Symmetry, vibrational energy redistribution and vibronic coupling: The internal conversion processes of cycloketones
,” J. Chem. Phys.
137
, 22A522
(2012
).22.
S.-H.
Xia
, X.-Y.
Liu
, Q.
Fang
, and G.
Cui
, “Excited-state ring-opening mechanism of cyclic ketones: A MS-CASPT2//CASSCF study
,” J. Phys. Chem. A
119
, 3569
–3576
(2015
).23.
L.
Liu
and W.-H.
Fang
, “New insights into photodissociation dynamics of cyclobutanone from the AIMS dynamic simulation
,” J. Chem. Phys.
144
, 144317
(2016
).24.
M.
Larsen
, A.
Stephansen
, and T.
Sølling
, “Coherent motion of excited state cyclic ketones: The have and the have-nots
,” Chem. Phys. Lett.
683
, 495
–499
(2017
).25.
M.-H.
Kao
, R. K.
Venkatraman
, M. N. R.
Ashfold
, and A. J.
Orr-Ewing
, “Effects of ring-strain on the ultrafast photochemistry of cyclic ketones
,” Chem. Sci.
11
, 1991
–2000
(2020
).26.
T. S.
Kuhlman
, T. I.
Sølling
, and K. B.
Møller
, ““Coherent motion reveals non-ergodic nature of internal conversion between excited states
,” ChemPhysChem
13
, 820
–827
(2012
).27.
M.
Centurion
, T. J.
Wolf
, and J.
Yang
, “Ultrafast imaging of molecules with electron diffraction
,” Annu. Rev. Phys. Chem.
73
, 21
–42
(2022
).28.
R. E.
Blankenship
, D. M.
Tiede
, J.
Barber
, G. W.
Brudvig
, G.
Fleming
, M.
Ghirardi
, M.
Gunner
, W.
Junge
, D. M.
Kramer
, A.
Melis
et al, “Comparing photosynthetic and photovoltaic efficiencies and recognizing the potential for improvement
,” Science
332
, 805
–809
(2011
).29.
M.
Staniforth
, W.-D.
Quan
, T. N.
Karsili
, L. A.
Baker
, R. K.
O’Reilly
, and V. G.
Stavros
, “First step toward a universal fluorescent probe: Unravelling the photodynamics of an amino–maleimide fluorophore
,” J. Phys. Chem. A
121
, 6357
–6365
(2017
).30.
G.
Simone
, M. J.
Dyson
, S. C.
Meskers
, R. A.
Janssen
, and G. H.
Gelinck
, “Organic photodetectors and their application in large area and flexible image sensors: The role of dark current
,” Adv. Funct. Mater.
30
, 1904205
(2020
).31.
H.
Köppel
, W.
Domcke
, and L. S.
Cederbaum
, “Multimode molecular dynamics beyond the Born-Oppenheimer approximation
,” Adv. Chem. Phys.
57
, 59
–246
(1984
).32.
G. A.
Worth
and L. S.
Cederbaum
, “Beyond Born-Oppenheimer: Molecular dynamics through a conical intersection
,” Annu. Rev. Phys. Chem.
55
, 127
–158
(2004
).33.
J. P.
Zobel
, M.
Heindl
, F.
Plasser
, S.
Mai
, and L.
González
, “Surface hopping dynamics on vibronic coupling models
,” Acc. Chem. Res.
54
, 3760
–3771
(2021
).34.
T. J.
Penfold
and J.
Eng
, “Mind the GAP: Quantifying the breakdown of the linear vibronic coupling Hamiltonian
,” Phys. Chem. Chem. Phys.
25
, 7195
–7204
(2023
).35.
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
).36.
P. C.
Hariharan
and J. A.
Pople
, “The influence of polarization functions on molecular orbital hydrogenation energies
,” Theor. Chim. Acta
28
, 213
–222
(1973
).37.
W. J.
Hehre
, R.
Ditchfield
, and J. A.
Pople
, “Self-consistent molecular orbital methods. XII. Further extensions of Gaussian-type basis sets for use in molecular orbital studies of organic molecules
,” J. Chem. Phys.
56
, 2257
–2261
(1972
).38.
Y.
Tawada
, T.
Tsuneda
, S.
Yanagisawa
, T.
Yanai
, and K.
Hirao
, “A long-range-corrected time-dependent density functional theory
,” J. Chem. Phys.
120
, 8425
–8433
(2004
).39.
N. T.
Maitra
, “Perspective: Fundamental aspects of time-dependent density functional theory
,” J. Chem. Phys.
144
, 220901
(2016
).40.
D. J.
Tozer
and N. C.
Handy
, “On the determination of excitation energies using density functional theory
,” Phys. Chem. Chem. Phys.
2
, 2117
–2121
(2000
).41.
S.
Hirata
and M.
Head-Gordon
, “Time-dependent density functional theory within the Tamm–Dancoff approximation
,” Chem. Phys. Lett.
314
, 291
–299
(1999
).42.
I.
Seidu
, M.
Krykunov
, and T.
Ziegler
, “Applications of time-dependent and time-independent density functional theory to Rydberg transitions
,” J. Phys. Chem. A
119
, 5107
–5116
(2015
).43.
F.
Neese
, “The ORCA program system
,” Wiley Interdiscip. Rev.: Comput. Mol. Sci.
2
, 73
–78
(2012
).44.
F.
Neese
, “Software update: The ORCA program system-Version 5.0
,” Wiley Interdiscip. Rev.: Comput. Mol. Sci.
12
, e1606
(2022
).45.
B. G.
Levine
, C.
Ko
, J.
Quenneville
, and T. J.
MartÍnez
, “Conical intersections and double excitations in time-dependent density functional theory
,” Mol. Phys.
104
, 1039
–1051
(2006
).46.
J. T.
Taylor
, D. J.
Tozer
, and B. F. E.
Curchod
, “On the description of conical intersections between excited electronic states with LR-TDDFT and ADC(2)
,” J. Chem. Phys.
159
, 214115
(2023
).47.
E.
Tapavicza
, I.
Tavernelli
, U.
Rothlisberger
, C.
Filippi
, and M. E.
Casida
, “Mixed time-dependent density-functional theory/classical trajectory surface hopping study of oxirane photochemistry
,” J. Chem. Phys.
129
, 124108
(2008
).48.
F.
Aquilante
, J.
Autschbach
, A.
Baiardi
, S.
Battaglia
, V. A.
Borin
, L. F.
Chibotaru
, I.
Conti
, L.
De Vico
, M.
Delcey
, I.
Fdez Galván
et al, “Modern quantum chemistry with [Open]Molcas
,” J. Chem. Phys.
152
, 214117
(2020
).49.
G.
Li Manni
, I. F.
Galván
, A.
Alavi
, F.
Aleotti
, F.
Aquilante
, J.
Autschbach
, D.
Avagliano
, A.
Baiardi
, J. J.
Bao
, S.
Battaglia
et al, “The OpenMolcas web: A community-driven approach to advancing computational chemistry
,” J. Chem. Theory Comput.
19
, 6857
–7434
(2023
).50.
B. O.
Roos
, P. R.
Taylor
, and P. E.
Sigbahn
, “A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
,” Chem. Phys.
48
, 157
–173
(1980
).51.
J.
Finley
, P.-Å.
Malmqvist
, B. O.
Roos
, and L.
Serrano-Andrés
, “The multi-state CASPT2 method
,” Chem. Phys. Lett.
288
, 299
–306
(1998
).52.
T. H.
Dunning
, “Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
,” J. Chem. Phys.
90
, 1007
–1023
(1989
).53.
R. A.
Kendall
, T. H.
Dunning
, and R. J.
Harrison
, “Electron affinities of the first-row atoms revisited. systematic basis sets and wave functions
,” J. Chem. Phys.
96
, 6796
–6806
(1992
).54.
N.
Forsberg
and P.-Å.
Malmqvist
, “Multiconfiguration perturbation theory with imaginary level shift
,” Chem. Phys. Lett.
274
, 196
–204
(1997
).55.
J. C.
Tully
and R. K.
Preston
, “Trajectory surface hopping approach to nonadiabatic molecular collisions: The reaction of H+ with D2
,” J. Chem. Phys.
55
, 562
–572
(1971
).56.
J. C.
Tully
, “Molecular dynamics with electronic transitions
,” J. Chem. Phys.
93
, 1061
(1990
).57.
L.
Verlet
, “Computer “experiments” on classical fluids. I. Thermodynamical properties of Lennard-Jones molecules
,” Phys. Rev.
159
, 98
(1967
).58.
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
).59.
G.
Granucci
and M.
Persico
, “Critical appraisal of the fewest switches algorithm for surface hopping
,” J. Chem. Phys.
126
, 134114
(2007
).60.
G.
Granucci
, M.
Persico
, and A.
Zoccante
, “Including quantum decoherence in surface hopping
,” J. Chem. Phys.
133
, 134111
(2010
).61.
G.
Granucci
, M.
Persico
, and A.
Toniolo
, “Direct semiclassical simulation of photochemical processes with semiempirical wave functions
,” J. Chem. Phys.
114
, 10608
–10615
(2001
).62.
F.
Plasser
, M.
Ruckenbauer
, S.
Mai
, M.
Oppel
, P.
Marquetand
, and L.
González
, “Efficient and flexible computation of many-electron wave function overlaps
,” J. Chem. Theory Comput.
12
, 1207
–1219
(2016
).63.
E.
van Lenthe
, E.-J.
Baerends
, and J. G.
Snijders
, “Relativistic regular two-component Hamiltonians
,” J. Chem. Phys.
99
, 4597
–4610
(1993
).64.
E.
van Lenthe
, E.-J.
Baerends
, and J. G.
Snijders
, “Relativistic total energy using regular approximations
,” J. Chem. Phys.
101
, 9783
–9792
(1994
).65.
E.
van Lenthe
, J.
Snijders
, and E.
Baerends
, “The zero-order regular approximation for relativistic effects: The effect of spin–orbit coupling in closed shell molecules
,” J. Chem. Phys.
105
, 6505
–6516
(1996
).66.
F.
Salvat
, A.
Jablonski
, and C. J.
Powell
, “ELSEPA—Dirac partial-wave calculation of elastic scattering of electrons and positrons by atoms, positive ions and molecules
,” Comput. Phys. Commun.
165
, 157
–190
(2005
).67.
J. P.
Figueira Nunes
, L. M.
Ibele
, S.
Pathak
, A. R.
Attar
, S.
Bhattacharyya
, R.
Boll
, K.
Borne
, M.
Centurion
, B.
Erk
, M.-F.
Lin
et al, “Monitoring the evolution of relative product populations at early times during a photochemical0 reaction
,” J. Am. Chem. Soc.
6
, 1 (2024).68.
J.
Hemminger
, H. A.
Carless
, and E. K.
Lee
, “Laser-excited fluorescence emission from cis and trans isomers of 2,3- and 2,4-dimethylcyclobutanone. Ultra-short-lived excited molecules
,” J. Am. Chem. Soc.
95
, 682
–685
(1973
).69.
R.
Crespo-Otero
and M.
Barbatti
, “Spectrum simulation and decomposition with nuclear ensemble: Formal derivation and application to benzene, furan and 2-phenylfuran
,” Theor. Chem. Acc.
131
, 1237
(2012
).© 2024 Author(s). Published under an exclusive license by AIP Publishing.
2024
Author(s)
You do not currently have access to this content.
