Time-resolved photoionization measurements were performed on o-nitrophenol pumped with UV laser pulses at a central wavelength of 255 nm (4.9 eV) and probed with vacuum ultraviolet (VUV) pulses at 153 nm (8.1 eV). The photoelectron spectrum and time of flight mass spectrum for ions were recorded at each pump–probe delay. The measurements are interpreted with the aid of electronic structure calculations for both the neutral and ionic states. Evidence is found for the formation of a bicyclic intermediate followed by NO dissociation through a process of internal conversion and intersystem crossing. The combination of photoelectron and photoion spectroscopy, together with computational results, provides strong evidence of intersystem crossing that is difficult to establish with only a single technique.
REFERENCES
1.
Y.-C.
Cheng
and G. R.
Fleming
, “Dynamics of light harvesting in photosynthesis
,” Annu. Rev. Phys. Chem.
60
, 241
–262
(2009
).2.
C.
Canuel
, M.
Mons
, F.
Piuzzi
, B.
Tardivel
, I.
Dimicoli
, and M.
Elhanine
, “Excited states dynamics of DNA and RNA bases: Characterization of a stepwise deactivation pathway in the gas phase
,” J. Chem. Phys.
122
, 074316
(2005
).3.
T.
Gustavsson
, R.
Improta
, and D.
Markovitsi
, “DNA/RNA: Building blocks of life under UV irradiation
,” J. Phys. Chem. Lett.
1
, 2025
–2030
(2010
).4.
J.-M. L.
Pecourt
, J.
Peon
, and B.
Kohler
, “Ultrafast internal conversion of electronically excited RNA and DNA nucleosides in water
,” J. Am. Chem. Soc.
122
, 9348
–9349
(2000
).5.
I.
McConnell
, G.
Li
, and G. W.
Brudvig
, “Energy conversion in natural and artificial photosynthesis
,” Chem. Biol.
17
, 434
–447
(2010
).6.
C.
Jin
, E. Y.
Ma
, O.
Karni
, E. C.
Regan
, F.
Wang
, and T. F.
Heinz
, “Ultrafast dynamics in van der Waals heterostructures
,” Nat. Nanotechnol.
13
, 994
–1003
(2018
).7.
A.
Stolow
, A. E.
Bragg
, and D. M.
Neumark
, “Femtosecond time-resolved photoelectron spectroscopy
,” Chem. Rev.
104
, 1719
–1758
(2004
).8.
S. P.
Weathersby
, G.
Brown
, M.
Centurion
, T. F.
Chase
, R.
Coffee
, J.
Corbett
, J. P.
Eichner
, J. C.
Frisch
, A. R.
Fry
, M.
Gühr
et al, “Mega-electron-volt ultrafast electron diffraction at SLAC national accelerator laboratory
,” Rev. Sci. Instrum.
86
, 073702
(2015
).9.
J.
Yang
, X.
Zhu
, J. P. F.
Nunes
, J. K.
Yu
, R. M.
Parrish
, T. J. A.
Wolf
, M.
Centurion
, M.
Gühr
, R.
Li
, Y.
Liu
et al, “Simultaneous observation of nuclear and electronic dynamics by ultrafast electron diffraction
,” Science
368
, 885
–889
(2020
).10.
Y.
Liu
, S. L.
Horton
, J.
Yang
, J. P. F.
Nunes
, X.
Shen
, T. J.
Wolf
, R.
Forbes
, C.
Cheng
, B.
Moore
, M.
Centurion
et al, “Spectroscopic and structural probing of excited-state molecular dynamics with time-resolved photoelectron spectroscopy and ultrafast electron diffraction
,” Phys. Rev. X
10
, 021016
(2020
).11.
B.
Stankus
, H.
Yong
, N.
Zotev
, J. M.
Ruddock
, D.
Bellshaw
, T. J.
Lane
, M.
Liang
, S.
Boutet
, S.
Carbajo
, J. S.
Robinson
et al, “Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation
,” Nat. Chem.
11
, 716
–721
(2019
).12.
Y.
Liu
, T.
Rozgonyi
, P.
Marquetand
, and T.
Weinacht
, “Excited-state dynamics of CH2I2 and CH2IBR studied with UV-pump VUV-probe momentum-resolved photoion spectroscopy
,” J. Chem. Phys.
153
, 184304
(2020
).13.
I.
Bejan
, Y.
Abd El Aal
, I.
Barnes
, T.
Benter
, B.
Bohn
, P.
Wiesen
, and J.
Kleffmann
, “The photolysis of ortho-nitrophenols: A new gas phase source of HONO
,” Phys. Chem. Chem. Phys.
8
, 2028
–2035
(2006
).14.
Y.-Q.
Wang
, H.-G.
Wang
, S.-Q.
Zhang
, K.-M.
Pei
, X.
Zheng
, and D.
Lee Phillips
, “Resonance Raman intensity analysis of the excited state proton transfer dynamics of 2-nitrophenol in the charge-transfer band absorption
,” J. Chem. Phys.
125
, 214506
(2006
).15.
H. A.
Ernst
, T. J. A.
Wolf
, O.
Schalk
, N.
González-García
, A. E.
Boguslavskiy
, A.
Stolow
, M.
Olzmann
, and A.-N.
Unterreiner
, “Ultrafast dynamics of o-nitrophenol: An experimental and theoretical study
,” J. Phys. Chem. A
119
, 9225
–9235
(2015
).16.
Y.
Nitta
, O.
Schalk
, H.
Igarashi
, S.
Wada
, T.
Tsutsumi
, K.
Saita
, T.
Taketsugu
, and T.
Sekikawa
, “Real-time probing of an atmospheric photochemical reaction by ultrashort extreme ultraviolet pulses: Nitrous acid release from o-nitrophenol
,” J. Phys. Chem. Lett.
12
, 674
–679
(2021
).17.
C.
Xu
, L.
Yu
, C.
Zhu
, and J.
Yu
, “Photoisomerization reaction mechanisms of o-nitrophenol revealed by analyzing intersystem crossing network at the MRCI level
,” J. Phys. Chem. A
119
, 10441
–10450
(2015
).18.
C.
Xu
, L.
Yu
, C.
Zhu
, J.
Yu
, and Z.
Cao
, “Intersystem crossing-branched excited-state intramolecular proton transfer for o-nitrophenol: An ab initio on-the-fly nonadiabatic molecular dynamic simulation
,” Sci. Rep.
6
, 26768
(2016
).19.
C.
Xu
, F. L.
Gu
, and C.
Zhu
, “Ultrafast intersystem crossing for nitrophenols: Ab initio nonadiabatic molecular dynamics simulation
,” Phys. Chem. Chem. Phys.
20
, 5606
–5616
(2018
).20.
L.
Vereecken
, H. K.
Chakravarty
, B.
Bohn
, and J.
Lelieveld
, “Theoretical study on the formation of H- and O-atoms, HONO, OH, NO, and NO2 from the lowest lying singlet and triplet states in ortho-nitrophenol photolysis
,” Int. J. Chem. Kinet.
48
, 785
–795
(2016
).21.
A.
Ciavardini
, M.
Coreno
, C.
Callegari
, C.
Spezzani
, G.
De Ninno
, B.
Ressel
, C.
Grazioli
, M.
de Simone
, A.
Kivimäki
, P.
Miotti
et al, “Ultra-fast-VUV photoemission study of UV excited 2-nitrophenol
,” J. Phys. Chem. A
123
, 1295
–1302
(2019
).22.
M.
Beutler
, M.
Ghotbi
, F.
Noack
, and I. V.
Hertel
, “Generation of sub-50-fs vacuum ultraviolet pulses by four-wave mixing in argon
,” Opt. Lett.
35
, 1491
–1493
(2010
).23.
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
).24.
T. K.
Allison
III, “Femtosecond molecular dynamics studied with vacuum ultraviolet pulse pairs
,” Ph.D. thesis, University of California
, Berkeley
, 2010
.25.
Y.
Liu
, “Combining spectroscopic and structural probes of molecular dynamics
,” Ph.D. thesis, Stony Brook University
, 2021
.26.
NIST Mass Spectrometry Data Center
, “Mass spectra
,” in NIST Chemistry WebBook, NIST Standard Reference Database Number 69
, edited by P.
Linstrom
and W.
Mallard
(National Institute of Standards and Technology
, 2014
).27.
S. L.
Horton
, “Photoionizaion as a probe of ultrafast molecular dynamics
,” Ph.D. thesis, Stony Brook University
, 2018
.28.
M.
Assmann
, T.
Weinacht
, and S.
Matsika
, “Surface hopping investigation of the relaxation dynamics in radical cations
,” J. Chem. Phys.
144
, 034301
(2016
).© 2023 Author(s). Published under an exclusive license by AIP Publishing.
2023
Author(s)
You do not currently have access to this content.
