Fluorescence-detected multidimensional electronic spectroscopy (fMES) promises high sensitivity compared to conventional approaches and is an emerging spectroscopic approach toward combining the advantages of MES with the spatial resolution of a microscope. Here, we present a visible white light continuum-based fMES spectrometer and systematically explore the sensitivity enhancement expected from fluorescence detection. As a demonstration of sensitivity, we report room temperature two-dimensional coherence maps of vibrational quantum coherences in a laser dye at optical densities of ∼2–3 orders of magnitude lower than conventional approaches. This high sensitivity is enabled by a combination of biased sampling along the optical coherence time axes and a rapid scan of the pump–probe waiting time T at each sample. A combination of this approach with acousto-optic phase modulation and phase-sensitive lock-in detection enables measurements of room temperature vibrational wavepackets even at the lowest ODs. Alternative faster data collection schemes, which are enabled by the flexibility of choosing a non-uniform undersampled grid in the continuous T scanning approach, are also demonstrated.
REFERENCES
1.
D. M.
Jonas
, “Optical analogs of 2D NMR
,” Science
300
(6 June
), 1515
–1517
(2003
).2.
W. P.
Aue
, E.
Bartholdi
, and R. R.
Ernst
, “Two-dimensional spectroscopy. Application to nuclear magnetic resonance
,” J. Chem. Phys.
64
(5
), 2229
–2246
(1976
).3.
D.
Finkelstein-Shapiro
, P.-A.
Mante
, S.
Sarisozen
, L.
Wittenbecher
, I.
Minda
, S.
Balci
, T.
Pullerits
, and D.
Zigmantas
, “Understanding radiative transitions and relaxation pathways in plexcitons
,” Chem
7
(4
), 1092
–1107
(2021
).4.
J.
Cao
, R. J.
Cogdell
, D. F.
Coker
, H. G.
Duan
, J.
Hauer
, U.
Kleinekathöfer
, T. L. C.
Jansen
, T.
Mančal
, R. J. D.
Miller
, J. P.
Ogilvie
, V. I.
Prokhorenko
, T.
Renger
, H. S.
Tan
, R.
Tempelaar
, M.
Thorwart
, E.
Thyrhaug
, S.
Westenhoff
, and D.
Zigmantas
, “Quantum biology revisited
,” Sci. Adv.
6
(14
), eaaz4888
(2020
).5.
P. D.
Dahlberg
, A. F.
Fidler
, J. R.
Caram
, P. D.
Long
, and G. S.
Engel
, “Energy transfer observed in live cells using two-dimensional electronic spectroscopy
,” J. Phys. Chem. Lett.
4
(21
), 3636
–3640
(2013
).6.
J.
Dostál
, J.
Pšenčík
, and D.
Zigmantas
, “In situ mapping of the energy flow through the entire photosynthetic apparatus
,” Nat. Chem.
8
, 705
(2016
).7.
F. D.
Fuller
and J. P.
Ogilvie
, “Experimental implementations of two-dimensional Fourier transform electronic spectroscopy
,” Annu. Rev. Phys. Chem.
66
(1
), 667
–690
(2015
).8.
V.
Tiwari
, “Multidimensional electronic spectroscopy in high-definition - combining spectral, temporal and spatial resolutions
,” J. Chem. Phys.
154
, 230901
(2021
).9.
S.
Roeding
and B.
Tobias
, “Coherent two-dimensional electronic mass spectrometry
,” Nat. Commun.
9
(1
), 2519
(2018
).10.
L.
Bruder
, U.
Bangert
, M.
Binz
, D.
Uhl
, R.
Vexiau
, N.
Bouloufa-Maafa
, O.
Dulieu
, and F.
Stienkemeier
, “Coherent multidimensional spectroscopy of dilute gas-phase nanosystems
,” Nat. Commun.
9
(1
), 4823
(2018
).11.
J. A.
Cina
, “Wave-packet interferometry and molecular state reconstruction: Spectroscopic adventures on the left-hand side of the Schrödinger equation
,” Annu. Rev. Phys. Chem.
59
(1
), 319
–342
(2008
).12.
S.
Mueller
, J.
Lüttig
, P.
Malý
, L.
Ji
, J.
Han
, M.
Moos
, T. B.
Marder
, U. H. F.
Bunz
, A.
Dreuw
, C.
Lambert
, and T.
Brixner
, “Rapid multiple-quantum three-dimensional fluorescence spectroscopy disentangles quantum pathways
,” Nat. Commun.
10
(1
), 4735
(2019
).13.
P. F.
Tekavec
, G. A.
Lott
, and A. H.
Marcus
, “Fluorescence-detected two-dimensional electronic coherence spectroscopy by acousto-optic phase modulation
,” J. Chem. Phys.
127
(21
), 214307
–214327
(2007
).14.
S.
Goetz
, D.
Li
, V.
Kolb
, J.
Pflaum
, and T.
Brixner
, “Coherent two-dimensional fluorescence micro-spectroscopy
,” Opt. Express
26
(4
), 3915
–3925
(2018
).15.
V.
Tiwari
, Y. A.
Matutes
, A. T.
Gardiner
, T. L. C.
Jansen
, R. J.
Cogdell
, and J. P.
Ogilvie
, “Spatially-resolved fluorescence-detected two-dimensional electronic spectroscopy probes varying excitonic structure in photosynthetic bacteria
,” Nat. Commun.
9
(1
), 4219
(2018
).16.
A. K.
De
, D.
Monahan
, J. M.
Dawlaty
, and G. R.
Fleming
, “Two-dimensional fluorescence-detected coherent spectroscopy with absolute phasing by confocal imaging of a dynamic grating and 27-step phase-cycling
,” J. Chem. Phys.
140
(19
), 194201
(2014
).17.
J. N.
Mastron
and A.
Tokmakoff
, “Fourier transform fluorescence-encoded infrared spectroscopy
,” J. Phys. Chem. A
122
(2
), 554
–562
(2018
).18.
D.
Agathangelou
, A.
Javed
, F.
Sessa
, X.
Solinas
, M.
Joffre
, and J. P.
Ogilvie
, “Phase-modulated rapid-scanning fluorescence-detected two-dimensional electronic spectroscopy
,” J. Chem. Phys.
155
(9
), 094201
(2021
).19.
J. A.
Moon
, “Optimization of signal-to-noise ratios in pump-probe spectroscopy
,” Rev. Sci. Instrum.
64
(7
), 1775
–1778
(1993
).20.
G.
Auböck
, C.
Consani
, R.
Monni
, A.
Cannizzo
, F.
van Mourik
, and M.
Chergui
, “Femtosecond pump/supercontinuum-probe setup with 20 kHz repetition rate
,” Rev. Sci. Instrum.
83
(9
), 093105
(2012
).21.
B.
Lang
, “Photometrics of ultrafast and fast broadband electronic transient absorption spectroscopy: State of the art
,” Rev. Sci. Instrum.
89
(9
), 093112
(2018
).22.
M.
Bradler
and E.
Riedle
, “Temporal and spectral correlations in bulk continua and improved use in transient spectroscopy
,” J. Opt. Soc. Am. B
31
(7
), 1465
–1475
(2014
).23.
J. N.
Sanders
, S. K.
Saikin
, S.
Mostame
, X.
Andrade
, J. R.
Widom
, A. H.
Marcus
, and A.
Aspuru-Guzik
, “Compressed sensing for multidimensional spectroscopy experiments
,” J. Phys. Chem. Lett.
3
(18
), 2697
–2702
(2012
).24.
J.
Lavoie
, T.
Landes
, A.
Tamimi
, B. J.
Smith
, A. H.
Marcus
, and M. G.
Raymer
, “Phase-modulated interferometry, spectroscopy, and refractometry using entangled photon pairs
,” Adv. Quantum Technol.
3
(11
), 1900114
(2020
).25.
J.
Kasprzak
, B.
Patton
, V.
Savona
, and W.
Langbein
, “Coherent coupling between distant excitons revealed by two-dimensional nonlinear hyperspectral imaging
,” Nat. Photonics
5
(1
), 57
–63
(2011
).26.
T. M.
Autry
, G.
Moody
, J.
Fraser
, C.
McDonald
, R. P.
Mirin
, and K.
Silverman
, “Single-scan acquisition of multiple multidimensional spectra
,” Optica
6
(6
), 735
–744
(2019
).27.
E. W.
Martin
, J.
Horng
, H. G.
Ruth
, E.
Paik
, M.-H.
Wentzel
, H.
Deng
, and S. T.
Cundiff
, “Encapsulation narrows and preserves the excitonic homogeneous linewidth of exfoliated monolayer MoSe2
,” Phys. Rev. Appl.
14
(2
), 21002
(2020
).28.
G.
Nardin
, T. M.
Autry
, K. L.
Silverman
, and S. T.
Cundiff
, “Multidimensional coherent photocurrent spectroscopy of a semiconductor nanostructure
,” Opt. Express
21
(23
), 28617
–28627
(2013
).29.
K. J.
Karki
, J. R.
Widom
, J.
Seibt
, I.
Moody
, M. C.
Lonergan
, T.
Pullerits
, and A. H.
Marcus
, “Coherent two-dimensional photocurrent spectroscopy in a PbS quantum dot photocell
,” Nat. Commun.
5
, 5869
(2014
).30.
N. F.
Scherer
, R. J.
Carlson
, A.
Matro
, M.
Du
, A. J.
Ruggiero
, V.
Romero‐Rochin
, J. A.
Cina
, G. R.
Fleming
, and S. A.
Rice
, “Fluorescence-detected wave packet interferometry: Time resolved molecular spectroscopy with sequences of femtosecond phase-locked pulses
,” J. Chem. Phys.
95
(3
), 1487
–1511
(1991
).31.
D. M.
Jonas
, “Two-dimensional femtosecond spectroscopy
,” Annu. Rev. Phys. Chem.
54
, 425
–463
(2003
).32.
E. J.
Heller
, “The semiclassical way to molecular spectroscopy
,” Acc. Chem. Res.
14
(12
), 368
–375
(1981
).33.
J.
Ryu
, S. D.
Park
, D.
Baranov
, I.
Rreza
, J. S.
Owen
, and D. M.
Jonas
, “Relations between absorption, emission, and excited state chemical potentials from nanocrystal 2D spectra
,” Sci. Adv.
7
(22
), eabf4741
(2021
).34.
I.
Amat-Roldán
, I.
Cormack
, P.
Loza-Alvarez
, E.
Gualda
, and D.
Artigas
, “Ultrashort pulse characterisation with SHG collinear-FROG
,” Opt. Express
12
(6
), 1169
–1178
(2004
).35.
G.
Stibenz
and G. n.
Steinmeyer
, “Interferometric frequency-resolved optical gating
,” Opt. Express
13
(7
), 2617
–2626
(2005
).36.
Y.
Coello
, V. V.
Lozovoy
, T. C.
Gunaratne
, B.
Xu
, I.
Borukhovich
, C.-h.
Tseng
, T.
Weinacht
, and M.
Dantus
, “Interference without an interferometer: A different approach to measuring, compressing, and shaping ultrashort laser pulses
,” J. Opt. Soc. Am. B
25
(6
), A140
–A150
(2008
).37.
J. K.
Ranka
, A. L.
Gaeta
, A.
Baltuska
, M. S.
Pshenichnikov
, and D. A.
Wiersma
, “Autocorrelation measurement of 6-fs pulses based on the two-photon-induced photocurrent in a GaAsP photodiode
,” Opt. Lett.
22
(17
), 1344
–1346
(1997
).38.
S.
Lochbrunner
, P.
Huppmann
, and E.
Riedle
, “Crosscorrelation measurements of ultrashort visible pulses: Comparison between nonlinear crystals and SiC photodiodes
,” Opt. Commun.
184
(1
), 321
–328
(2000
).39.
E. A.
Donley
, T. P.
Heavner
, F.
Levi
, M. O.
Tataw
, and S. R.
Jefferts
, “Double-pass acousto-optic modulator system
,” Rev. Sci. Instrum.
76
(6
), 63112
(2005
).40.
D.
Brinks
, R.
Hildner
, F. D.
Stefani
, and N. F.
van Hulst
, “Beating spatio-temporal coupling: Implications for pulse shaping and coherent control experiments
,” Opt. Express
19
(27
), 26486
–26499
(2011
).41.
S.
Pres
, L.
Kontschak
, M.
Hensen
, and T.
Brixner
, “Coherent 2D electronic spectroscopy with complete characterization of excitation pulses during all scanning steps
,” Opt. Express
29
(3
), 4191
–4209
(2021
).42.
P. D.
Dahlberg
, P.-C.
Ting
, S. C.
Massey
, M. A.
Allodi
, E. C.
Martin
, C. N.
Hunter
, and G. S.
Engel
, “Mapping the ultrafast flow of harvested solar energy in living photosynthetic cells
,” Nat. Commun.
8
, 988
–994
(2017
).43.
S.
Irgen-Gioro
, A. P.
Spencer
, W. O.
Hutson
, and E.
Harel
, “Coherences of bacteriochlorophyll a uncovered using 3D-electronic spectroscopy
,” J. Phys. Chem. Lett.
9
(20
), 6077
–6081
(2018
).44.
E.
Bartholdi
and R. R.
Ernst
, “Fourier spectroscopy and the causality principle
,” J. Magn. Reson.
11
(1
), 9
–19
(1973
).45.
D. M.
Jonas
, “Vibrational and nonadiabatic coherence in 2D electronic spectroscopy, the Jahn–Teller effect, and energy transfer
,” Annu. Rev. Phys. Chem.
69
(1
), 327
–352
(2018
).46.
B.
Cho
, V.
Tiwari
, R. J.
Hill
, W. K.
Peters
, T. L.
Courtney
, A. P.
Spencer
, and D. M.
Jonas
, “Absolute measurement of femtosecond pump–probe signal strength
,” J. Phys. Chem. A
117
(29
), 6332
–6345
(2013
).47.
B.
Cho
, V.
Tiwari
, and D. M.
Jonas
, “Simultaneous all-optical determination of molecular concentration and extinction coefficient
,” Anal. Chem.
85
(11
), 5514
–5521
(2013
).48.
J. D.
Hybl
, A.
Albrecht Ferro
, and D. M.
Jonas
, “Two-dimensional Fourier transform electronic spectroscopy
,” J. Chem. Phys.
115
(14
), 6606
–6622
(2001
).49.
R. J.
McIntyre
, “Multiplication noise in uniform avalanche diodes
,” IEEE Trans. Electron Devices
ED-13
(1
), 164
–168
(1966
).50.
R.
Gvishi
and R.
Reisfeld
, “An investigation of the equilibrium between various forms of oxazine-170 by means of absorption and fluorescence spectroscopy
,” Chem. Phys. Lett.
156
(2
), 181
–186
(1989
).51.
V. V.
Kostjukov
, “Photoexcitation of oxazine 170 dye in aqueous solution: TD-DFT study
,” J. Mol. Model.
27
(11
), 311
(2021
).52.
M.
Vogel
, W.
Rettig
, U.
Fiedeldei
, and H.
Baumgärtel
, “Non-radiative deactivation via biradicaloid charge-transfer states in oxazine and thiazine dyes
,” Chem. Phys. Lett.
148
(4
), 347
–352
(1988
).53.
M. S.
Zakerhamidi
and S. G.
Sorkhabi
, “Solvent effects on the molecular resonance structures and photo-physical properties of a group of oxazine dyes
,” J. Lumin.
157
, 220
–228
(2015
).54.
A. L.
Dobryakov
, S. A.
Kovalenko
, A.
Weigel
, J. L.
Pérez-Lustres
, J.
Lange
, A.
Müller
, and N. P.
Ernsting
, “Femtosecond pump/supercontinuum-probe spectroscopy: Optimized setup and signal analysis for single-shot spectral referencing
,” Rev. Sci. Instrum.
81
(11
), 113106
(2010
).55.
D. A.
Farrow
, E. R.
Smith
, W.
Qian
, and D. M.
Jonas
, “The polarization anisotropy of vibrational quantum beats in resonant pump-probe experiments: Diagrammatic calculations for square symmetric molecules
,” J. Chem. Phys.
129
(17
), 174509
(2008
).56.
V.
Butkus
, J.
Alster
, E.
Bašinskaitė
, R.
Augulis
, P.
Neuhaus
, L.
Valkunas
, H. L.
Anderson
, D.
Abramavicius
, and D.
Zigmantas
, “Discrimination of diverse coherences allows identification of electronic transitions of a molecular nanoring
,” J. Phys. Chem. Lett.
8
(10
), 2344
–2349
(2017
).57.
M.
Bradler
, P.
Baum
, and E.
Riedle
, “Femtosecond continuum generation in bulk laser host materials with sub-μJ pump pulses
,” Appl. Phys. B
97
(3
), 561
(2009
).58.
J.
Moses
, S.-W.
Huang
, K.-H.
Hong
, O. D.
Mücke
, E. L.
Falcão-Filho
, A.
Benedick
, F. Ö.
Ilday
, A.
Dergachev
, J. A.
Bolger
, B. J.
Eggleton
, and F. X.
Kärtner
, “Highly stable ultrabroadband mid-IR optical parametric chirped-pulse amplifier optimized for superfluorescence suppression
,” Opt. Lett.
34
(11
), 1639
–1641
(2009
).59.
W. P.
Carbery
, B.
Pinto-Pacheco
, D.
Buccella
, and D. B.
Turner
, “Resolving the fluorescence quenching mechanism of an oxazine dye using ultrabroadband two-dimensional electronic spectroscopy
,” J. Phys. Chem. A
123
(24
), 5072
–5080
(2019
).60.
R.
Zhu
, J.
Zou
, Z.
Wang
, H.
Chen
, and Y.
Weng
, “Electronic state-resolved multimode-coupled vibrational wavepackets in oxazine 720 by two-dimensional electronic spectroscopy
,” J. Phys. Chem. A
124
(45
), 9333
–9342
(2020
).61.
J.
Brazard
, L. A.
Bizimana
, T.
Gellen
, W. P.
Carbery
, and D. B.
Turner
, “Experimental detection of branching at a conical intersection in a highly fluorescent molecule
,” J. Phys. Chem. Lett.
7
(1
), 14
–19
(2016
).62.
M. S.
Barclay
, J. S.
Huff
, R. D.
Pensack
, P. H.
Davis
, W. B.
Knowlton
, B.
Yurke
, J. C.
Dean
, P. C.
Arpin
, and D. B.
Turner
, “Characterizing mode anharmonicity and Huang–Rhys factors using models of femtosecond coherence spectra
,” J. Phys. Chem. Lett.
13
(24
), 5413
–5423
(2022
).63.
D. V.
Le
, J. M.
de la Perrelle
, T. N.
Do
, X.
Leng
, P. C.
Tapping
, G. D.
Scholes
, T. W.
Kee
, and H.-S.
Tan
, “Characterization of the ultrafast spectral diffusion and vibronic coherence of TIPS-pentacene using 2D electronic spectroscopy
,” J. Chem. Phys.
155
(1
), 014302
(2021
).64.
V.
Tiwari
, Y. A.
Matutes
, A.
Konar
, Z.
Yu
, M.
Ptaszek
, D. F.
Bocian
, D.
Holten
, C.
Kirmaier
, and J. P.
Ogilvie
, “Strongly coupled bacteriochlorin dyad studied using phase-modulated fluorescence-detected two-dimensional electronic spectroscopy
,” Opt. Express
26
(17
), 22327
–22341
(2018
).65.
P.
Malý
and T.
Brixner
, “Fluorescence-detected pump–probe spectroscopy
,” Angew. Chem., Int. Ed.
60
(34
), 18867
–18875
(2021
).66.
E.
van den Berg
and M. P.
Friedlander
, “Probing the Pareto Frontier for basis pursuit solutions
,” SIAM J. Sci. Comput.
31
(2
), 890
–912
(2009
).67.
Z.
Wang
, S.
Lei
, K. J.
Karki
, A.
Jakobsson
, and T.
Pullerits
, “Compressed sensing for reconstructing coherent multidimensional spectra
,” J. Phys. Chem. A
124
(9
), 1861
–1866
(2020
).68.
S. S.
Senlik
, V. R.
Policht
, and J. P.
Ogilvie
, “Two-color nonlinear spectroscopy for the rapid acquisition of coherent dynamics
,” J. Phys. Chem. Lett.
6
(13
), 2413
–2420
(2015
).69.
D.
Li
, C.
Trovatello
, S.
Dal Conte
, M.
Nuß
, G.
Soavi
, G.
Wang
, A. C.
Ferrari
, G.
Cerullo
, and T.
Brixner
, “Exciton-phonon coupling strength in single-layer MoSe2 at room temperature
,” Nat. Commun.
12
(1
), 954
(2021
).© 2023 Author(s). Published under an exclusive license by AIP Publishing.
2023
Author(s)
You do not currently have access to this content.
