Cavity Catalysis by Cooperative Vibrational Strong Coupling of Reactant and Solvent Molecules

Article abstract of DOI:10.1002/anie.201905407

Here, we report the catalytic effect of vibrational strong coupling (VSC) on the solvolysis of para-nitrophenyl acetate (PNPA), which increases the reaction rate by an order of magnitude. This is observed when the microfluidic Fabry–Perot cavity in which the VSC is generated is tuned to the C=O vibrational stretching mode of both the reactant and solvent molecules. Thermodynamic experiments confirm the catalytic nature of VSC in the system. The change in the reaction rate follows an exponential relation with respect to the coupling strength of the solvent, indicating a cooperative effect between the solvent molecules and the reactant. Furthermore, the study of the solvent kinetic isotope effect clearly shows that the vibrational overlap of the C=O vibrational bands of the reactant and the strongly coupled solvent molecules is critical for the catalysis in this reaction. The combination of cooperative effects and cavity catalysis confirms the potential of VSC as a new frontier in chemistry.

Full text of DOI:10.1002/anie.201905407

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Cavity Catalysis by Cooperative Vibrational Strong Coupling of
Reactant and Solvent Molecules
Authors: Jyoti Lather, Pooja Bhatt, Anoop Thomas, Thomas W.
Ebbesen, and Jino George
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201905407
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10.1002/anie.201905407
Angewandte Chemie International Edition
COMMUNICATION
Cavity Catalysis by Cooperative Vibrational Strong Coupling of
Reactant and Solvent Molecules
Jyoti Lather[1], Pooja Bhatt[1], Anoop Thomas[2], Thomas W. Ebbesen[2]*, Jino George[1]*
Abstract: Here we report the catalytic effect of vibrational
to the transition dipole moment d and the electric field (퐸) of
strong coupling (VSC) on the solvolysis of para-nitrophenyl
acetate (PNPA) whereby the reaction rate is increased by an
order of magnitude. This is observed when the microfluidic
Fabry-Perot cavity, in which the VSC is generated, is tuned
to the C=O vibrational stretching mode of both the reactant
and solvent molecules. Thermodynamic experiment confirms
the catalytic nature of VSC of the system. The change in the
reaction rate follows an exponential relation with respect to
the coupling strength of the solvent indicating a cooperative
effect between the solvent molecules and the reactant.
Furthermore, the study of the solvent kinetic isotope effect
clearly shows that the vibrational overlap of C=O vibrational
bands of reactant and the strongly coupled solvent molecules
is critical to observe the catalysis in this reaction. The
combination of cooperative effect and cavity catalysis
confirms the potential of VSC as a new frontier in chemistry.
the electromagnetic mode of the cavity:
ℏ휔
ℏ훺 ∝ 2푑 ⋅ 퐸 ×
푛
+ 1; 퐸 =
(1)
√
√
VR
ph
2휀
0
푉
where 휀0 s hhe acuuu per shhsash, 휔 s hhe asbrchsoncl
frequenu, 푉 s hhe oee aolu e of hhe ucash, cne 푛ph hhe
nu ber of phohon snaolaee sn hhe uouplsng proue . When
hhe lchher goe ho zero c re seucl Rcbs plshhsng energ,
re csn eaen sn hhe ecrk eue ho hhe uouplsng ho hhe zero-posnh
energ, of hhe ucash,. I porhcnhl, ℏ훺 s proporhsoncl ho
VR
⁄
푁 푉 ~ 퐶 where N s hhe nu ber cne C hhe uonuenhrchson
√
√
of hhe uouplee oleuule snhercuhsng hrongl, wshh hhe ucash,
oee. [1-3]
In hhs uo unsuchson we reporh hhe olaol, s of PNPA
uchcl, ee b, VSC uneer uooperchsae hrong uouplsng effeuh
behween hhe recuhcnh cne hhe olaenh oleuule . In ohher
wore when hhe olaenh cne hhe recuhcnh oleuule hcae hhe
c e asbrchsoncl bcne buh onl, hhe olaenh s ch uffsusenhl,
hsgh uonuenhrchson ho be hrongl, uouplee ho hhe ucash, oee
sh snurec e hhe recuhson rche ore hhcn one oreer of
cgnshuee ch roo he perchure.
Strong light-matter coupling offers a unique way of
controlling internal reaction coordinates by coupling
molecular transitions to the vacuum field (zero-point energy)
[1-7]
of a cavity mode.
VSC was introduced to couple
selectively a vibrational mode,[8,9] which is easily achieved in
the liquid state in a microfluidic Fabry-Perot (FP) cavity.[10]
Thomas et al., observed the modification of the rate of a C-Si
bond breaking process and more recently demonstrated
changes to the branching ratio of products by selective VSC
of silane derivatives.[3,6] Recently, Hiura et al reported the
possibility of accelerating reactions by vibrational ultra-
strong coupling of water molecules involved in hydrolysis
reactions.[7] In both cases, reactants were directly coupled to
cavity modes and the reaction rates could be controlled by
moving the physical distance between the mirrors of a FP
cavity, i.e. by tuning the coupling to a given vibrational
resonance. Recent theoretical studies confirm that potential
energy surfaces and reactivity can be modified by coupling to
the vacuum field, although the critical role of the solvent is
hard to simulate. [11-16]
(a)
Vibrational States
Hybrid
State
Cavity
Modes
v₄
v₃
v₂
v₁
1
0
ℏ훺
v₀
Reaction co-ordinateof C=O
(b)
VSC condition can be achieved by injecting a molecular
liquid into an FP cavity in which the vibrational transition
interacts with the cavity mode (Figure 1a) to generate two
new eigen states, called vibro-polaritonic states (P+ and P-).
The interaction energy (Rabi energy; ℏ훺VR) is proportional
Figure 1. a) Schematic representation of vibro-polaritonic states formed
from a molecular vibrational state and a F-P cavity mode. b) The
hydrolysis of PNPA in ethyl acetate (EtOAc).
The FP ucashse u ee sn hhe pre enh expers enh were
prepcree wshh Au srror puhheree on ho IR hrcn pcrenh BcF2
wsneow b, followsng c reporhee proueeure.[10] The Au
srror were proheuhee wshh 100 n of puhheree SsOx. The
pcusng behween hhe srror u ee for hhe uurrenh hue, s eh
ho 18  ho uouple hhe C=O hrehuhsng oee of PNPA
oleuule (Fsgure 2c). Suuh F-P ucashse ucn hole up ho 3 L
aolu e of recuhsng oluhson. The non-ucash, expers enh
were ucrrsee ouh sn c suroflusesu uell cee of hhe c e
wsneow wshhouh hhe Au srror . See Supporhsng Infor chson
(SI) for furhher eehcsl . The PNPA olaol, s [17-19] sn hhs hue,
[1]
J. Lather, P. Bhatt and Dr. J. George
Department of Chemical Sciences, Indian Institute of Science
Education and Research (IISER) Mohali, Punjab-140306, India.
*E-mail: jgeorge@iisermohali.ac.in
[2]
Dr. A. Thomas and Prof. T. W. Ebbesen
University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge,
67000 Strasbourg, France.
*E-mail: ebbesen@unistra.fr
Supporting information for this article is given via a link at the end
of the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201905407
Angewandte Chemie International Edition
COMMUNICATION
wc ucrrsee ouh uneer sle bc su uoneshson proaseee b, C=O asbrchsoncl bcne sn hhe IR hhe snfluenue of hrong
hehrcbuh,lc onsu fluorsee (TBAF) c uhe chsucll, uouplsng on hhe recuhson rche s besng onshoree sn hhe UV-
hown sn Fsgure 1b. TBAF sn Ehh,l cuehche (EhOAu) nor cll, Vs regson. Ths uoneshson help ho caose uo plsuchson uuh
follow bc e uchcl, ee cu,l (BAu2) bone brecksng euhcns c fslher effeuh cne ohher s ue
( ee SI cne Suhe e S1). EhOAu wc uho en c hhe olaenh
beucu e sh ucrbon,l hrehuhsng hrcn shson oaerlcp wshh hhch
0.030
Cell
1.0
0.8
0.6
0.4
0.2
0.0
(a)
(b)Cavity ON
0.025
0.020
0.015
0.010
0.005
10 min
0 min
Cell
Cavity OFF
375 400 425 450
0
10 20 30 40 50 60 70 80
Wavelength/ nm
Time/ s
1900
100
1850
1800
1750
1700
1650
1600
100
80
60
40
20
0
99
98
97
96
(c)
12EtOAc
13EtOAc
of hhe recuhcnh PNPA (Fsgure 2b; ree hrcue ). Bohh PNPA cne
TBAF oluhson were prepcree epcrchel, sxee ouh see cne
snjeuhee snho hhe FP ucash,.
10th mode
12EtOAc_cavity
0.025
0.020
0.015
0.010
0.005
0.000
12EtOAc_non-cavity
13EtOAc_cavity
(d)
Figure 2. a) Partsof a flow cell micro cavity-QED reactor. b) IR transmission
spectra of 10% EtOAc (red trace) in hexane and 100 times magnified 0.1 M
PNPA (dotted red trace). Vibro-polaritonic states P+ and P- formed by
coupling to the 10th cavity mode (black trace; pathlength is approx. 18 m)
with TMM simulation (dotted black trace).
13EtOAc_non-cavity
Shrong uouplsng of hhe C=O hrehuhsng oee of nech
12EhOAu ho hhe 10hh oee of hhe F-P ucash, gsae c Rcbs
-1
plshhsng of 155 u whsuh s equsaclenh ho 4.4 % uhcnge sn
hhe cuhucl hrcn shson energ, wshh P+ cne P- ch 1840 u -1 cne
-1
1685 u re peuhsael, (Fsgure 2b cne Fsgure S2). In hhe
1900
1850
1800
1750
1700
1650
1600
Wavenumber/ cm-1
recuhsae sxhure hhe PNPA repre enh onl, 0.1w% of hhe
sxhure cne s hhu uncble ho uneergo hrong uouplsng ho hhe
FP ucash, ch uuh low uonuenhrchson . [1] One of hhe que hson
we ceere here s whehher VSC of 12EhOAu ucn neaerhhele
snfluenue hhe recuhsash, of PNPA sn uuh uoneshson eaen
hhough sh s noh c recuhcnh.
Figure 3. a) Absorption spectra shows the evolution of PNP- species during
the ester hydrolysis. b) Pseudo first order kinetic traces measured at 407 nm
for cavity ON-resonance (blue circle; 1.6x10-2), cavity OFF-resonance (blue
hollow circle; 0.16x10-2) and non-cavity (red circle; 0.18x10-2) for 12EtOAc.
c) Carbonyl stretching modes of pure PNPA (ATR spectrum; black trace);
FTIR spectra of 12EtOAc (blue trace) and 13EtOAc (red trace) molecules (10
% in hexane). d) The corresponding kinetic traces measured by tuning the
cavity (12EtOAc blue circle; 13EtOAc red circle) and non-cavity (12EtOAc
blue empty circle; 13EtOAc red empty circle); 10th mode of the cavity overlap
with the carbonyl stretching mode of 12EtOAc and PNPA. The dashed curves
are guides to the eye.
The cjor proeuuh of hhe PNPA olaol, s s hhe pcrc-nshro
phenoxsee (PNP-) hcasng cn snhen e cb orphson peck ch 407
n . Ssnue hhe hrcn pcrenu, regson of BcF2 wsneow exhene
well sn ho hhe UV (uc. 200 n ) hhe progre of hhe recuhson
ucn be ec sl, onshoree b, followsng hhe he porcl rs e of
PNP- cb orphson peck c hown sn Fsgure 3c ( ee cl o Fsgure
S6). In ohher wore whsle hhe FP ucash, s eh ho uouple hhe
relchee ho hhe FP ucash, uonfsgurchson. B, hcasng c henfole
exue of PNPA c uo pcree ho TBAF (0.1 M a 0.01M) c
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10.1002/anie.201905407
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finding is that the entropy of activation (S‡) also decreases
significantly from -70.9 J/K/mol to -206.2 J/K/mol offsetting
partially the change in H‡. This large decrease in S‡
indicates that the TS is far more polar under VSC thereby
structuring the solvent cage which also decreases H‡. In
other words the solvent-solute interactions are much stronger
under VSC, thereby favouring BAc2 mechanism by stabilizing
the intermediates.
p eueo-fsr h oreer ksnehsu s ob eraee. Appcrenh rche
uon hcnh (kapp) were eeher snee b, lsnecr regre son ehhoe
(Fsgure 3b).[17] In hhe nor cl non-ucash, hhe cppcrenh rche
uon hcnh (kcppnu) s on hhe oreer of 0.2 x 10-2 (Fsgure 3b).
-1
To prepcre cn ON-re oncnue ucash, hhe e ph, ucash, s hunee
lowl, ho hhe ee sree pchhlenghh cne s keph unes hurbee for
30 snuhe (Supporting Information). Sub equenhl, hhe
recuhson sxhure s snjeuhee snho hhe ucash, cne hhe ksnehsu
hrcue cre reuoreee. Uneer ON-re oncnue uoneshson sn ohher
wore when hhe ucash, s hunee ho 12C=O hrehuhsng oee of
ehh,lcuehche (12EhOAu) hhe kappcav snurec ee b, ore hhcn one
oreer of cgnshuee (2.5 x 10-2 -1) uo pcree ho hhe non-ucash,
-3
Cavity
Non-cavity
(a)
cav
c hown sn Fsgure 3b. kapp leael off ho nor cl aclue
-4
-5
-6
-7
(kappnc) when hhe ucash, s eehunee fro hhe C=O oee of
12EhOAu (hhe OFF-re oncnue ec ure enh ) c hown sn
Fsgure 3e. Plec e nohe hhch hhe non-ucash, cne hhe ucash,
uoneshson cre excuhl, hhe c e exueph hhe pre enue of Au
srror sn ucash, cne kappnc s uncffeuhee b, cll acrschson sn
hhe pcuer hhsukne (blue e ph, usrule sn hhe Fsgure 3e).
cav
Inhere hsngl, hhe snurec e sn kapp follow hhe asbrchson
enaelope of C=O hrehuhsng oee of 12EhOAu oleuule hhch
s uouplee ho ucash, oee (Fsgure 3u cne e) followsng sh full
wsehh-hclf cxs u (FWHM; 25 u -1). Ths ugge h c
uooperchsae effeuh behween hhe hrongl, uouplee olaenh cne
hhe recuhcnh.
0.00320
0.00325
0.00330
1/T
0.00335
0.00340
0.00345
1
0.1
In order to confirm this cooperativity effect, we have
conducted kinetic isotope effect (KIE) experiments using the
12C=O (12EtOAc) and 13C=O (13EtOAc) isotopes with
carbonyl vibrational resonances at 1750 and 1706 cm-1,
respectively (Figure 3c). Outside the cavity, the use of
13EtOAc gives an apparent rate one order of magnitude lower
(13kapp = 2.4x10-4 s-1) with respect to the rate with the 12EtOAc
isotope. This large change in the reaction rate can be due to a
secondary isotope effect in which the 12EtOAc is coupled to
PNPA carbonyl vibrational state, facilitating external
vibrational energy transfer in the system.[20] Please note that
the rate determining step for the BAc2 mechanism is the attack
of nucleophile on the electron deficient carbonyl carbon
atom.[17-19] Very interestingly, under VSC of 13EtOAc, the
reaction rates are not modified. Kinetic action spectra
measured as a function of cavity tuning, Figure 3d, shows no
change in the rate for the 13EtOAc solvent system relative to
rate outside the cavity, in contrast to 12EtOAc. This is a
confirmation that the VSC of 12EtOAc is acting cooperatively
and perturbing the PNPA internal reaction coordinate so as to
affect its bond dissociation energy as will be discussed again
(b)
0.01
1E-3
1E-4
1E-5
0.00
0.01
0.02
0.03
0.04

Figure 4. (a) Eyring plot for reaction inside the cavity (blue circles) and
non-cavity (cell; red circles); (b) Apparent rate constant as a function of
Rabi splitting under VSC of 12EtOAc. Dotted lines are the corresponding
linear fitting.
We hhen lookee snho hhe recuhson rche acrschson wshh
re peuh ho uooperchsae uouplsng hrenghh of hhe 12EhOAu
oleuule . To eo hhs we fsxee hhe uonuenhrchson of PNPA (0.1
M) whsle acr,sng hhe 12EhOAu uonuenhrchson sn c sxee
cns ole - 12EhOAu oluhson. We uho e cns ole c c uo- olaenh;
hhe relchsae olaenh polcrsh, esfferenue s onl, 0.03 uo pcree
ho EhOAu cne hhe rche s e enhscll, hhe c e sn cns ole cne
12EhOAu sn hhe cb enue of VSC (Fsgure S3) (12EhOAu ho
recuhcnh rchso s ulo e ho 1000 we c u e hhch hhe asbrchsoncl
bchh s hsll pre eraee ch hhe lower uonuenhrchson of 12EhOAu).
An exponenhscl rs e sn hhe recuhson rche s ob eraee upon
snurec sng hhe uonuenhrchson of 12EhOAu uneer hrong
uouplsng uoneshson sn ohher wore wshh hhe Rcbs plshhsng
(Fsgure 4b). Suuh cn exponenhscl eepeneenue hc cl o been
ob eraee for bohh c lowsng ee slcnchson recuhson[3] cne for cn
further down in agreement with recent theoretical predictions.
[21]
To clarify how the VSC is affecting the reaction barrier
and whether it is truly catalysing the reaction, the temperature
dependence of the reaction rate was analysed to extract the
thermodynamics activation parameters. As it is immediately
apparent from the slopes in Figure 4a, the activation energy
drops under VSC. The enthalpy of activation (H‡) calculated
from Eyring equation decreases substantially from 53.2
kJ/mol to 7.9 kJ/mol (Figure 4a; Supporting Information),
indicating that the transition state (TS) is far more stable
under VSC of 12EtOAc molecules. Another very interesting
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cuuelerchsng h,erol, s recuhson.[7] Ths probcbl, posnh ho c [2] J. A. Hutchison, T. Schwartz, C. Genet, E. Devaux, T.
ore genercl fechure hhch hhe cuhsachson energ, acrse lsnecrl,
wshh hhe Rcbs plshhsng sn whsuheaer esreuhson hhe bcrrser s
oasng uneer VSC.
W. Ebbesen, Angew. Chem. Int. Ed. 2012, 51, 1592-
1596.
[3] A. Thomas, J. George, A. Shalabney, M. Dryzhakov, S.
J. Varma, J. Moran, T. Chervy, X. Zhong, E. Devaux,
C. Genet, Angew. Chem. Int. Ed. 2016, 55, 11462-
11466.
[4] B. Munkhbat, M. Wersäll, D. G. Baranov, T. J.
Antosiewicz, T. Shegai, Sci. Adv. 2018, 4, eaas9552.
[5] V. N. Peters, M. O. Faruk, J. Asane, R. Alexander, D.
A. Peters, S. Prayakarao, S. Rout, M. A. Noginov,
Optica, 2019, 6, 318–325.
[6] A. Thomas, L. Lethuillier-Karl, K. Nagarajan, R. M.
Vergauwe, J. George, T. Chervy, A. Shalabney, E.
Devaux, C. Genet, J. Moran, Science 2019, 363, 615-
619.
[7] H. Hiura, A. Shalabney, J. George, 2018, DOI
10.26434/chemrxiv.7234721.v3.
[8] A. Shalabney, J. George, J. Hutchison, G. Pupillo, C.
Genet, T. W. Ebbesen, Nat. Commun. 2015, 6, 5981.
[9] J. P. Long, B. S. Simpkins, ACS Photonics 2015, 2, 130-
136.
[10] J. George, A. Shalabney, J. A. Hutchison, C. Genet, T.
W. Ebbesen, J. Phys. Chem. Lett. 2015, 6, 1027-1031.
[11] J. Flick, M. Ruggenthaler, H. Appel, A. Rubio, Pro. Nat.
Acad. Sci. 2017, 114, 3026-3034.
[12] M. Ruggenthaler, N. Tancogne-Dejean, J. Flick, H.
Appel, A. Rubio, Nat. Rev. Chem. 2018, 2, 0118.
[13] M. Du, R. F. Ribeiro, J. Yuen-Zhou, Chem 2019, DOI
10.1016/j.chempr.2019.02.009.
In uonulu son hhe hher oe,nc su echc how
unequsaoucll, hhch hhe recuhson s uchcl,zee uneer VSC of hhe
olaenh. The lcrge eeurec e sn hhe enhrop, of cuhsachson
snesuche hhch hhe eleuhron een sh, es hrsbuhson s hrongl,
oesfsee sn hhe TS uneer VSC re ulhsng sn c ore polcr
cuhsachee uo plex. The olaenh uonuenhrchson eepeneenue
cne hhe ksnehsu s ohope effeuh ee on hrche hhch VSC ucn be
hrcn ferree fro hhe olaenh ho hhe oluhe c long c hhesr
asbrchsoncl re oncnue oaerlcp. Ths peuhrcl oaerlcp s noh sn
sh elf enough ho hrcn fer VSC fro hhe olaenh ho hhe recuhcnh.
Clecrl, hhe oluhe- olaenh snhercuhson u h be hrong e.g.
espolcr uouplsng ho sneuue hhe hrcn fer c hc reuenhl, been
hown sn c hheorehsucl hue, of en e ble sneuuee hrong
uouplsng effeuh on sngle qucnhu objeuh .[21] Ohher
hheorehsucl huese hcae uon seeree uhe sucl recuhsash, uneer
VSC sn hhe gc phc e cne uonfsr hhch hhe recuhsash, houle
be oesfsee.[13-16] In asew of hhe s porhcnh role of olachson sn
hhe TS furhher hheorehsucl huese hcksng snho cuuounh
olachson effeuh uneer VSC woule be aer, helpful. On hhe
expers enhcl see cn, ore ulc e of recuhson neee ho be
huesee sn oreer ho exhrcuh genercl prsnusple hhch goaern
recuhson uneer VSC. The u e of uooperchsae effeuh c
ee on hrchee here houle grechl, fcuslshche hhs hc k snue sh
re oae hhe requsre enh of hsgh uonuenhrchson of recuhcnh ho
cuhseae hhe hrong uouplsng uoneshson. Auhson peuhrc uneer
VSC ucn be u ee c c peuhro uopsu hool ho help ho eluuseche
whsuh asbrchson plc, c role sn hhe recuhson pchh. The e
fsnesng houle hcae lcrge s pcuh on uonhrollsng cne
uneer hcnesng uhe sucl recuhsash, hhrough VSC.
[14] J. C. G. Angulo, R. F. Ribeiro, J. Yuen-Zhou, 2019,
arXiv:1902.10264 [cond-mat, physics:physics,
physics:quant-ph].
[12] F. Herrera, F. C. Spano, Phys. Rev. Lett. 2016, 116,
238301.
[13] F. Herrera, F. C. Spano, ACS Photonics 2018, 5, 65-79.
[14] J. Galego, F. J. Garcia-Vidal, J. Feist, Nat. Commun.
2016, 7, 13841.
Acknowledgements
[15] C. Climent, J. Galego, F. J. Garcia-Vidal, J. Feist,
Angew. Chem. Int. Ed. 2019, 0, DOI
J.G. would like to thank Department of Chemical Sciences,
IISER Mohali for using the facilities; DST-SERB, Core
Research Grant (EMR/2017/003455) is also acknowledged. J.
L. and P. B. thank IISER Mohali for research funding. TWE
acknowledges support of the International Center for Frontier
Research in Chemistry (icFRC, Strasbourg), the ANR
Equipex Union (ANR-10-EQPX-52-01), the Labex NIE
projects (ANR-11-LABX-0058 NIE) and CSC (ANR-10-
LABX- 0026 CSC) wshhsn hhe Inae hs e enh e’Aaensr
program ANR-10-IDEX-0002-02 and the ERC (project no
788482 MOLUSC).
10.1002/anie.201901926.
[16] J. Galego, C. Climent, F. J. Garcia-Vidal, J. Feist,
2018, arXiv:1807.10846 [physics, physics:quant-ph].
[17] J. H. Park, B. P. Meriwether, P. Clodfelder, L. W.
Cunningham, J. Bio. Chem. 1961, 236, 136-141.
[18] C. Mitton, R. Schowen, M. Gresser, J. Shapley, J. Am.
Chem. Soc. 1969, 91, 2036-2044.
[19] C. G. Mitton, M. Gresser, R. L. Schowen, J. Am. Chem.
Soc. 1969, 91, 2045-2047.
[20] J.C. Owrutsky, A. D. Raftery, R. M. Hochstrasser, Ann.
Rev. Phys. Chem. 1994, 45, 519-555.
[21] S. Schütz, J. Schachenmayer, D. Hagenmüller, V.
Sandoghdar, T. W. Ebbesen, C. Genes, G. Pupillo,
2019, arXiv:1904.08888 [quant-ph].
Keywords: Cavity Catalysis • Cooperativity • Vibrational
Strong Coupling • Polaritonic Chemistry •
[1] T. W. Ebbesen, Acc. Chem. Res. 2016, 49, 2403-2412.
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10.1002/anie.201905407
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
Cavity catalysis: The solvolysis
reaction of para-nitrophenyl acetate
is accelerated by an order of
magnitude through cooperative
vibrational strong coupling of the
reactant and solvent molecules at
room temperature. The reaction
mixture is injected into a Fabry-
Perot (FP) cavity and the cavity
mode is tuned to the carbonyl
stretching mode of both the reactant
and solvent molecules together to
achieve strong coupling.
Jyoti Lather, Pooja Bhatt, Anoop
Thomas, Thomas W. Ebbesen, Jino
George
Page No. – Page No.
Cavity Catalysis by Cooperative
Vibrational Strong Coupling of
Reactant and Solvent Molecules
This article is protected by copyright. All rights reserved.