Quantum-Logic-Assisted Molecular Precision Measurements

Using a Network for The Distribution of the Swiss Frequency Standard

Aleksandr Shlykov1*, Ziv Meir1, Mudit Sinhal1, Kaveh Najafian1, Gregor Hegi1 and Stefan Willitsch1*


1Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland. * [email protected], [email protected]

The application of quantum-logic techniques to the spectroscopy of trapped molecular ions has enabled the determination of molecular properties at unprecedented levels of precision[1,2].
We have laid the experimental and theoretical foundations for hyperfine-state initialisation of the molecular ions and addressing the suitable extremely narrow infrared transitions[3-6] and currently are establishing a
complete toolbox for high-precision spectroscopy of single molecules using quantum-logic methods, their initialisation, coherent manipulation and non-destructive interrogation by coupling them to a co-trapped
single atomic ion[7,11,12].
Here, we present first results on the quantum non-demolition detection[8] of the spin-rovibrational quantum state of a single trapped molecular ion using state-dependent coherent motional excitation of a Ca+-N2+ two-
ion string. We demonstrate the application of this method to spectroscopy of dipole-allowed electronic transitions and discuss its adaption to precision measurements of vibrational spectra.
These advancements will pave the way for using molecules as new high-precision frequency standards[3,13,14] and clocks and for addressing fundamental physical problems such as determination of possible
temporal variations of fundamental physical constants[15,16]. Further improvement of the measurement accuracy will be enabled through the implementation of network for the distribution of the Swiss frequency
standard[9-17].
While we use N2+ as a prototype molecule, our methods can be extended to a general class of diatomic and polyatomic molecules.

he was able to carry out an analysis of the rotational structure

Loading Single Molecules into an Ion Trap Quantum-Logic Non-Demolition State Detection of the 4-2, 3-1, and 2-0 bands. An analysis of the 1-0 band was
13/2
b) likewise undertaken and was successful in the case of one of
The experimental setup State-selective [2+1’]
a)
N+ N+ We use state-dependent forces to entangle the state of the molecular ion with the common-mode motion of the atomic and
4 N2+ 4 the spin components.
N2
Ca+
Coherent consists of an ion trap resonance-enhanced multi- X+ 2Σ+g
3
2 X+ 2Σ+g
3
2
the molecular ions in the trap. We implement the force via 11/2
a state-dependent ac-Stark shift which is modulated resonantly at
Time-of-flight
Spectrometer

Ca+
Cooling
Ionization Control
N2+ coupled to a molecular photon ionisation [REMPI] is +
v =0 1
0
v+=0 1
0
the trap frequency leading to excitation of coherent motion9/2 inAsthehas
two ion the
been case [7,
crystal 11]. a
with Thenumber of auroral
modulated features,
ac-Stark shift arises
Detection
13/2
Ca
beam machine. Lasers for used to ionise a single molecule due to two counter-propagating beams detuned from the A-X(2,0) have been suggested
mechanismsdipole-allowed
several electronic as the
transition in modes of ex-1D lattice
a running
375 nm 7/2 5
NEG
Ionization
ionisation of Ca and N2 in a rovibrational ground state in O(2)
configuration. We readout the resultant motional state 5/2usingcitation
11/2
for the
resolved Meinel bands
sideband in the auirora.
thermometry Olmholt
on the pointed ion. The
atomic
Pump
neutrals, and cooling & the center of the trap[10] with a” 1Σ+g
212 nm O(2)
measurement leave the molecular rotation and spin-states to the likelihood
unperturbed
13/2 3/2
of the
leading to charge exchange
its quantum reaction
non-demolition nature.
Pulsed Valve 1/2
coherent manipulations of possible improvements to v’=0 9/2 3
Skimmer Skimmer
Ca
Ion trap
Turbo
Pump the ions are also shown. achieve hyperfine selectivity[5].
N’ N’ O+( 2 D) + N2 (X l1g ) - O( P) + N2+(A 2ll,, V = 1).
4 4
a” 1Πg
a) b) 11/2 7/2
Source In-vacuum 3 3 a) Electronic-vibrational level structure6of N2+ showing the electronic
lens
A pulsed valve is used to a) Current REMPI scheme Gattinger and(AJones interpret their au- (B2Σu+)
the other
Onground (X2hand,
2 2
5/2
Turbo Pump Turbo Pump 1 v'=6 1
Σg+), first-excited 2∏u) and second-excited
N2+ create internally cold employing ns pulsed laser 0 0 9/2
13/2 roral
3/2
measurements indicating
as vibronic that direct electron exci-
Detection N2+ Ca+ 2 x 202 nm S(0) 1/2 states. The A-X(2,0) transition is employed for our state-
packets of neutral beams at 202 and 375 nm.
scheme. responsible for the population of the v
is principally
Cooling
Coherent
Control
2 x 255 nm S(0)
A 2Πu (3/2)
 7/2 tation
detection
Molecular Beam UHV Ion trap chamber molecules which pass b) In development novel high- v=2 11/2
5/2 = 0 and v = 1 levels of the A 2fl, state leading to auroral
through the centre of the selective REMPI scheme via N” N2 N” 3/2
4 4 b) Possible
Meinel transitions from the N = 0 (blue), N = 2, J = 3/2 (green)
emission.
a”1Пg state with selectivity better X 1 +
Σg 3 X1 +
Σg 3 J9/2
ion trap and can be v”=0
2
v”=0
2
4
and the N = 2, J = 5/2 (orange) spin-rotation states in the A-X(2,0)
ionised. then 99%[18].
1
0
1
0
3
7/2 It will be noted that charge exchange cross sections such as
manifold.
2 5/2 that suggested above have a frequency dependence given by
3/2
a resonance denominator.
c) Theoretical the ac-Starkthe
simulation ofAccordingly, shiftrelative impor- by N2+
as experienced

Energy (cm-1)
1
0
4
in N of
= such
0 or N = 2 states
a process willas a function
depend of laser
critically detuning
on the proximity(same colour
Sympathetic Doppler Cooling of a Single N2+ Ion 3
tance
ofscheme
the levelsasinb).the
Resonant
incomingmodulation
and outgoing of the shiftspecies.
ionic at the trap
Forfrequency
X 2Σ+g

2 theforcase
a particular lattice-laser
of the A 2Il,, the lowestwavelength
lying excited (dashed
state line)
of N 2generates
+, a
Coulomb crystal

v=0
4P3/2 (6.8ns) 1
state-dependent
A small crystal of ~30 Doppler cooled Ca+ ions (at secular 0
rotational levels for optical-dipole forcecomponent,
only one spin-orbit (ODF) leading to coherent
the II1/2,
of Ca+

1.0 1.2 o 1.4 1.6 N 1.8

4P1/2 (6.9ns) r (A) motional
have excitation
been thus (CME) for
far measured in the
v = 1two-ion
and no crystal.
levels at Simulation
all have of the
mJ temperatures of a few mK) is used to quickly sympathetically
c) 6
10 of the
4 ODFmeasured
been experienced for vby= 0.the ions for beam intensities of 2x106 W/m2 is
+5/2 cool the N2+ molecular ion to mK temperatures. FIG. 1. 10Potentialenergycurves for the five lowestelectronicstates
+3/2
nitrogen molecular ion N2 +. The Meinel system constitutestransitions also shown on the same plot.
+1/2 2 Thus, if justification be needed for the present investiga-
1 N2+ trapped

5
betweenthe A llU and the groundstate X2+.
3
3D5/2 (1.16s) 10 10
after REMPI

-1/2
10 -3
d) Experimental
tion, we may invokesimulation of red-sideband
the requirement of chargesignals on Ca
exchange + - N2+ due
cal-
-3/2 6
3D3/2 (1.19s) -5/2 10
4
10
2 to different
culations for ac-shifts experienced byofNA
refined determinations for 500us
2+ 211 lattice pulse
excitation
No directly observed molecular bands were associated with

FODF [yN]
|"E| [Hz]

Then, a series of reduction 4

2
duration. Here,
mechanisms. Inonly the Ca+
addition, of experienced the ac-Stark
course, the work serves toshifts.
pro-
steps, in which the trap depth is 2 the nitrogen A 2flU state until the work of Meinel in 1950.
3 In
for the first time measurements of levels defining the
10 1
10
vide
Reduction of Ca+

+1/2 +

August of that year, he photographed the spectrum of the e) Schematic diagram depicting the implementation of the ODF. The
+ N2
4S1/2 Ca
x

lowered for a short time, is used 0

of the potential energy curve of the nitrogen molecular
a

-1/2 bottom
Ca+ - N2+ is prepared in the motional ground state of the trap. One of
aurora 10in the near infrared and recorded six bands of similar
ions

2 0
Cooling Coherent to remove all Ca+ ions but one -2 10

ion control ion

N=0; J=1/2; F=1/2 ion's
the lattice excited isstate.
lowest beams shifted in frequency by the N2+ - Ca+ common-
while keeping the N2+ ion. -4 shape in two N=2;clear sequences. These features were, in fact,
J=3/2; F=3/2
1 -1
Energy levels of Ca+ (not to scale) -6
10 N=2; J=5/2; F=5/2
3-1, and 4-2787as well as787.5
the 2-0, 786.5
10
the 3-0, 4-1,788and 5-2 bands of mode motional frequency generating a running 1D lattice leading to
Sympathetically 788.5
0 0.02 0.04
q
0.06 0.08 0.1
Laser Cooled Ca+
Cooled N2 + the A2nfl X 21system of6 N[nm]
2 +. laser
a state-dependent modulated ac-Stark shift.
EXPERIMENTAL
x

Position of N2+ and Ca+ on the ion trap Experimental sequence depicting X 22g
The first laboratory production of the A 211, -* The source for the production of the Meinel system emis-
time

d) 1 e)
stability diagram during reduction. loading of one N2+ ion with one Ca+ ion. 3 4
was achieved by Dalby and Douglas and
bands 0.9 Douglas
2.4 kHz
3.6 kHz
sion is a hollow cathode lamp designed and constructed at the
obtained high-resolution photographic spectra 4.8from
kHz which Argonne National Laboratory in collaboration with H. M.
0.8 6 kHz
7.2 kHz Crosswhite. It is shown in operation in Fig. 2. In the design
Sympathetic Ground-State Cooling of the N2+ Ion
8.4 kHz
0.7
9.6 kHz of the lamp we were guided by the requirements for optimum
10.8 kHz n=3
performance from a helium-nitrogen discharge. In practice,
0.6 12 kHz
0.5
a 13.1 kHz Torr of
we have found the best Meinel emission from about 2n=2
PD

0.5
flaser+fwith flowingflaser
trap just a trace of nitrogen in a pumped, n=1
0.4
Carrier
helium
Excitation Probability

-IP +IP
Excerpt of a resolved-sideband spectrum of a Doppler-
0.4
0.3
cooled Ca+-N2+ string showing the in-phase (IP) and system.
0.2
-2*IP
0.3 + + n=0
-OP +IP-OP -IP+OP +OP
out-of-phase (OP) motional modes. A bar of copper with a longitudinal cavity of rectangular
0.1
0.2 cross section comprises the main body of the lamp, that is, the
0
-1 -0.8 -0.6 -0.4 -0.2 0
f-f carrier [MHz]
0.2 0.4 0.6 0.8
0.1 cathode. The cavity is 10 X 25 X 250 mm, dimensions chosen
0.7
b
0.7
c d 0
to match the slits and angular apertures of relatively fast
0.6 0.6 Sympathetic sideband cooling of a single ion was N2+ 0 10 20 30 40 50
Excitation Probability

0.5 0.5
implemented and a ground-state population of over 98% t 729 [ s]
0.4 0.4
3D5/2
was achieved with a heating-rate of 4 quanta in one TABLE I. Deslandres table of the band origins of the analyzed bands in
Experimental Observation
0.3 0.3

0.2 0.2 second[11]. Angstroms(vacuumwavelengths).

0.1 0.1

0
-0.5 -0.49 -0.48
0
0.47 0.48 0.49 0.5 4S1/2 f) 0 v 0 1 2
f - f carrier [MHz]
N = 0; J = 1/2 Quantum non-demolition state detection of the N = 0, J = 1/2 state
Fit, "E = 8.48+/-0.29 kHz
0.2 N>0
in the electronic-vibrational ground quantum state of N2+.
0 11091.367
BG
Precision Hyperfine Spectroscopy of N2+ Using a Network for The 0.4
1
f) Experimentally
2
9 183.206
7measured
853.711 red-sideband Rabi signals as measured on
Distribution of the Swiss Frequency Standard FIG.2. Hollowcathode radiationsource. Basicallya hollowed-outand Ca+ for 3a Ca+ - N26874.664
+ ion string (same 8083.142
colour scheme as Fig. b and Fig. c).
PD

water-cooledbar of copper 250 mm in length,this tube has windows on Different4 N2+ spin states lead to different CME for the same
7064.775 lattice detuning
8324.664
0.6 and a copper-to-glassseal cementedinto a hole in the top. The as shown
both ends 5 in Fig. c). A lattice pulse durations of 500 μs was used in this
7 264.364
The transitions around 4.5 μm in N2+ are of interest for precision fs
hfs
F’
9/2
J’ = 5/2
lens focuses the emissionbands onto the spectrometer slit.
2
spectroscopy, fundamental physics tests and has many good clock J’ = 5/2 7/2
5/2
3/2
experiment. Purple trace shows the fit in accordance with d).
1/2
N’ = 2
0.8
qualities[15,16]. The X2Σg+(1<-0) transition at 4574 nm in 14N2+ has no v’ = 1
1/2
Benesch 793
et al.experimental
1.5 J’ = 3/2
J’ = 3/2 3/2
5/2 793 J. Opt. Soc. Am., Vol. 70, No. 7, July 1980 g) Shows the evolution of the average photon trace per run
permanent electric-dipole moment in its electronic ground state:
Intensity (arb.)

7/2

S(0)
which is indicative of the molecular state. The molecule begins in the state
• No E1 rovibrational transitions. 1
1
0 10 20 30 40 50 N = 0 leading to strong CME (green) at our lattice wavelengths. After
• Extremely narrow E2 transitions (nHz)[3].
F”
N” = 0 J” = 1/2 5/2
v” = 0

I=0 I=2
3/2
t 729 [7s] several experimental runs, the molecule makes a quantum jump out of the
• No Stark and BBR shifts to first order. -17 0.5
g)
N = 0 state which experiences no ac-Stark shift (and hence no CME). The
• Q(2) transitions can be measured to 10 fractional uncertainty[15]. 1
Avg. Photon

red-sideband Rabi signal the is the same as the measurement

Count

280
v = 0, N = 0, J = 1/2. F = 3/2
1.5
0 0.5 background (yellow) when the lattice is switch off.
v = 1, N = 2, J = 5/2. F = 5/2
−600 −400 −200 0 200 400 600
1 Frequency (MHz) 0 0.5 1 1.5 2 2.5 3
260
Calculated hyperfine spectrum of the (v=0->1) S(0) band of N2+. t ODF [s]
0.5
+65539 GHz

240
By solving the Zeeman Hamiltonian numerically, “magic” transitions have been identified
0
that are insensitive to magnetic-field fluctuations at a given applied field. Molecular quantum jump
-140
-0.5
Left) Zeeman splitting of the hyperfine levels in N2+. Arrows indicate two transitions which are
-160
-1 magnetic-field insensitive for the specific magnetic field value.
Right) The derivative of the transitions energy with respect to the magnetic field. Circles mark the
-180
0 2 4 6 8 10
-1.5
0 2 4 6 8 10
positions of first-order magnetic field insensitivity. Phase-Sensitive Force Spectroscopy
h) 106
0
Heat
N=0; J=1/2; F=1/2; m=1/2 The state detection red-side signal is directly linked to the force
Experimental data and the ac-shift experienced by the molecule. We used this to
0.1 Fit, "E = 7.09+/-0.2 kHz
BG

The rovibrational transition in the  electronic ground  state will be driven with a narrow-linewidth quantum-cascade
0.2

0.3

0.4
perform spectroscopy across the R11(1/2) transition of the A-X
laser (QCL), phase locked to a narrowed frequency comb. The comb will be referenced to the Swiss national frequency
PD

0.5

(2,0) manifold. Theoretical calculations (neglecting the hyperfine

0.6

standard[9] via a phase-stabilised optical fiber link[17] for long-term frequency stability.

0.7

0.8

10
5 0.9

1
structure) is shown in blue. Red data points are ac-Stark shift
|"E| [Hz]

0 10 20 30 40 50

a) METAS b) 729nm TA
c)
-30
Free running QCL
Partially phase locked
t 729 [7s]
values extracted from the red-sideband signal (inset).
PDH Stabilized -35
f (<1KHz linewidth) QCL - To Exp.
Opt. Ref.

Ultra Stable Laser Current Feedback PPLN

729 - To Dump
-40 Since the v = 1 states in the X2Σg+ manifold of N2+ experience a
(Fast) QCL
Power [dBm]

Cs Fountain
much weaker ac-shift at these detunings, the same technique is
~105 Kms
Fiber Link

Unibas Locking Electronics PZT Feedback -45

4
SFG 629nm

Toptica mFALC (Slow) 10 readily adaptable for precision spectroscopy on the X2Σg+(1<-0)
Ultra Stable Laser
Opt. Ref.

Regeneration -50
Amplifier
ZX60-100VH+
transitions.
~100 Kms

f -55
To ETH
Beat Note

Coupler LP (DC-105MHz)
ZX75LP-105-S+
Beat Note PD
HF-ULE Cavity ZX30-9-4-S+ Comb 629nm
SFG -60
QCL
35 37.5 40
Frequency [MHz]
42.5 45
787.4 787.45 787.5 787.55
729 nm Laser Spectrum
Analyzer 6laser [nm]
Exp. " ECa + = 1.8 kHz, " EN+ = 5.3 kHz
The phase of the force flips its sign when crossing from red to blue i) j)
1
2

a) Frequency distribution scheme based on the Cs-fountain frequency standard, FoCs-2, currently operational with a fractional- across the R11(1/2) resonance. We use the atomic Ca+ and the Out-of-Phase (OP) 0.9
OP, N+ in X '+ , N = 0
2 2 g
IP, N+ in X '+ , N = 0
frequency accuracy better than 2 x 10-15 [9] at the Federal Institute of Metrology METAS, Switzerland. The QCL is being phase-locked to FCa+ FN2+
2 2 g

lattice as a phase reference to the phase of the force experienced 0.8 + +

N2 in X2 'g , N > 0

a stabilised frequency comb at University of Basel, Switzerland after frequency up conversion via a non-linear SFG process with an 0.7
by the molecule. + +
ultra-stable 729nm ECDL. 0.6
PD

i) The phase and amplitude of the force on the atomic ion is always fixed due to 0.5

In-Phase (IP) 0.4

b) Detailed stabilisation schematic of the QCL at University of Basel. SFG between the ultra-stable 729 nm ECDL and QCL occurs in a the large detuning from the atomic resonance. The phase of the force on the
molecular ion with respect to the atomic ion is determined by the sign of the probe FCa+ FN2+ 0.3
PPLN leading to generation of light at 629 nm. This light is interfered with the comb. The resultant beat-note is used to feedback and 0.2
beam detuning and the lattice phase difference between the two ions. + +
phase-lock the QCL. 0.1

0
j) We see destructive interference (red) and constructive interference (blue) in the 0 10 20 30 40 50

c) Partial phase-lock of the QCL to the frequency comb. The lock was limited by unwanted optical feedback into the QCL. force signal when we are blue detuned with respect to the resonance as expected.
t 729 [7s]

[1] Wolf et al., Nature 530 (2016), 457. [10] Tong et al., Phys. Rev. Lett. 105 (2010), 143001.
[2] Chou et al., Nature 545 (2017), 203. [11] Meir et al,. Far. Disc. 217, 561 (2019).
[3] Germann et al., Nature Physics 10 (2014), 820. [12] Schmidt et al., Science 309 (2005), 749.
[4] Germann et al., J. Chem. Phys. 145 (2016), 044314. [13] Biesheuvel et al., Nat. Commun. 7, 10385 (2016).
[5] Germann et al., J. Chem. Phys. 145 (2016), 044315. [14] Alighanbari et al,. Nat. Phys. 14, 555 (2018).
[6] Germann et. al, Mol. Phys. 114, 769-773 (2016). [15] Kajita, PRA 92 (2015), 043423.
[7] Hume et al., PRL 107 (2011), 243902. [16] Schiller, Bakalov and Korobov, PRL 113 (2014), 023004.
[8] Hume et. al, PRL 99 (2007), 120502. [17] Calonico et al., Appl. Phys. B 117 (2014), 979.
[9] Jallageas et al., Metrologia 55 (2018), 366. [18] Gardner et al., Sci. Rep. 9 (2019), 506.