Witnessing Quantum Coherence: from

solid-state to biological systems

SUBJECT AREAS:
Che-Ming Li1,2,3, Neill Lambert3, Yueh-Nan Chen4, Guang-Yin Chen4 & Franco Nori3,5
QUANTUM PHYSICS
QUANTUM OPTICS
1
Department of Engineering Science, National Cheng Kung University, Tainan 701, Taiwan, 2Supercomputing Research Center,
BIOPHYSICS
National Cheng Kung University, Tainan 701, Taiwan, 3Advanced Science Institute, RIKEN, Saitama 351-0198, Japan,
4
PHYSICS Department of Physics and National Center for Theoretical Sciences, National Cheng Kung University, Tainan 701, Taiwan,
5
Department of Physics, University of Michigan, Ann Arbor, Michigan 48109-1040 USA.

Received
30 July 2012 Quantum coherence is one of the primary non-classical features of quantum systems. While protocols such
as the Leggett-Garg inequality (LGI) and quantum tomography can be used to test for the existence of
Accepted quantum coherence and dynamics in a given system, unambiguously detecting inherent ‘‘quantumness’’ still
24 October 2012 faces serious obstacles in terms of experimental feasibility and efficiency, particularly in complex systems.
Here we introduce two ‘‘quantum witnesses’’ to efficiently verify quantum coherence and dynamics in the
Published time domain, without the expense and burden of non-invasive measurements or full tomographic processes.
26 November 2012 Using several physical examples, including quantum transport in solid-state nanostructures and in
biological organisms, we show that these quantum witnesses are robust and have a much finer resolution in
their detection window than the LGI has. These robust quantum indicators may assist in reducing the
experimental overhead in unambiguously verifying quantum coherence in complex systems.
Correspondence and
requests for materials

Q
should be addressed to uantum coherence, or superposition, between different states is one of the main features of quantum
C.-M.L. (cmli@mail. systems. This distinctive property, coherence, ultimately leads to a variety of other phenomena, e.g.,
ncku.edu.tw); N.L. entanglement1,2. It is also thought to be the power behind several ‘‘quantum tools’’, including quantum
([email protected])
information processing3, metrology4, transport5, and recently, some functions in biological organisms6 (e.g.,
efficient energy transport).
or Y.-N.C. (yuehnan@
Identifying quantum coherence and dynamics in an efficient way, given limited system access, is indispensable
mail.ncku.edu.tw) for ensuring reliable quantum applications in a variety of contexts. Furthermore, the question of whether
quantum coherence can really exist in biological organisms in vivo, e.g., in a photosynthetic complex or in an
avian chemical compass, surrounded by a hot and wet environment, has triggered a surge of interest into the
relationship between quantum coherence and biological function7,8. In these cases, full-system access is often very
limited, and signatures of quantum coherence are often indirect.
The existing methods for identifying quantum coherent behavior can be generally classified into two types. The
first type are based on imposing what can be thought of as a classical constraint9, such as macroscopic realism and
non-invasive measurements in the Leggett-Garg inequality (LGI)10, or realism and locality in Bell’s Inequality.
Even though inequalities like the LGI were originally envisaged as a fundamental test of physical theories, a
violation of the LGI can also be considered as a tool for classifying the behavior observed in experiment as
quantum or classical. However, the Leggett-Garg inequality faces severe experimental difficulties when used as
such a tool as it requires noninvasive measurements, e.g., via quantum nondemolition (QND) measurement11,12,
weak measurement13, or quantum-gate-assisted ideal non-invasive measurements14. Because of this only a few
tests of the LGI have been reported14–18.
The second type of test is based on deduction; do the results of a given experiment sufficiently correspond to the
predictions of quantum theory (or classical theory, depending on the approach). Quantum witnesses can be
considered as one such test, as they use the knowledge of a quantum state or of some quantum dynamics to
determine whether an experimental system possesses quantum properties. Some examples that have been
employed elsewhere include witnesses of entanglement19,20, direct measurement of coherence terms of density
matrices, or the analysis of process tomography21 for non-classical state evolutions. The experimental realization
of this kind of verification usually needs tomographic techniques, and then the required experimental resources in
terms of measurement settings increases exponentially with the system complexity19,21,22. Moreover, quantum
state and process tomography are still difficult to implement in general systems and for general state evolutions,
e.g., particularly in systems like charge transport through nanostructures, the transfer of electronic excitations in a
photosynthetic complex, or systems where the state space is large.

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In this work, we introduce two quantum witnesses to verify of time t0, to reach the state rSR(t0) (during which time one hopes
quantum coherence and dynamics in the time domain, both of which the state has acquired significant coherence due to its internal
have various advantages and disadvantages. Both are efficient in the dynamics). The second step is to implement a quantum witness using
sense that there is no need to perform noninvasive measurements or a ‘‘correlation check’’ between the state rSR(t0) and its state at another
to use quantum tomography, dramatically reducing the overhead later time t $ t0, rSR(t) (see Figure 1b). The goal of this correlation
and complexity of unambiguous experimental verification of check is to investigate non-classical properties in these two-time
quantum phenomena. state-state correlations (see Figure 1c). If the state rSR(t0) can be
We apply these quantum witnesses to five examples: (1) electron- detected then by our quantum witness as having quantum properties,
pair tunnelling in a Cooperpair box and coherent evolution of single- this implies that either the system state rS(t0) 5 TrR[rSR(t0)] pos-
transmon qubit, (2) charge transport through double quantum dots, sesses significant quantum coherence or that the state rSR(t0) is an
(3) non-equilibrium energy transfer in a photosynthetic pigment- entangled system-bath state.
protein complex, (4) vacuum Rabi oscillation in lossy cavities, and
(5) coherent rotations of photonic qubits. Furthermore, as we will
illustrate in these examples, our quantum witnesses possess a finer Results
detection resolution than the LGI. In order to find a signature of quantum dynamics we start by seeking
Both witnesses, which we will introduce shortly, involve the fol- characteristic features of classical dynamics or states23. All separable
lowing steps: (Figure 1a) first, we prepare the system in a known mixtures of system-reservoir states, with no coherent components,
product state with its environment (or reservoir, here we use both which we call classical states, obey the following relation for their
terms interchangeably) rSR(0). We then let rSR(0) evolve for a period two-time correlations:

Figure 1 | Detecting quantum coherence and dynamics. Generic procedure for detecting quantum coherence: We need (a) state preparation and (b) a
correlation check. With the freedom to manipulate the system state, the initial state of the total system can be reasonably prepared as a product state rSR(0)
5 rS(0) fl rR(0), where rR(0) is the reservoir state. (b) and (c) show the correlation check, or measurements, we base our quantum witnesses on.
Assuming the system state at time t0 is rS(t0) 5 Qn(t0), the probability of being in a state Qm at later time t is determined by the n R m propagator Vmn(t,
t0). The general quantum correlator is defined by ÆQm(t)Qn (t0)æQ (upper green path) and the classical one is defined by pn(t0)Vmn(t, t0) (lower brown
track). In this expression, Vmn(t, t0) is the probability of measuring the system in state m at time t given that it was in the state n at time t0. Both definitions
describe the connections between Qn(t0) and Qm(t) for arbitrary states rS(t0) with a distribution of state populations {pn(t0)}. As shown in the Methods, all
classical dynamics should satisfy the relation, ÆQm(t)Qn(t0)æQ 5 pn(t0)Vmn(t, t0). While our quantum witnesses are derived from this ‘‘correlation check’’,
the experimental requirements for each witness differ.

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hQm ðt ÞQn ðt0 ÞiQ ~pn ðt0 ÞVmn ðt,t0 Þ: ð1Þ Witness 1. Our first practical witness (which is the main result of this
work) can be derived from Eq. (1) by including normalization.
See Methods for the proof. Succinctly put, equation (1) implies it is Noting that all classical system-reservoir states obey,
possible to define all future behavior based on only the system’s Xd
instantaneous expectation values pn(t0). However, most quantum hQm ðt Þi~ pn ðt0 ÞVmn ðt,t0 Þ, ð3Þ
correlation functions also obey this relation under certain measure- n~1
ment conditions. For example, a correlation function constructed
where d is the number of states n in, or dimensionality of, the system
from two-time projective measurements has this form as the mea-
state space, we define our first quantum witness as
surement at t0 destroys the coherence in the state at that time. Here Qi  
 X 
is an observable which measures if the system is in the state i. This  
W Q : ~hQm ðt Þi{ pn ðt0 ÞVmn ðt,t0 Þ: ð4Þ
state is assumed to have a classical meaning (e.g., localized charge  n

state, etc) and the observable is normalized so that its expectation
value is directly equal to the probability of observing the system in If W Q w0, we can define the state at t0 as quantum. Compared with
that state ÆQiæ 5 pi. The propagator Vmn(t, t0) is the probability of the witness W QQ and the tests of the LGI, W Q can always be directly
measuring the system in state m at time t given that it was in the state measured, and ideal non-invasive measurements are not necessary.
n at time t0 (and which in principle depends on the state of the In experimental realizations, measuring the population-related
reservoir, so can include classical non-Markovian correlations, see quantities, or expectation values, ÆQm(t)æ and {pn(t0)}, is generally
Methods). Several other recent tests of quantumness18,24–27 rely on more feasible than constructing full correlation functions,
imposing Markovianity on Vnm(t, t0). In our first witness we avoid particularly in systems which rely on destructive (e.g.,
taking that approach so that we can still distinguish quantum from fluorescence) measurements. Where correlation functions can be
classical non-Markovian dynamics. However we will use it in our measured with projective measurements, the second term can of
second witness. course be replaced with Sn pn(t0)Vmn(t, t0) ; SnÆQm(t)Qn(t0)æ.
In principle, one could use Eq. (1) to construct a quantum witness However, determining all the propagators Vmn(t, t0) with which to
of the form: construct the witness requires, in principle, that we can prepare the
  system in each one of it states n exactly (or, alternatively if correla-
 
W QQ : ~hQm ðt ÞQn ðt0 ÞiQ {pn ðt0 ÞVmn ðt,t0 Þ: ð2Þ tion functions constructed from projective measurements are avail-
able, it requires that we measure every possible cross-correlation
Where a non-zero result W QQ w0, implies the state at t0 can be SnÆQm(t)Qn(t0)æ). In the former case (where we use state prepara-
considered as quantum in that it contains quantum coherence which tion) we trade-off the need to do non-invasive state measurement
affects its future evolution. However, as mentioned above, most with the need to perform ideal state preparation. In complex systems
quantum correlation functions also obey equation (1), which will it may be difficult to prepare the system in each one of its states to
give W QQ ~0. Is it ever possible to observe a non-zero W QQ ? In some construct these propagators, and in some cases we may not even
cases coherence, or ‘‘amplitude’’, sensitive correlation functions are have knowledge of the full state-space of the system.
encountered in quantum optics28, and in linear-response theory29. Importantly, this problem can be easily overcome by noticing that
However, these are typically extracted from spectral functions in the the individual terms in the sum in Eq. (4) are always positive. Thus
steady state, or put in a symmetrized form, in which case any effect on when constructing the sum we can stop as soon as the witness is
the correlation function from the initial state coherence may be lost. violated by this partial summation (i.e., when the terms in the sum-
In all the examples we consider in this work this witness W QQ cannot mation together are larger than ÆQm(t)æ), reducing the experimental
be directly measured, as the initial coherence is of course destroyed overhead substantially (see Figure 4 for a practical example, where we
by the first (projective) measurement. Fortunately, W QQ , via Eq. (1), show it is sufficient to include just one term in the sum of Eq. (4)).
gives us a way to develop a more generally applicable and valid Note that with this witness we do not distinguish between just
witness. system-coherence or quantum correlations (entanglement) between

Figure 2 | Detecting quantum oscillations. (a) shows a schematic circuit of a single-Cooper-pair box36,37. Its Hamiltonian is described by HCB 5 EC(1–
2ng)/2( | 2æÆ2 | 2 | 1æÆ1 | )2EJ/2( | 1æÆ2 | 1 | 2æÆ1 | ), where EJ and EC are the Josephson energy and the single-Cooper-pair charging energy of the box,
respectively. The relative energy of the state with no excess Cooper pairs in the box | 1æ and the state with one excess Cooper pair | 2æ, is controlled through
the gate voltage, which is parametrized by ng. The resonance of the states | 1æ and | 2æ can be brought from the initial state | 1æ by the applied voltage pulse
for ng 5 0.5. (b), Detecting quantum dynamics in the resonance of the two charge states (ng 5 0.5) with the quantum witness W V21 . We use the realistic
parameter EJ 5 51.8 meV. The positive regions are identified as the quantum areas.

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system and bath/reservoir (see Methods). In addition, if there are Witness 2. For our second  witness we impose the extra condition
classical correlations between system and reservoir, i.e., classical that Vmn ðt,t0 Þ~Vmn t 0 ,t00 for t{t0 ~t 0 {t00 ~t, for any time
non-Markovian effects30, then some additional experimental over- interval t. This assumption restricts us to a widely-studied subset
head is needed to eliminate this from giving a ‘‘false positive’’. If this of quantum processes where the system-bath/reservoir interaction
overhead is ignored this represents a ‘‘loop-hole’’ in this witness, and is Markovian. We will show that, under the assumption that our
in some situations may be an obstacle for its unambiguous applica- system lies within this subset, quantum properties can be
tion. We will discuss this explicitly later with an example of a pho- identified without needing to explicitly measure propagators (i.e.,
tosynthetic light-harvesting complex where the system and reservoir neither exact state initialization or non-invasive measurements are
are strongly correlated both classically and quantum mechanically. required). The trade-off in this case is that the witness cannot
distinguish certain types of classical dynamics (e.g., classical non-
Markovian), from quantum properties of the system. Still, this
witness exceeds the tests proposed in earlier works under the same
constraints which still required either non-invasive measurements or
state preparation18,25.
This subset of quantum processes can be described as having weak
coupling between system and reservoir so that system-reservoir state
is always a product state, and the bath/reservoir state does not evolve
in time, i.e., rR(t) 5 rR(0). A large number of systems exist in this
regime30, with well-developed models such as the master equation
under the Born approximation operating within this class (see, e.g.30–32).
For such cases, we can extend the first witness so that we replace
the need to prepare the system state with that of needing to repeat-
edly measure expectation values (not correlation functions) a number of
times that scales linearly with system size. To show this, we consider an
extension of Eq. (3) involving a system of d linear equations represented
in matrix multiplication form as follows:
Pj Vmj ~Qmj ð5Þ

where the d 3 d matrix Pj has elements [Pj]kn 5 pn(t0[j,k]), and Vmj and
Qmj are d 3 1 column vectors with elements [Vmj]n1 5 Vmn[j](t) and
[Q mj]k1 5 ÆQm(t[j,k])æ, respectively. Here, t0[j,k] and t[j,k] constitute the jth
nontrivial time-domain set Tj:{t0[j,k], t[j,k]jt[j,k] – t0[j,k] 5 t; k 5 1, 2, …,
d}. For a given time difference t and a time pair (t0[j,k], t[j,k]) g Tj, one
can use the most experimentally-feasible method of measurement, i.e.,
invasive measurement, to obtain the information about the state popu-
lations, pn(t0[j,k]) and the expectation values ÆQm(t[j,k])æ.
Given a set of measurement results to sufficiently describe the state
populations, the vector Vmj can be determined by simple algebraic
methods.
 For nonzero determinant det(Pj), we have Vmn½ j ðtÞ~
.
ðnÞ   ðnÞ
det Pmj det Pj , where Pmj is the matrix formed by replacing
the nth column of Pj by Qmj. For an arbitrary pair of time-domain
sets, say Tj and Tj 0 , we impose an additional condition (not used in
the earlier witnesses) that their propagators should be identical for all
classical systems (within the subset described above): Vmj ~Vmj0 . If
the system and its environment are classically-correlated, i.e., they
are not in a product state, this assumption does not hold. Any com-
parison between Vmj and Vmj0 can be considered as a quantum
witness for this subset, such as the vector-element comparison:
        
 ðnÞ ðnÞ 
W Vmn : ~det Pmj det Pj0 {det Pmj0 det Pj : ð6Þ
Figure 3 | Detecting quantum transport through a double quantum dot.
(a) Schematic of a single-electron double quantum dot (DQD). Here we If W Vmn w0, and under the assumptions described earlier, we can
assume that the DQD is weakly coupled to leads under a large bias. Its again assume that some of the (set) of initial states are quantum.
Hamiltonian is HDQD 5 D( | LæÆR | 1 | RæÆL | ) with the electron state basis Since measuring W Vmn requires the information about state popula-
{ | Læ, | Ræ, | 0æ} where D is the tunnelling amplitude between the left-dot and tions only and can be performed with invasive observations, imple-
right-dot electron states | Læ, | Ræ. The transport
X between dots and leads is menting W Vmn can be more practical than implementing W QQ (2)
 { {
described by the self-energy, S½r~{1=2 a~L,R Ca sa sa r{2sa rsa and W Q (4).
{
zrsa sa , where sL 5 | 0æÆL | , sR 5 | RæÆ0 | , and CL and CR are the left and
right tunnelling rates, respectively. We assume charge detectors (CDs) are Examples. To illustrate the effectiveness of our witnesses we now
used for the measurements, but invasive current measurements are also present five example systems where they could be applied. For each
sufficient (not shown here). (b,c) Verifying quantum transport through example we choose which ever witness is more appropriate, given the
DQD with W Q [Eq. (4) for t 2 t0 5 t] and W V32 [Eq. (6)], respectively. properties of that system.
Here we define | 0æ, | Læ, and | Ræ by | 1æ, | 2æ, and | 3æ, respectively. For the
setting CL 5 4, CR 5 0.1, and D 5 1, the non-vanished W Q and cW V32 Rabi oscillations in superconducting qubits. The oscillations of
indicate the quantum-transport regions, where c 5 (p1p2p3)21 for the state populations are commonly thought of as a signature of
stationary state. quantum dynamics. The measurement of these kind of oscillations

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Figure 4 | Detecting quantum properties of the FMO complex. Magnitude of the first witness W Q [Eq. (4) for t 2 t0 5 t] for the FMO complex assuming
the final measurement is done on site m 5 1 of the seven site FMO complex, for both (a) T 5 77 K and (b) T 5 300 K. A detection via our first witness is
clearly visible for an initial evolution greater than t0 5 0.3 ps at 77 K. In comparison, for same parameters we employ for the witness, the LG inequality
only reveals a violation for upto 0.035 ps44. (c) and (d) show the first witness with only limited access, i.e. with only state preparation and measurement on
site 1. Quantum coherence is only detected when p1(t0)V11(t, t0) . ÆQ1(t)æ. In all figures the bath parameters used were c21 5 50 fs and l 5 35 cm21, and
the Hamiltonian is the same as that used in Ref. 8. For the Hierarchy calculation, we used the ‘‘Ishizaki-Tanimura’’ truncation scheme and truncation as
taken at K 5 0 and Nc 5 8 (see Methods, or Ref. 8, for the meaning of these parameters).

is widely employed for many experiments. The observation of design the microwave pulse for such a gate (E H ) with a process
such oscillations alone, however, is not definitive evidence for fidelity of about 94%. We use the first witness W Q in the form:
the existence of quantum coherent dynamics and can even be  
 X 1 
mimicked by the solutions of classical autonomous rate equations,  
W Q : ~h0ðE 2H Þi{ pn ðE H ÞV0n ðE H Þ, ð8Þ
e.g., Ref. 33,34.  n~0

As a first example of the application of our witnesses we apply
W Vmn (6) to a two-level system composed of the two lowest-energy to show that the process E H creates coherent rotations. When setting
states in a single-Cooper-pair box35–37, Figure 2a. We can take n 5 1, the input state as j0æ, the value of our witness is about W Q <0:45,
m 5 2, for example together with the designation Tj: {t0[j,k] 5 (k 1 j – which certifies the quantumness of E H .
1)t0, t[1,k] 5 (k 1 j – 1)t0 1 tjk 5 1, 2} for j 5 1, 2, Figure 2b illustrates
that the quantum witness W V21 detects the presence of quantumness Quantum transport in quantum dots. Experimentally disting-
in the Cooper-pair tunneling. Since only information about state uishing quantum from classical transport through nanostructure
populations is required, this witness is easy to apply in practice with remains a critical challenge in studying transport phenomena and
simple invasive measurements and can be readily applied to the designing quantum electronic devices. As mentioned in the intro-
existing experiments in the time domain36,37 without any additional duction, using time-domain methods to verify quantum coherence,
experimental overhead. such as by testing the Leggett-Garg inequality, can be very demand-
One can also consider an application of our witnesses to single- ing. We illustrate here how our witnesses are valid in a non-
and multiple-transmon qubits coupled to transmission lines in cir- equilibrium transport situation by modelling single-electron tran-
cuit quantum electrodynamics38,39, where qubit-state measurements sport through double quantum dots (Figure 3a). Compared with
are performed by monitoring the transmission through the micro- the time periods identified by the Leggett-Garg-type approach25,
wave cavity39. For the simplest case of one-qubit rotation, the coher- the quantum witnesses W Q (Figure 3b) and W Vmn (Figure 3c) can
ent evolution is driven by the Hamiltonian38 detect a much larger quantum coherence window. For W Vmn , we
H~hVj1ih1jzeðt Þðj0ih1jzj1ih0jÞ, ð7Þ employ the settings Tj: {t0[j,k] 5 [k 1 c9(j – 1)]t0, t[1,k] 5 [k 1 c9(j –
1)]t0 1 tjk 5 1, 2 , 3} for j 5 1, 2. Here c9 is large such that the whole
where e(t) is the microwave pulse to induce transitions between qubit system is stationary in T2.
states j0æ and j1æ with an energy difference hv. Through properly
choosing the pulse e(t), a reliable single-qubit gate, e.g., the Energy transfer in a light-harvesting complex. As an example of the
Hadamard transformation (H), can be created. Here, we use the effect of strong interactions with a bath we use a model from bio-
quantum-process-tomography-based optimal control theory40 to physics; energy transport in the Fenna–Matthews–Olson (FMO)

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Figure 5 | Detecting vacuum Rabi oscillations in a lossy cavity. Here we Figure 6 | Detecting coherent rotations of photonic qubits. The first
use the experimental data reported in Ref. 47 to illustrate coherence- witness W Q , Eq. (4), adapted from the time-domain to the domain of the
verification using our second witness Eq. (6). The circular Rydberg states angles of several applied transformations, detects quantum coherence in
with principle quantum numbers 51 and 50 for transition v0 5 51.1 GHz almost the whole range of the prepared states r0 (see text) as a function of
are considered as the states | eæ and | gæ, respectively. The atom-field different angle settings of wave plates (w, h): 0 # w # p/4 and 0 # h # p/2.
coupling is vR/2p 5 47 KHz. For a high-Q cavity with Q 5 7 3 107, the
vacuum Rabi oscillation is detected by use of W Vmn where m 5 n 5 1. As a
Hierarchical equations of motion7,8, an exact model (given a bath
comparison we also checked the case when the Q-factor is so low that 2vR
with a Drude spectral density) valid for both strong system-bath
, v0/Q. For such a low-Q cavity (e.g., Q 5 7 3 105), the state evolution is
in the regime of irreversible transitions and obeys the classical constraint
coupling and long-bath memory time. We use the parameters used
(3). Hence the value of the witness is zero.
by Ishizaki and Fleming in Refs. 7,8, and in Figure 4 we show how this
model is detected as quantum by our witness W Q , even at room
temperature. We also show, in Figure 4c and 4d, how only partial
pigment-protein complex, where there is thought to be significant
information about the terms in propagator is needed to find a detec-
system-bath entanglement and coherence8. As mentioned earlier,
tion at small times, thus reducing the experimental overhead. In
this example enables to discuss the issue of whether classical-
constructing the propagator terms for the sum in Eq. (4) in this case
correlations between system and bath can cause a violation of our
we discard all coherence terms in the physical density matrix but
first witness W Q (the second witness is not valid in this regime).
retain the state of the bath, as in43. In this way we account for the state
In the methods section we impose a classical condition based on an
of the bath at time t0, as discussed above. However, accounting for the
assumption of a class of classical states. States which violate this
classical correlations with the reservoir seems beyond the capability
assumption possess coherences (either in the internal system degrees
of current experiments. We also point out that the full witness detects
of freedom, or in the system-bath degrees of freedom, i.e., entangle-
coherence on timescales greater than t0 5 0.3 ps at 77 K, which is a
ment). However, to prevent classical correlations between system
much larger detection window than the Leggett-Garg inequality
and bath from causing a false positive, the propagators Vmn(t, t0)
(0.035 ps) for the same parameters44.
in our witness (4), which we construct by preparing the system in one
(or more) of its states, must also capture the classical correlations
Vacuum Rabi oscillation in a lossy cavity. We now consider a
between system and reservoir present at time t0. In the other exam-
Rydberg atom placed in a single-mode cavity which is in resonance
ples we discuss in this work, this is trivial since the system and bath
with an atomic transition frequency, v0, for an adjacent pair of
are always in a product state. However, in systems like the FMO
circular Rydberg states45 jeæ and jgæ. Let us consider the case when
complex we discuss here, this is not the case. Thus to account for
the cavity field are initially prepared in the excited state jeæ and the
these correlations when constructing Vmn(t, t0) in a general case we
vacuum state j0æp, respectively (denoted by j1æ 5 jeæ j0æp). In this case,
must do the following: prepare the system-bath product state at t 5 0,
the atom-field state becomes j2æ 5 jgæ j1æp due to spontaneous
evolve to time t0, and perform a measurement on the system to
emission and then periodically oscillates between the states jeæ j0æp
project it, without preserving coherence, onto one of it states n.
and jgæ j1æp at the vacuum Rabi frequency vR. If the field irreversibly
We then evolve again, retaining the post-measurement system-bath
decays due to photon loss out of the cavity, the atomfield
state, and deduce the propagator by measuring the occupation of the
stochastically evolves to j3æ 5 jgæ j0æp from j2æ. Summarizing the
state m at final time t. If we can do ideal projective (non-coherence
above, the time evolution of the atom-field state r can be described
preserving) measurements this accounts for the classical system-bath
by the following master equation46
correlation loophole (as long as we can consistently prepare the t 5 0
separable system-bath state). If we are doing destructive or invasive d i k 
r~{ ½HJC ,r{ ^a{ ^arzr^a{ ^a zk^ar^a{ ð9Þ
measurements then we must be able to re-prepare the destroyed dt h 2
system state, at time t0, on a time scale faster than the bath/envir-  
onment dynamics. Since there is no need for measurements on where HJC ~ hVR ^asz z^a{ s{ is the interaction Hamiltonian of
2
superpositions of basis states, this procedure can be performed with- the system. Here k 5 v0/Q, and Q is the quality factor of the cavity.
out quantum tomography. We now use our second witness to detect the vacuum-Rabi oscil-
We illustrate this with the FMO complex, a seven-site struc- lation between the atom and cavity field states. Here we choose the
ture used by certain types of bacteria to transfer excitations from a time-domain set as Tj: {t0[j,k] 5 (k 1 j – 1)t0, t[1,k] 5 (k 1 j – 1)t0 1 tjk
light-harvesting antenna to a reaction center. It has been the focus of 5 1, 2, 3} for j 5 1, 2. Figure 5 shows the value of the witness for
a great deal of attention due to experimental observation of apparent vacuum-Rabi oscillations in a high-Q cavity. Using the experimental
‘‘quantum coherent oscillations’’ at both 77 K and room temper- parameters from47, where 2VR ?V0 =Q, the damped coherent oscil-
ature. To fully capture the non-Markovian and non-perturbative lations of the atom-cavity state are detected as quantum by our
system-bath interactions of this complex system we employ the second witness. In comparison, for a low-Q cavity, where 2vR ,

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v0/Q, irreversible spontaneous emission out of the cavity will dom- structures, biological systems, and perhaps even large-arrays of
inate the state evolution. The value of the witness W Vmn is zero for qubits used in adiabatic quantum computing51. After this paper went
this case. The measurements on atom states we require to construct to press, we became aware of this preprint52, which has related results.
the witness are experimentally available by using field-ionization
detectors45 for selecting atom states jeæ and jgæ.
Methods
Coherent rotations of photonic quantum bits. Photon polarization Proof of equation (1). The quantum two-time state-state correlation ÆQm(t)Qn(t0)æQ
is defined by31:
states jHæ (horizontal) and jVæ (vertical) have been widely used to
achieve linear optical quantum information processing, quantum hQm ðt ÞQn ðt0 ÞiQ
communication, and quantum metrology3,48,49. As a qubit, polari-
~trSR ½rSR ð0ÞQm ðt ÞQn ðt0 Þ ð15Þ
zation states can be coherently manipulated by half-wave plates 
(HWP) and quarter-wave plates (QWP). Arbitrary qubit rotations ~trS Qm ð0ÞtrR U ðtÞrSR ðt0 ÞQn ð0ÞU { ðtÞ ,
can be performed by using these linear optics elements. Here we will
where rSR(t0) is the system-reservoir state and U(t) is the system-reservoir evolution
use our first quantum witness W Q to detect the quantum coherence operator for t 5 t – t0. If rSR(t0) is a classical state with no coherent components, then
of polarization states created by these rotations. The transformations we have
of HWP and QWP can be represented by the following50:
rSR ðt0 ÞQn ð0Þ~pn ðt0 ÞQn ð0ÞRðt0 Þ ð16Þ
Hwp ðwÞ~ cosð2wÞðjH ihH j{jV ihV jÞ
ð10Þ where pn(t0) is the probability of measuring the system state n at time t0 for the
{ sinð2wÞðjH ihV jzjV ihH jÞ, classical mixture rSR(t0), and R(t0) is the reservoir state at time t0 (which in principle
depends on the measurement result Qn if the system and reservoir are classically
1 correlated, i.e., are separable but in a mixture of product states). Then we have
Qwp ðhÞ~ pffiffiffi ½ði{ cosð2hÞÞjH ihH jzðiz cosð2hÞÞjV ihV j
2 ð11Þ hQm ðt ÞQn ðt0 ÞiQ

z sinð2hÞðjH ihV jzjV ihH jÞ: ~pn ðt0 ÞtrS Qm ð0ÞtrR U ðtÞQn ð0ÞRðt0 ÞU { ðtÞ :
The term describing the system’s evolution trR[U(t)Qn(0)R(t0)U{(t)] can be
As a concrete example, one can set a HWP at w 5 p/8 to create a
described by the operator-sum representation21,30:
photonic Hadamard gate Hwp(p/8). X

To detect the coherent rotations created by R(w, h) 5 trR U ðtÞQn ð0ÞRðt ÞU { ðtÞ ~ Ej ðtÞQn ð0ÞEj{ ðtÞ,
Qwp(h)Hwp(w), we use the first quantum witness to probe the coher- j

ence between states jHæ and jVæ. While the witness is originally con- P pffiffiffiffiffiffi 
where Ej ðtÞ~ k prk rj U ðtÞjrk i. The the reservoir state is assumed to be R(t0) 5
structed in the time domain, it can be rephrased in terms of the Sk prk jrkæÆrkj. Hence the correlation ÆQm(t)Qn(t0)æQ for the system-reservoir classical
settings (w, h). Assuming that both the wave plates are perfect and mixture at the time t0 is
there is no photon loss in the birefringent crystals of the wave plates,
hQm ðt ÞQn ðt0 ÞiQ
we have the following correspondences: ( )
 X
hQm ðw,hÞi~tr jmihmjRðw,hÞr0 R{ ðw,hÞ , ð12Þ ~pn ðt0 ÞtrS Qm ð0Þ Ej ðtÞQn ð0ÞEj{ ðtÞ
j
and ð17Þ
X
2 ~pn ðt0 Þ Vðmn
jÞ
ðt,t0 Þ
Vmn ðw,hÞ~jhmjRðw,hÞjnij , ð13Þ j

where r0 is some initial state created by R. Here m 5 H and n 5 V ~pn ðt0 ÞVmn ðt,t0 Þ,
denote the different measurement basis for the horizontal and ver- P jÞ
where Vmn ðt,t0 Þ : ~ j Vðmn ðt,t0 Þ is the propagator, i.e., the probability of finding
tical polarizations. In this example, we set the initial state as r0 5 the state m at the time t when the state at an earlier time t0 is initialized at n.
R{(w, h) jmæÆmj R(w, h) and then the witness becomes
1 The Hierarchy model for FMO. The Hierarchy model was originally developed by
j
W Q ~ 1{
16
½10z2 cosð4hÞz2 cosð4h{8wÞz: Tanimura and Kubo41, and has been applied extensively to light-harvesting
complexes7,8. We will not give a full description here, but will just summarize the main
ð14Þ
equation and parameters. It is always assumed that at t 5 0 the system and bath are
cosð8h{8wÞz cosð8wÞ : j separable rð0Þ~rS ð0Þ6rB ð0Þ, and that the bath is in a thermal equilibrium state
ðBÞ
. h ðBÞ
i
rB ð0Þ~e{bH Tr e{bH , b~1=KB T. The bath is assumed to have a Drude
Figure 6 shows this quantum witness for different prepared states r0, spectral density
as a function of the angles h and w. 
The usual approach to strictly probe the coherent superposition of 2lj cj V
Jj ðVÞ~ , ð18Þ
states jHæ and jVæ is via quantum state tomography50. Compared to h V2 zc2j
such tomographic measurements on single qubit states, which where cj is the ‘‘Drude decay constant’’ and each site j is assumed to have its own
require three local measurement settings, only one setting of a local independent bath. In addition, lj is the reorganisation energy, and is proportional to
measurement is now sufficient to implement our first witness. the system-bath coupling strength. The correlation function for the bath is then given
by,
Discussion X
?  
In summary, we have formulated a set of quantum witnesses that Cj ~ cj,m exp {mj,m t ð19Þ
m~0
allow the efficient detection of quantum coherence, without the re-
striction of non-invasive measurements. Compared to some of the where mj,0 5 cj, and mj,m 5 2pm/hb when m $ 1. The coefficients are
existing methods, such as the Leggett-Garg inequality or employing   .  .
cj,0 ~cj lj cot bhcj 2 {i h ð20Þ
general quantum tomography, our approach can drastically reduces
the overhead and complexity of unambiguous experimental detec- and
tion of quantum phenomena, and has a larger detection window. As 4lj cj mj,m
illustrated by the five physical examples, these witnesses are robust cj,m§1 ~ : ð21Þ
bh2 m2j,m {c2j
and can be readily used to explore the presence of quantum coher-
ence in a wide-range of complex systems, e.g., transport in nano- Under these assumptions, the Hierarchy equations of motion are given by,

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measurements of photons. Proc. Natl Acad. Sci. 108, 1256 (2011). partial support from the National Science Council, Taiwan, under Grant No. NSC
18. Waldherr, G., Neumann, P., Huelga, S. F., Jelezko, F. & Wrachtrup, J. Violation of 101-2112-M-006-016-MY3, No. NSC 101-2738-M-006-005, and No. NSC 103-2911-I-006
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(Cambridge University Press, 2000). Quantum Cybernetics, and Funding Program for Innovative R&D on S&T (FIRST).

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Author contributions License: This work is licensed under a Creative Commons

C.-M.L. devised the basic model. C.-M.L., N.L. and Y.-N.C. established the final framework. Attribution-NonCommercial-NoDerivs 3.0 Unported License. To view a copy of this
C.-M.L. and N.L. performed calculations and wrote the paper. G.-Y.C. attended the license, visit http://creativecommons.org/licenses/by-nc-nd/3.0/
discussions. F.N. supervised the project and wrote the paper. How to cite this article: Li, C., Lambert, N., Chen, Y., Chen, G. & Nori, F. Witnessing
Quantum Coherence: from solid-state to biological systems. Sci. Rep. 2, 885; DOI:10.1038/
srep00885 (2012).
Additional information
Competing financial interests: The authors declare no competing financial interests.

SCIENTIFIC REPORTS | 2 : 885 | DOI: 10.1038/srep00885 9