Home | About | Journals | Submit | Contact Us | Français |

**|**HHS Author Manuscripts**|**PMC2895415

Formats

Article sections

- Abstract
- 1. Introduction
- 2. SNGF Expressions for DFG
- 3. DFG with classical optical modes
- 4. DFG with entangled optical modes
- 5. Two-photon fluorescence
- 6. Conclusions
- References and links

Authors

Related links

Opt Express. Author manuscript; available in PMC 2010 July 1.

Published in final edited form as:

PMCID: PMC2895415

NIHMSID: NIHMS212384

Chemistry Department, University of California, Irvine, California 92697-2025, USA

Oleksiy Roslyak: ude.icu@kaylsoro; Shaul Mukamel: ude.icu@lemakums

The publisher's final edited version of this article is available at Opt Express

See other articles in PMC that cite the published article.

In response to quantum optical fields, pairs of molecules generate coherent nonlinear spectroscopy signals. Homodyne signals are given by sums over terms each being a product of Liouville space pathways of the pair of molecules times the corresponding optical field correlation function. For classical fields all field correlation functions may be factorized and become identical products of field amplitudes. The signal is then given by the absolute square of a susceptibility which in turn is a sum over pathways of a single molecule. The molecular pathways of different molecules in the pair are uncorrelated in this case (each path of a given molecule can be accompanied by any path of the other). However, entangled photons create an entanglement between the molecular pathways. We use the superoperator nonequlibrium Green’s functions formalism to demonstrate the signatures of this pathway-entanglement in the difference frequency generation signal. Comparison is made with an analogous incoherent two-photon fluorescence signal.

Recent progress in developing novel sources of entangled photons [1, 2, 4] had raised considerable interest in using them as a spectroscopic tool. It was predicted [5, 6] and experimentally verified [3, 7, 4] that sum-frequency generation (SFG) and two-photon fluorescence(TPF) signal intensities obtained with entangled photon pairs scale linearly rather than quadratically with the incoming field intensity [3]. The entangled photon pairs thus act as a single particle (bi-photon). For example, experiments proposed by Teich et. al., use twin entangled photons (**k**_{1}, **k**_{2}) generated by parametric-down-conversion (PDC) [8, 9, 7, 10]. The SFG [11, 12, 10, 13] signal generated with continuous-wave degenerate entangled photon pairs reveals certain off-resonant molecular energy levels (virtual-state transitions). Spectroscopic information on material optical transitions is contained in the entangled-photon absorption cross section when measured over a range of entanglement (*T _{e}*) and delay times

We have recently calculated resonant frequency-domain *incoherent* heterodyne detected nonlinear optical signals induced by entangled photons. In an incoherent process each molecule independently interacts with the optical fields and the signal scales linearly with the number of molecules *N* in the active region. Nonlinear optical signals induced by classical optical fields or quantum fields in a coherent state [15] are determined by susceptibilities *χ*^{(}^{n}^{)}(−*ω _{s}*; ±

Application of this formalism to self-heterodyne-detected (pump-probe, PP) signals [18] showed how entangled photons separate quantum pathways which scale linearly with the pump field intensity from ordinary paths which scale quadratically. At low field intensity the latter may be neglected and the spectrum is considerably simplified.

In this paper we employ the same formalism to compute homodyne detected *coherent* signals [15]. Such cooperative signals are given by sums of contributions of *pairs* of molecules and therefore scale as the number of molecular pairs *N*(*N* − 1). Incoherent signals (such as PP) reveal the entanglement of a single molecule with the optical modes, whereas coherent signals can entangle two molecules with the field.

We consider difference-frequency generation [14] carried out with entangled modes. These are generated by a PDC process and further mixed by Mach-Zehender interferometer (MZI) which controls the degree of entanglement [19]. All degrees of freedom: the PDC/MZI generated entangled modes, the spontaneously emitted **k**_{3} mode (initially in the vacuum state), and the molecular pairs are treated as coupled quantum mechanical systems. The signal generated in the **k**_{3} = **k**_{1} − **k**_{2} mode is given by a sum of products of the Liouville pathways for each molecule of the pair, multiplied by a corresponding correlation function of the field.

The signals will be displayed as (*ω*_{1},*ω*_{2}) correlation plots with the frequencies varying across the material optical transitions. When the **k**_{1} and **k**_{2} fields are classical, all relevant field correlation functions are identical and the signal is given by the absolute square of the susceptibility of a single molecule. The pathways of different molecules are not correlated in this case. However, at low pump intensity the DFG signal induced by an entangled photon pair differs from the classical one due to the *path entanglement* of molecules in each pair. The signal is given by a sum of products of the pathways in the pair, each multiplied by a corresponding entangled photon correlation functions. The signal can no longer be recast as the square of single molecule amplitudes (susceptibility). The Liouville pathways of the two molecules in the pair are correlated. This correlation is controlled by the degree of entanglement between the photons. We compare this coherent signal with its incoherent counterpart, two-photon fluorescence (TPF) [18].

We consider an assembly of *N* three-level molecules |*g*, |*e*, |*f* interacting with two incoming modes **k**_{1}, **k**_{2} to generate a coherent signal at **k**_{3} = **k**_{1} − **k**_{2}. The molecules are initially in the ground state |*g*. Modes **k**_{1}, **k**_{2} and **k**_{3} are resonant with the transitions *ω _{fg}*,

DFG: (A) wave-vector configuration of the optical fields corresponding to the phase matching **k**_{3} = **k**_{1} − **k**_{2}. (B) molecular level scheme. (C) Liouville space pathways for the pair of molecules contributing to the signal molecule *a* (C1,C2) and *b* (C1*,C2*) **...**

The light/matter interaction in the rotating-wave-approximation is:

$${H}_{\mathit{int}}=\sum _{\alpha =1,2,3}{H}_{\alpha}={E}^{\alpha}(\mathbf{r},t){V}^{\alpha ,\u2020}(\mathbf{r},t)+c.c.$$

(1)

Here the raising (positive frequency) dipole operator

$$\begin{array}{l}{V}^{\alpha ,\u2020}(\mathbf{r},t)=\sum _{j=1}^{N}\delta (\mathbf{r}-{\mathbf{R}}_{j}){e}^{-{iH}_{0}t}{V}_{j}^{\alpha ,\u2020}{e}^{i{H}_{0}t}\\ {V}_{j}^{\alpha ,\u2020}={\mu}_{ge}^{\alpha}\mid g\rangle \langle e\mid +{\mu}_{ef}^{\alpha}\mid e\rangle \langle f\mid +{\mu}_{gf}^{\alpha}\mid g\rangle \langle f\mid \end{array}$$

(2)

is written in the interaction picture where the time dependence is with respect to the molecular Hamiltonian *H*_{0}. The optical transition dipole moments of a molecule located at **R*** _{j}* are
${\mu}_{eg}^{\alpha}={\mathbf{e}}^{\alpha}\langle e\mid \mu \mid g\rangle ,{\mu}_{ef}^{\alpha}={\mathbf{e}}^{\alpha}\langle f\mid \mu \mid e\rangle ,{\mu}_{gf}^{\alpha}={\mathbf{e}}^{\alpha}\langle f\mid \mu \mid g\rangle $ projected on the optical mode |

The positive-frequency component of the optical field is:

$${E}^{\alpha}(\mathbf{r},t)=\sqrt{\frac{2\pi {\omega}_{\alpha}}{\mathrm{\Omega}}}{e}^{i{\mathbf{k}}_{\alpha}\mathbf{r}-i{\omega}_{\alpha}t}{a}_{\alpha}$$

(3)

where *a _{α}* is the photon-annihilation operator and Ω is the mode quantization volume.

We shall calculate the time-averaged photon flux in the spontaneously generated **k**_{3} mode using the SNGF formalism[15, 14, 20]. We first expand it to first order in interaction superoperator Hamiltonian w(*H*_{3})_{−} with mode **k**_{3} in eq.(1):

$${S}_{\mathit{HOM}}({\omega}_{3})=\mathfrak{J}\frac{4\pi i{\omega}_{3}}{\mathrm{\Omega}}\int \int d{\mathbf{r}}_{6}d{\mathbf{r}}_{5}\sum _{a,b\ne a}exp\phantom{\rule{0.16667em}{0ex}}(i{\mathbf{k}}_{3}({\mathbf{r}}_{6}-{\mathbf{r}}_{5}))\times \underset{-\infty}{\overset{\infty}{\int}}d{t}_{6}d{{t}_{5}}^{-i{\omega}_{3}({t}_{6}-{t}_{5})}{\langle {\langle {V}_{L}^{3}({\mathbf{r}}_{6},{t}_{6})\rangle}_{a}{\langle {V}_{R}^{3,\u2020}({\mathbf{r}}_{5},{t}_{5})\rangle}_{b}\rangle}_{F}$$

(4)

where * _{a}* and

We next expand each of the material SNGF *V _{L}*(

(5)

The factor
$\sum _{a=1}^{N}}{\displaystyle \sum _{b\ne a}}exp(i({\mathbf{k}}_{3}+{\mathbf{k}}_{2}-{\mathbf{k}}_{1})({\mathbf{R}}_{a}-{\mathbf{R}}_{b}))=N(N-1)$ is characteristic to coherent phase-matched processes [15]. Each term in the above equation is given by a product of three SNGF factors corresponding respectively to molecule *a*, molecule *b* and the optical field modes **k**_{1}, **k**_{2}. The signal mode **k**_{3} has been taken care of by our perturbative expansion (4) and need not be considered explicitly any further. This is why we have a four point rather then six point field correlation function. The operator maintains bookkeeping of the possible time orderings of the interactions.

The material SNGF’s of each term in eq. (5) can be represented by the closed time path loop diagrams (CTPL) shown in Fig. 1(C). The diagram rules are given in ref.[15].

The corresponding SNGF’s for the optical field are represented by the CTPL diagrams in Fig. 2. These will be calculated below for classical and entangled states of the **k**_{1} and **k**_{2} modes.

Assuming that modes **k**_{1} and **k**_{2} are classical continuous-waves *E ^{α}*(

$$\langle {E}^{2,\u2020}({t}_{4})\rangle \langle {E}^{1}({t}_{2})\rangle \langle {E}^{2}({t}_{3})\rangle \langle {E}^{1,\u2020}({t}_{1})\rangle =\phantom{\rule{0.16667em}{0ex}}{\mid {\mathcal{E}}_{1}\mid}^{2}{\mid {\mathcal{E}}_{2}\mid}^{2}exp\phantom{\rule{0.16667em}{0ex}}(i{\omega}_{2}({t}_{4}-{t}_{3})-i{\omega}_{1}({t}_{2}-{t}_{1}))$$

(6)

Substituting eq. (6) into (5) and performing the time integrations we obtain the standard frequency-domain expression for the DFG signal[20]:

$${S}_{\mathit{DFG}}^{(C)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})=N(N-1)\phantom{\rule{0.16667em}{0ex}}\left(\frac{4\pi {\omega}_{3}}{\mathrm{\Omega}}\right){\mid {\mathcal{E}}_{1}\mid}^{2}{\mid {\mathcal{E}}_{2}\mid}^{2}{\left|{\chi}_{+--}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\right|}^{2}\delta ({\omega}_{3}+{\omega}_{2}-{\omega}_{1})$$

(7)

where
${\chi}_{+--}^{(2)}$ is the second order susceptibility. In the *L, R* representation we have:

$${\chi}_{+--}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})=\frac{1}{2}\left[{\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})+{\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\right]$$

(8)

The susceptibility is defined by the Fourier transform of the material SNGF’s:

(9)

where *ν _{j}* =

The superoperator notation used in eq. (8) provides a compact bookkeeping device for various time orderings in the signal (7). At the end, calculations are performed by switching to Hilbert space where each material SNGF becomes a combination of ordinary time ordered correlation functions:

(10)

Hereafter we assume that all optical fields are linearly polarized and parallel. For our model
${\chi}_{+--}^{(2)}$ is given by a sum of two pathways (8). Substituting (10) into (7) we obtain the *LLL* pathway (diagram (*C*1) in Fig. 1) contribution:

$${\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})=\frac{-1}{2!}{\mu}_{ge}{\mu}_{ef}{\mu}_{fg}{I}_{ge}({\omega}_{3}){I}_{fg}({\omega}_{1})$$

(11)

Here we have introduced the retarded Green’s function for the forward in time propagation on the left branch of the loop:

$${I}_{\nu {\nu}^{\prime}}(\omega )=\frac{1}{\omega -{\omega}_{\nu {\nu}^{\prime}}+i{\gamma}_{\nu {\nu}^{\prime}}}$$

(12)

where *γ* is the dephasing rate, and *ν*, *ν*′ = {*g, e, f*}.

For the *LLR* pathway (Fig. 1(C2)) we similarly obtain:

$${\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})=\frac{1}{2!}{\mu}_{ge}{\mu}_{ef}{\mu}_{fg}{I}_{ef}({\omega}_{2}){I}_{fg}({\omega}_{1})$$

(13)

The pathways
${\chi}_{\mathit{RRR}}^{(2)}$ and
${\chi}_{\mathit{RLR}}^{(2)}$ are the complex conjugates of
${\chi}_{\mathit{LLL}}^{(2)}$ and
${\chi}_{\mathit{LRL}}^{(2)}$ respectively (Fig. 1, panels (*C*1^{}), (*C*2^{})).

Equation (7) is given by a product of the susceptibilities of pairs of molecules. The pathways of molecules *a* and *b* are not correlated, i.e. each pathway of molecule *a* can be accompanied by any pathway of molecule *b* and the response can be obtained by computing the susceptibility of a single molecule. The only signature of cooperatively in eq. (7) is the *N*(*N* −1) pre-factor. One
${\chi}_{+--}^{(2)}$ factor represents molecule *a* and its complex conjugate represents molecule *b*. Note that eq. (5) may not be generally recast as a square of a transition amplitude. This is only possible when the fields are classical.

To derive a formal expression for the DFG signal when both **k**_{1} and **k**_{2} are quantum modes we recast eq. (5) in the form:

$${S}_{\mathit{DFG}}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})=N(N-1){\omega}_{1}{\omega}_{2}{\omega}_{3}\delta ({\omega}_{3}+{\omega}_{2}-{\omega}_{1})\mathfrak{J}{\left(\frac{i\pi}{\mathrm{\Omega}}\right)}^{3}\sum _{n=1}^{4}{S}_{n}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})$$

(14)

were *S*_{1}*, S*_{2}*, S*_{3} and *S*_{4} represent the four terms of eq. (5) respectively.

Proceeding along the loop clockwise (Fig. 1 (*C*1,*C*1), Fig. 2(1)) we obtain for the first term:

$${S}_{1}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})={\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RRR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\langle {a}_{1}^{\u2020}{a}_{2}{a}_{2}^{\u2020}{a}_{1}\rangle $$

(15)

The first factor is the pathway of molecule *a* (Fig. 1(*C*1)) and the second (its complex conjugate) is the pathway of molecule *b* (Fig. 1(*C*1)); the third factor is the field correlation function deduced from diagram (1) Fig. 2. Interactions with molecule *a*(*b*) are given on the left(right) branch of diagram (1) in Fig. 2 and are marked by red (blue) arrows.

The field SNGF in the second term in eq. (14) is similarly given by the four terms corresponding to diagrams (2.1–2.4):

$${S}_{2}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})={\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\times (\langle {a}_{1}^{\u2020}{a}_{2}^{\u2020}{a}_{2}{a}_{1}\rangle +\langle {a}_{1}^{\u2020}{a}_{2}^{\u2020}{a}_{1}{a}_{2}\rangle +\langle {a}_{2}^{\u2020}{a}_{1}^{\u2020}{a}_{2}{a}_{1}\rangle +\langle {a}_{2}^{\u2020}{a}_{1}^{\u2020}{a}_{1}{a}_{2}\rangle )$$

(16)

Interactions from the left (right) now occur with both molecules, hence the various possible time orderings within each branch must be considered. Molecules *a* and *b* follow conjugate pathways.

In *S*_{3} the molecules do not follow conjugate pathways. Time ordering within each branch results in three optical SNGF for diagrams (3.1–3.3):

$${S}_{3}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})={\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})(\langle {a}_{1}^{\u2020}{a}_{2}^{\u2020}{a}_{2}{a}_{1}\rangle +\langle {a}_{1}^{\u2020}{a}_{2}^{\u2020}{a}_{1}{a}_{2}\rangle +\langle {a}_{1}^{\u2020}{a}_{2}{a}_{2}^{\u2020}{a}_{1}\rangle )$$

(17)

Finally *S*_{4} is represented by diagrams (4.1–4.3):

$${S}_{4}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})={\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RRR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})(\langle {a}_{1}^{\u2020}{a}_{2}{a}_{2}^{\u2020}{a}_{1}\rangle +\langle {a}_{1}^{\u2020}{a}_{2}^{\u2020}{a}_{2}{a}_{1}\rangle +\langle {a}_{2}^{\u2020}{a}_{1}^{\u2020}{a}_{2}{a}_{1}\rangle )$$

(18)

To compute the optical field correlation functions in eq. (15–18) we must specify the initial state of the **k**_{1} and **k**_{2} modes.

We shall assume entangled photon pairs created by PDC of a single pump beam from gaining in a birefringent crystal[14]. The two beams then pass through the Mach-Zehender interferometer made of two beam-splitters which mix the radiation modes (Fig. 3). The phase shift in one of the interferometer arms controls the degree of entanglement. The PDC/MZI apparatus setup generates new modes *a*_{1}*, a*_{2} which are related to the original (canonical) modes *a*′_{1}*, a*′_{2} by the non-unitary transformation[19]:

$$\begin{array}{l}{a}_{1}=\frac{1}{2}[(1-{e}^{i\phi})(U{{a}^{\prime}}_{1}+V{{a}^{\prime}}_{2}^{\u2020})-i(1+{e}^{i\phi})(U{{a}^{\prime}}_{2}+V{{a}^{\prime}}_{1}^{\u2020})]\\ {a}_{2}=\frac{1}{2}[-i(1+{e}^{i\phi})(U{{a}^{\prime}}_{1}+V{{a}^{\prime}}_{2}^{\u2020})-(1-{e}^{i\phi})(U{{a}^{\prime}}_{2}+V{{a}^{\prime}}_{1}^{\u2020})]\end{array}$$

(19)

Nonlinear spectroscopy with entangled photons. A non-linear parametric down conversion *χ* ^{(2)} crystal PDC is used to obtain entangled photon pairs from the classical pump beam by parametric down conversion. BS are balanced 50 : 50 beam splitters. **...**

Here *V* = −*i*sinh *ν*, *U* = cosh *ν*. The parameter *ν*~ *χ*^{(2)} * _{p}L* is determined by the crystal non-linearity

The output field of the PDC/MZI setup is given by a product of two vacuum states in the original canonical basis |0′ = |0′_{1}|0′_{2}. This serves as the input for the homodyne-detected DFG experiment. We only retain the terms that scale as |* _{p}*|

Pathways (1), (3.3), (4.1) in Fig. 2 contain the field correlation functions $\langle {a}_{1}^{\u2020}{a}_{2}{a}_{2}^{\u2020}{a}_{1}\rangle ,\langle {a}_{1}^{\u2020}{a}_{2}{a}_{2}^{\u2020}{a}_{1}\rangle ,\langle {a}_{1}^{\u2020}{a}_{2}{a}_{2}^{\u2020}{a}_{1}\rangle $. Proceeding clockwise we have a sequence of photon absorption, emission, absorption, emission in all paths. By computing these expectation values with respect to the input state |0′ using the transformation (19) we find that they are all identical:

$$\langle {a}^{\u2020}{aa}^{\u2020}a\rangle ={\mid V\mid}^{4}(\frac{3}{4}+\frac{1}{2}cos2\phi )$$

(20)

The field correlation functions for all other pathways are absorption, absorption, emission, emission type: $\langle {a}_{1}^{\u2020}{a}_{2}^{\u2020}{a}_{2}{a}_{1}\rangle ,\langle {a}_{1}^{\u2020}{a}_{2}^{\u2020}{a}_{1}{a}_{2}\rangle ,\langle {a}_{2}^{\u2020}{a}_{1}^{\u2020}{a}_{2}{a}_{1}\rangle ,\langle {a}_{2}^{\u2020}{a}_{1}^{\u2020}{a}_{1}{a}_{2}\rangle $ and can be calculated similarly:

$$\langle {a}^{\u2020}{a}^{\u2020}aa\rangle ={\mid V\mid}^{2}\left[(\frac{1}{2}+\frac{1}{2}cos2\phi )+{\mid V\mid}^{2}(\frac{3}{2}+\frac{1}{2}cos2\phi )\right]$$

(21)

For a maximally-entangled state ( = 0) and at sufficiently low pump intensity (|*V*|^{2} 1) the signal is given by *S*_{2} + *S*_{3} + *S*_{4} (eq. (16), (17), (18)) with pathways ((2.1–2.4), (3.1), (3.2), (4.2), (4.3)) in Fig. 3 :

$${S}_{2}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\sim 4{\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\mid {\mathcal{E}}_{p}\mid}^{2}$$

(22)

$${S}_{3}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\sim 2{\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\mid {\mathcal{E}}_{p}\mid}^{2}$$

(23)

$${S}_{4}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\sim 2{\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RRR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\mid {\mathcal{E}}_{p}\mid}^{2}$$

(24)

All of these pathways contain the same field factor (eq.(21)).

Substituting eq. (22), (23), (24) into (14) and noting that ${S}_{4}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})={S}_{3}^{\u2605}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})$ we obtain the DFG signal induced by entangled photons at low pumping intensity:

$${S}_{\mathit{DFG}}^{(E)}({\omega}_{1},{\omega}_{2})\sim N(N-1){\mid {\mathcal{E}}_{p}\mid}^{2}\times \mathfrak{R}[{\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})+{\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})]$$

(25)

Unlike the classical field expression (7), entangled photons create entanglement between pathways of pairs of molecules. Photon absorption (emission) by molecule *a* is followed by emission (absorption) by molecule *b* along the loop (diagrams (2.1–2.4), (3.1), (3.2), (4.2), (4.3) in Fig. 3). This constraints the pathways of the molecules in the pair. And the signal is not given by the square of a transition amplitude.

For comparison, in Appendix A, we calculate the signal assuming that both modes **k**_{1} and **k**_{2} are in a coherent state (CS). For strong fields we recover the classical result in eq. (7). When |_{2}|^{2} |_{1}|^{2}, only pathways (1), (3.3), (4.1) in Fig. 3 contribute to the signal. From eq. (32), (33) and (34) we obtain for the signal:

$${S}_{\mathit{DFG}}^{(CS)}({\omega}_{1},{\omega}_{2})\sim N(N-1){\mid {\mathcal{E}}_{1}\mid}^{2}\times \mathfrak{R}[{\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})+{\chi}_{\mathit{RRR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})]$$

(26)

The signals (26) and (25) are both different from the classical signal. The first term (non-conjugate molecular pathways) in these expressions is identical, and difference comes from the second term where the molecules of the pair follow their conjugate pathways.

The following simulation illustrates the signatures of pathway entanglement. In our model the single exciton manifold |*e* has three states *ω _{eg}* = {0.5, 0.53, 0.56} in dimensionless units. The doubly-excited manifold |

Panel (A) in Fig. 4 shows the DFG signal (7) for classical **k**_{1}, **k**_{2} modes. The three peaks at *ω*_{2} < 0.5 are determined by the *S*_{1} term. Molecules *a* and *b* interact with optical fields along the pathway
${\chi}_{\mathit{LLL}}^{(2)}$ and its conjugate
${\chi}_{\mathit{RRR}}^{(2)}$ pathway respectively. The resonances are observed at ω_{1} − ω_{2} ≈ ω* _{eg}*, ω

Panels (A–C) are 2D spectra of coherent DFG signals. (A) generated by classical fields, (B) generated by maximally entangled photons (PDC/MZI) in the low pump intensity limit. (C) generated by fields in a coherent state of low intensity. (D) the **...**

The resonances at *ω*_{2} > 0.5 are given by the *S*_{2} term, which describes the coherent evolution of two molecules along the two conjugate pathways
${\chi}_{\mathit{LRL}}^{(2)},{\chi}_{\mathit{RLR}}^{(2)}$. This gives resonances at *ω*_{2} ≈ *ω _{eg}*,

When the DFG signal is generated by maximally entangled photons (PDC/MZI) at low pump intensity the contribution from *S*_{1} term and the corresponding peaks are suppressed as shown in Fig. 4(B). Similarly *S*_{2} is suppressed if modes **k**_{1} and **k**_{2} are weak intensity coherent states (Fig. 4(C)). The suppressed cross-peaks are the signature of the entanglement between the pathways of the molecular pair (See Fig. 5). However, as we show in the next section, the DFG signal (14) with CS becomes a coherent analog of two photon fluorescence (scales as ~ *N*(*N* − 1) rather then as ~ *N*). They both show the same resonances in the spectral region of interest *ω*_{2} < 0.5, *ω*_{1} < 1, where the contribution from the conjugate molecular pathways is dominating (See Fig. 4(C) and (D)).

We now compare the coherent DFG signals (7), (25), (26) with an analogous incoherent two-photon fluorescence signal where photons are spontaneously emitted in mode **k**_{3} which is initially in the vacuum state and populated by interaction with classical or quantum modes **k**_{1}, **k**_{2}.

The incoherent signal can be expanded to first order in (*H*_{3})_{−}:

(27)

This equation is analogous to (4), but with all interactions now occurring with the same molecule *a*. Both positive and negative frequency components of modes **k**_{1} and **k**_{2} contribute to the signal. Equation (27) can be expanded to second order in (*H*_{1})_{−}, and (*H*_{2})_{−}. By setting *ω*_{1} ≈ *ω _{fg}* we obtain the incoherent phase-insensitive TPF signal:

(28)

Comparing with eq. (5) we note that both signals are given by the product of a four-point optical and a six-point molecular SNGF’s. Recall that, for the coherent signal in eq. (5) the latter can be factorized into a product of two three-point SNGF’s corresponding to the molecular pairs.

A single loop diagram (Fig. 6(A)) now describes both material and optical SNGF, compared to four molecular and eleven optical pathways required for coherent DFG. The TPF signal is:

$${S}_{\mathit{TPF}}({\omega}_{1},{\omega}_{2})=NA\frac{\pi {\omega}_{3}}{\mathrm{\Omega}}\mathfrak{J}{\chi}_{\mathit{LLLRRR}}^{(5)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1},{\omega}_{2},{\omega}_{3},-{\omega}_{1})$$

(29)

(A) The incoherent TPF pathway contributing at *ω*_{3} ≈ *ω*_{1} − *ω*_{2} resonance. Mode **k**_{3} is spontaneously generated by classical modes **k**_{1}, **k**_{2}. (B) CTPL diagram for conventional incoherent two-photon emitted fluorescence (TPEF) **...**

Expansion in the molecular eigenstates yields:

$$\mathfrak{J}{\chi}_{\mathit{LLLRRR}}^{(5)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1},{\omega}_{2},{\omega}_{3},-{\omega}_{1})=\frac{1}{5!}{\mid {\mu}_{ge}^{x}{\mu}_{ef}^{x}{\mu}_{fg}^{y}\mid}^{2}\delta ({\omega}_{1}-{\omega}_{2}-{\omega}_{3}-{\omega}_{g{g}^{\prime}}){\mid \frac{1}{{\omega}_{1}-{\omega}_{fg}+i{\gamma}_{fg}}\frac{1}{{\omega}_{1}-{\omega}_{2}-{\omega}_{eg}+i{\gamma}_{eg}}\mid}^{2}$$

(30)

The signal amplitude *A* depends on initial state of the modes **k**_{1} and **k**_{2}. When all modes are classical, the optical SNGF is given by eq. (6), and *A* = |_{1}|^{2}|_{2}|^{2}. When **k**_{1} and **k**_{2} are the entangled modes created by the PDC/MZI (19) we have *A* = |* _{p}*|

Using a coherent optical mode **k**_{1}, and low intensity coherent mode **k**_{2}, we obtain the conventional two-photon-emitted fluorescence (TPEF)[18]. This signal (29) is also described by CTPL shown in Fig. 6(B), but it now scales linearly with the intensity of **k**_{1} mode *A* = |_{1}|^{2}.

Equation (30) shows that TPF signals have resonances at *ω*_{1} − *ω*_{2} ≈ *ω _{eg}, ω*

We have used the superoperator nonequlibrium Green’s functions formalism to recast the coherent DFG in terms of products of quantum pathways for pairs of molecules and optical field correlation functions. The DFG signal is given by the homodyne-detected time averaged photon flux in the spontaneously generated mode. When the signal is generated by classical optical fields the molecules follow independent Liouville pathways. However entangled fields can entangle the pathways of both molecules. At low field intensity, coherent optical fields and MZI/PDC entangled photons produce complimentary signals with signatures of induced entanglement between the molecular pathways. We further compared the coherent signal with its incoherent analogue: two-photon fluorescence (TPF). The latter is given by single molecule Liouville space pathways multiplied by optical correlation functions. For classical optical fields the coherent and incoherent signals overlap spectrally and provide the same spectroscopic information about the matter. Non-classical optical fields may be used to spectrally separate the two contributions. Entangled photon-pairs can spectrally separate the coherent and incoherent signals. Photon entanglement further induces entanglement between the molecular pathways. It allows to study collective effects in the molecular response for systems with a small number of optically active molecules. However, not all coherent signals generated by entangled photons show the induced entanglement between the molecular pathways. For instance in the homodyne detected sum-frequency generation technique each molecule of the pair follow mutually conjugated pathways so that the pair pathway is fully determined by a single molecule path (See Appendix B). Note that eq. (5) may not be generally recast as the modulus square of a transition amplitude. This is only true either for classical fields (7) or for techniques which involve a single pathway for each molecule (such as SFG). The latter signal generated by a pair of entangled photons may be calculated by means of standard perturbation theory for the transition amplitude [13] and the SNGF formalism is not necessary in this case.

The quantum states of the radiation field in modes **k**_{1}, **k**_{2} that most closely resemble classical field are coherent states |*β*_{1}, |*β*_{2} given by eigenstates of the photon annihilation operators: *a*_{1}|*β*_{1} = *β*_{1}|*β*_{1},*a*_{2}|*β*_{2} = *β*_{2}|*β*_{2}. The optical correlation functions we shall calculate with respect to this initial coherent state |*t* = −∞ = |*β*_{1}|*β*_{2}.

Using this state the first contribution to the signal (14) becomes:

$${S}_{1}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})={\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RRR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})({\mid {\beta}_{1}\mid}^{2}+{\mid {\beta}_{1}\mid}^{2}{\mid {\beta}_{2}\mid}^{2})$$

(31)

The complex field amplitude is given by
$\mathcal{E}=\sqrt{2\pi \omega /\mathrm{\Omega}}\beta $. The optical field factor in (31) when substituted into (14) contains both linear |_{1}|^{2} and quadratic terms |_{2}|^{2} in the field intensities.

The second term in the signal eq.(14) scales with the product of intensities:

$${S}_{2}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})=4{\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\mid {\beta}_{1}\mid}^{2}{\mid {\beta}_{2}\mid}^{2}$$

(32)

The remaining two contributions to this signal are:

$${S}_{3}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\sim 2{\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RLR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})({\mid {\beta}_{1}\mid}^{2}+3{\mid {\beta}_{1}\mid}^{2}{\mid {\beta}_{2}\mid}^{2})$$

(33)

$${S}_{4}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})\sim 2{\chi}_{\mathit{LRL}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1}){\chi}_{\mathit{RRR}}^{(2)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1})({\mid {\beta}_{1}\mid}^{2}+3{\mid {\beta}_{1}\mid}^{2}{\mid {\beta}_{2}\mid}^{2})$$

(34)

For strong fields (|*β*| 1) the linear terms may be neglected and from (14) we recover the classical result (7). When |_{2}|^{2} |_{1}|^{2} the signal (14) becomes a coherent analog of TPF (which scales with *N*(*N* − 1) rather then *N*).

Two-photon induced fluorescence (TPIF) is the incoherent analogue of the coherent SFG signal. When generated by classical fields, both coherent and incoherent processes spontaneously emit at *ω*_{3} ≈ *ω*_{1} + *ω*_{2}. The coherent SFG signal is given by
${S}_{\mathit{SFG}}\sim N(N-1)A{\mid {\chi}_{\mathit{LLL}}^{(2)}(-{\omega}_{3};{\omega}_{2},{\omega}_{1})\mid}^{2}$ and scales with the signal amplitude *A* = |* _{p}*|

Modes **k**_{1}, **k**_{2} also generate an incoherent TPF signal as can be seen from the CTPL shown in Fig. 6(C):

$${S}_{\mathit{TPF}}^{(E)}({\omega}_{1},{\omega}_{2})\sim N\frac{\pi {\omega}_{3}}{\mathrm{\Omega}}\mathfrak{J}{\chi}_{\mathit{LLLRRR}}^{(5)}(-{\omega}_{3};{\omega}_{2},{\omega}_{1},{\omega}_{2},{\omega}_{3},-{\omega}_{1})$$

(35)

This has the same signal amplitudes as for the SFG but with different material SNGF:

$$\mathfrak{J}{\chi}_{\mathit{LLLRRR}}^{(5)}(-{\omega}_{3};-{\omega}_{2},{\omega}_{1},{\omega}_{2},{\omega}_{3},-{\omega}_{1})=\frac{1}{5!}{\mid {\mu}_{ge}^{x}{\mu}_{ef}^{x}{\mu}_{fg}^{y}\mid}^{2}\delta ({\omega}_{1}+{\omega}_{2}-{\omega}_{3}-{\omega}_{g{g}^{\prime}}){\mid \frac{1}{{\omega}_{1}-{\omega}_{eg}+i{\gamma}_{fg}}\frac{1}{{\omega}_{1}+{\omega}_{2}-{\omega}_{fg}+i{\gamma}_{fg}}\mid}^{2}$$

For a small number of the molecules, incoherent TPF and coherent SFG signals show the same resonances and may have compatible magnitudes. It is not possible to separate them spectrally by manipulating the quantum optical fields since each molecule in a pair can undergo a single pathway.

This work was supported by the National Science Foundation Grant CHE-0745892 and with the National Institutes of Health Grant GM59230.

1. Turchette QA, Wood CS, King BE, Myatt CJ, Leibfried D, Itano WM, Monroe C, Wineland DJ. Deterministic Entanglement of Two Trapped Ions. Phys Rev Lett. 1998;81:3631.

2. Walther P, Pan J, Aspelmeyer M, Ursin R, Gasparoni S, Zeilinger A. De Broglie wavelength of a nonlocal four-photon state. Nature. 2004;429:158. [PubMed]

3. Javanainen J, Gould P. Linear intensity dependence of a two-photon transition rate. Phys Rev A. 1990;41:5088. [PubMed]

4. Dayan B. Theory of two-photon interactions with broadband down-converted light and entangled photons. Phys Rev A. 2007;76:43813.

5. Lee D, Goodson T. Entangled Photon Absorption in an Organic Porphyrin Dendrimer. J Phys Chem B. 2006;110:25582. [PubMed]

6. Pe’er A, Dayan B, Friesem AA, Silberberg Y. Temporal Shaping of Entangled Photons. Phys Rev Lett. 2005;94:073601. [PubMed]

7. Hong CK, Mandel L. Theory of parametric frequency down conversion of light. Phys Rev A. 1985;31:2409. [PubMed]

8. Mandel L, Wolf E. Optical Coherence and Quantum Optics. Cambridge University Press; 1995.

9. Gerry C, Knight P. Introductory Quantum Optics. Cambridge University Press; 2005.

10. Fei H, Jost B, Popescu S, Saleh B, Teich M. Entanglement-Induced Two-Photon Transparency. Phys Rev Lett. 1997;78:1679–1682.

11. Lissandrin F, Saleh BEA, Sergienko AV, Teich MC. Quantum theory of entangled-photon photoemission. Phys Rev B. 2004;69:165317.

12. Teich M, Saleh B. Entangled-photon microscopy, spectroscopy, and display. US Patent. 5, 796,477 1998.

13. Saleh B, Jost B, Fei H, Teich M. Entangled-Photon Virtual-State Spectroscopy. Phys Rev Lett. 1998;80:3483.

14. Roslyak O, Marx C, Mukamel S. A unified description of sum frequency generation, parametric down conversion and two photon fluorescence. J Mol Phys. 2008 (submitted) [PMC free article] [PubMed]

15. Marx C, Harbola U, Mukamel S. Nonlinear optical spectroscopy of single, few, and many molecules: Nonequilibrium Green’s function QED approach. Phys Rev A. 2008;77:22110. [PMC free article] [PubMed]

16. Glauber R. The photon theory of optical coherence. Phys Rev. 1963;130:2529.

17. Glauber R. Quantum Theory of Optical Coherence: Selected Papers and Lectures. Wiley-VCH; 2007.

18. Roslyak O, Marx C, Mukamel S. Manipulating quantum pathways of matter with entangled photons. Phys Rev B. 2008 (submitted) [PMC free article] [PubMed]

19. Nagasako EM, Bentley SJ, Boyd RW, Agarwal GS. Nonclassical two-photon interferometry and lithography with high-gain parametric amplifiers. Phys Rev A. 2001;64:043802.

20. Mukamel S. Principles of nonlinear optical spectroscopy. Oxford University Press; New York: 1995.

PubMed Central Canada is a service of the Canadian Institutes of Health Research (CIHR) working in partnership with the National Research Council's national science library in cooperation with the National Center for Biotechnology Information at the U.S. National Library of Medicine(NCBI/NLM). It includes content provided to the PubMed Central International archive by participating publishers. |