Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

arXiv:0711.2094 · Physical Review A

Nonlinear optical spectroscopy of single, few, and many molecules: Nonequilibrium Green’s function QED approach

Christoph A. Marx, Upendra Harbola, Shaul Mukamel

Published Feb 19, 2008• 75 citations
arXivHTMLPDF

Abstract

Nonlinear optical signals from an assembly of N noninteracting particles consist of an incoherent and a coherent component, whose magnitudes scale ~ N and ~ N(N - 1), respectively. A unified microscopic description of both types of signals is developed using a quantum electrodynamical (QED) treatment of the optical fields. Closed nonequilibrium Green's function expressions are derived that incorporate both stimulated and spontaneous processes. General (n + 1)-wave mixing experiments are discussed as an example of spontaneously generated signals. When performed on a single particle, such signals cannot be expressed in terms of the nth order polarization, as predicted by the semiclassical theory. Stimulated processes are shown to be purely incoherent in nature. Within the QED framework, heterodyne-detected wave mixing signals are simply viewed as incoherent stimulated emission, whereas homodyne signals are generated by coherent spontaneous emission.

DOI
10.1103/physreva.77.022110

Related papers

Quantum-Field Effects in Ultrafast Nonlinear X-Ray and Optical Spectroscopy of Molecules

Kochise Bennett

Spectroscopy, the study of matter via its interactions with light, is a vast subject that includes many of humanity's principle means of probing the fundamental structure of matter. Though usually understood from the perspective of classical light, important effects arise due to the quantum nature of the electromagnetic field. Additionally, the quantum vacuum can serve as an effective couple between molecules in the system, generating many-body interactions and cooperative processes in the material. While many techniques are well-described classically, quantum-field corrections can dominate the desired signals in certain cases, such as cascading in higher-order n-wave mixing signals, and are key for experimental interpretation. Even spontaneous emission and light scattering are best understood from the perspective of quantum fields. In this thesis, we utilize a systematic procedure, based on the density matrix in Liouville space, to give a rigorous description of elementary quantum-field effects in nonlinear spectroscopy, with specific examples made to ultrafast x-ray and optical techniques.

•Jan 1, 2017•0 citations

Quantum Optics. II. Description of a Mode

I. R. Senitzky

Conceptual problems in quantum optics are investigated by a study of the physical significance of various types of description of the field of a single mode. The descriptions are examined through the effect of the field on matter. Both undamped and damped modes are considered, the descriptions being those of various degrees of precision in classical and quantum-mechanical formalisms. The matter consists of a large number of "molecules," and the interaction is studied by means of low-order perturbation theory. Formal expressions are obtained for the energy interchange between field and molecules in terms of the zeroth-order (uncoupled) operators, with the effect of the commutation properties of the field variables explicitly separated from that of the excitation of the field, in second order. The significance of taking expectation values of the operator results is discussed, and it is concluded that this procedure is justified only when the experiment under consideration involves an averaging process; thus, the molecular variables should be averaged, but not necessarily those of the field. Conditions under which the averaging process is justified are considered, and it is reasoned that, when such a process is not justified, a statistical description of the field can result only in a statistical description of the interaction process. Results of various field descriptions are compared, and it is shown that for induced emission and for spontaneous emission from coherently oscillating molecules, classical and quantum-mechanical fields are equivalent. However, for a self-consistent theory of spontaneous emission from molecules that are not oscillating coherently, the quantum-mechanical commutation properties of the field are essential if the molecules are treated quantum-mecahnically, and the field must be treated classically if the molecules are treated classically; the type of description used for the excitation of the field is inconsequential. Photoelectric emission is examined, and, within the approximation framework used, shown to be accurately described by a classical treatment of the field. It is pointed out that there does not necessarily exist a connection between "photon statistics," that is, the statistics associated with an ensemble of fields, and photocurrent fluctuations in one or more detectors coupled to the same field.

Physical Review•Oct 25, 1968•4 citations

RESEARCH ARTICLE A unified description of sum frequency generation, parametric down conversion and two-photon fluorescence

Oleksiy Roslyak, Shaul Mukamel

A superoperator non-equilibrium Green’s function formalism is presented for computing nonlinear optical processes involving any combination of classical and quantum optical modes. Closed correlation-function expressions based on superoperator time-ordering are derived for the combined effects of causal response and non-causal spontaneous fluctuations. Coherent three wave mixing (sum frequency generation and parametric down conversion) involving one and two quantum optical modes, respectively, are compared with their incoherent counterparts: two-photon-induced fluorescence and two-photon-emitted fluorescence.

•Jan 1, 2009•0 citations

Quantum Theory of Optical Homodyne and Heterodyne Detection

Matthew J. Collett, R. Loudon, Crispin W. Gardiner

The theory of balanced homodyne and heterodyne detection is developed for inputs in which the signal field is in an arbitrary quantum state and the local-oscillator field is in a highly excited coherent state. Exact expressions are derived for the photocount moment-generating functions in the special case of a coherent signal. For more general signals, the first two moments of the photocount probability distribution are determined. The moments are evaluated for the examples of a coherent signal with a chaotic noise component, and for squeezed light derived from a degenerate and from a non-degenerate parametric amplifier. The corresponding moments for direct detection are obtained so that comparisons can be made. The Kelley-Kleiner photocount distribution formula is adapted to balanced detection schemes. Light beams are characterized throughout by their energy fluxes, and the theory accordingly describes steady-state experiments.

Journal of Modern Optics•Jun 1, 1987•171 citations

Discriminating cascading processes in nonlinear optics: A QED analysis based on their molecular and geometric origin

Kochise Bennett, Vladimir Chernyak, Shaul Mukamel

The nonlinear optical response of a system of molecules often contains contributions whereby the products of lower-order processes in two separate molecules give signals that appear on top of a genuine direct higher-order process with a single molecule. These many-body contributions are known as cascading and complicate the interpretation of multidimensional stimulated Raman and other nonlinear signals. In a quantum electrodynamic treatment, these cascading processes arise from second-order expansion in the molecular coupling to vacuum modes of the radiation field, i.e., single-photon exchange between molecules, which also gives rise to other collective effects. We predict the relative phase of the direct and cascading nonlinear signals and its dependence on the microscopic dynamics as well as the sample geometry. This phase may be used to identify experimental conditions for distinguishing the direct and cascading signals by their phase. Higher-order cascading processes involving the exchange of several photons between more than two molecules are discussed.

arXiv:1702.00756•Physical Review A•Mar 29, 2017•5 citations

Photon statistics: Nonlinear spectroscopy of single quantum systems

Shaul Mukamel

A unified description of multitime correlation functions, nonlinear response functions, and quantum measurements is developed using a common generating function which allows a direct comparison of their information content. A general formal expression for photon counting statistics from single quantum objects is derived in terms of Liouville-space correlation functions of the material system by making a single assumption that a spontaneous emission is described by a master equation.

arXiv:cond-mat/0307768•Physical Review A•Dec 24, 2003•60 citations
Nonlinear optical signals from an assembly of N noninteracting particles consist of an incoherent and a coherent component, whose magnitudes scale ~ N and ~ N(N - 1), respectively. A unified microscopic description of both types of signals is developed using a quantum electrodynamical (QED) treatment of the optical fields. Closed nonequilibrium Green's function expressions are derived that incorporate both stimulated and spontaneous processes. General (n + 1)-wave mixing experiments are discussed as an example of spontaneously generated signals. When performed on a single particle, such signals cannot be expressed in terms of the nth order polarization, as predicted by the semiclassical theory. Stimulated processes are shown to be purely incoherent in nature. Within the QED framework, heterodyne-detected wave mixing signals are simply viewed as incoherent stimulated emission, whereas homodyne signals are generated by coherent spontaneous emission.
Spectroscopy, the study of matter via its interactions with light, is a vast subject that includes many of humanity's principle means of probing the fundamental structure of matter. Though usually understood from the perspective of classical light, important effects arise due to the quantum nature of the electromagnetic field. Additionally, the quantum vacuum can serve as an effective couple between molecules in the system, generating many-body interactions and cooperative processes in the material. While many techniques are well-described classically, quantum-field corrections can dominate the desired signals in certain cases, such as cascading in higher-order n-wave mixing signals, and are key for experimental interpretation. Even spontaneous emission and light scattering are best understood from the perspective of quantum fields. In this thesis, we utilize a systematic procedure, based on the density matrix in Liouville space, to give a rigorous description of elementary quantum-field effects in nonlinear spectroscopy, with specific examples made to ultrafast x-ray and optical techniques.
Conceptual problems in quantum optics are investigated by a study of the physical significance of various types of description of the field of a single mode. The descriptions are examined through the effect of the field on matter. Both undamped and damped modes are considered, the descriptions being those of various degrees of precision in classical and quantum-mechanical formalisms. The matter consists of a large number of "molecules," and the interaction is studied by means of low-order perturbation theory. Formal expressions are obtained for the energy interchange between field and molecules in terms of the zeroth-order (uncoupled) operators, with the effect of the commutation properties of the field variables explicitly separated from that of the excitation of the field, in second order. The significance of taking expectation values of the operator results is discussed, and it is concluded that this procedure is justified only when the experiment under consideration involves an averaging process; thus, the molecular variables should be averaged, but not necessarily those of the field. Conditions under which the averaging process is justified are considered, and it is reasoned that, when such a process is not justified, a statistical description of the field can result only in a statistical description of the interaction process. Results of various field descriptions are compared, and it is shown that for induced emission and for spontaneous emission from coherently oscillating molecules, classical and quantum-mechanical fields are equivalent. However, for a self-consistent theory of spontaneous emission from molecules that are not oscillating coherently, the quantum-mechanical commutation properties of the field are essential if the molecules are treated quantum-mecahnically, and the field must be treated classically if the molecules are treated classically; the type of description used for the excitation of the field is inconsequential. Photoelectric emission is examined, and, within the approximation framework used, shown to be accurately described by a classical treatment of the field. It is pointed out that there does not necessarily exist a connection between "photon statistics," that is, the statistics associated with an ensemble of fields, and photocurrent fluctuations in one or more detectors coupled to the same field.
A superoperator non-equilibrium Green’s function formalism is presented for computing nonlinear optical processes involving any combination of classical and quantum optical modes. Closed correlation-function expressions based on superoperator time-ordering are derived for the combined effects of causal response and non-causal spontaneous fluctuations. Coherent three wave mixing (sum frequency generation and parametric down conversion) involving one and two quantum optical modes, respectively, are compared with their incoherent counterparts: two-photon-induced fluorescence and two-photon-emitted fluorescence.
The theory of balanced homodyne and heterodyne detection is developed for inputs in which the signal field is in an arbitrary quantum state and the local-oscillator field is in a highly excited coherent state. Exact expressions are derived for the photocount moment-generating functions in the special case of a coherent signal. For more general signals, the first two moments of the photocount probability distribution are determined. The moments are evaluated for the examples of a coherent signal with a chaotic noise component, and for squeezed light derived from a degenerate and from a non-degenerate parametric amplifier. The corresponding moments for direct detection are obtained so that comparisons can be made. The Kelley-Kleiner photocount distribution formula is adapted to balanced detection schemes. Light beams are characterized throughout by their energy fluxes, and the theory accordingly describes steady-state experiments.
The nonlinear optical response of a system of molecules often contains contributions whereby the products of lower-order processes in two separate molecules give signals that appear on top of a genuine direct higher-order process with a single molecule. These many-body contributions are known as cascading and complicate the interpretation of multidimensional stimulated Raman and other nonlinear signals. In a quantum electrodynamic treatment, these cascading processes arise from second-order expansion in the molecular coupling to vacuum modes of the radiation field, i.e., single-photon exchange between molecules, which also gives rise to other collective effects. We predict the relative phase of the direct and cascading nonlinear signals and its dependence on the microscopic dynamics as well as the sample geometry. This phase may be used to identify experimental conditions for distinguishing the direct and cascading signals by their phase. Higher-order cascading processes involving the exchange of several photons between more than two molecules are discussed.