Molecular vibroic spectroscopy, where the transitions involve non-trivial Bosonic correlation due to the Duschinsky Rotation, is strongly believed to be in a similar complexity class as Boson Sampling. At finite temperature, the problem is represented as a Boson Sampling experiment with correlated Gaussian input states. This molecular problem with temperature effect is intimately related to the various versions of Boson Sampling sharing the similar computational complexity. Here we provide a full description to this relation in the context of Gaussian Boson Sampling. We find a hierarchical structure, which illustrates the relationship among various Boson Sampling schemes. Specifically, we show that every instance of Gaussian Boson Sampling with an initial correlation can be simulated by an instance of Gaussian Boson Sampling without initial correlation, with only a polynomial overhead. Since every Gaussian state is associated with a thermal state, our result implies that every sampling problem in molecular vibronic transitions, at any temperature, can be simulated by Gaussian Boson Sampling associated with a product of vacuum modes. We refer such a generalized Gaussian Boson Sampling motivated by the molecular sampling problem as Vibronic Boson Sampling.
Molecular vibroic spectroscopy, where the transitions involve non-trivial Bosonic correlation due to the Duschinsky Rotation, is strongly believed to be in a similar complexity class as Boson Sampling. At finite temperature, the problem is represented as a Boson Sampling experiment with correlated Gaussian input states. This molecular problem with temperature effect is intimately related to the various versions of Boson Sampling sharing the similar computational complexity. Here we provide a full description to this relation in the context of Gaussian Boson Sampling. We find a hierarchical structure, which illustrates the relationship among various Boson Sampling schemes. Specifically, we show that every instance of Gaussian Boson Sampling with an initial correlation can be simulated by an instance of Gaussian Boson Sampling without initial correlation, with only a polynomial overhead. Since every Gaussian state is associated with a thermal state, our result implies that every sampling problem in molecular vibronic transitions, at any temperature, can be simulated by Gaussian Boson Sampling associated with a product of vacuum modes. We refer such a generalized Gaussian Boson Sampling motivated by the molecular sampling problem as Vibronic Boson Sampling.
Boson Sampling represents a class of physical processes potentially intractable for classical devices to simulate. The Gaussian extension of Boson Sampling remains a computationally hard problem, where the input state is a product of uncorrelated Gaussian modes. Besides, motivated by molecular spectroscopy, Vibronic Boson Sampling involves operations that can generate Gaussian correlation among different Boson modes. Therefore, Gaussian Boson Sampling is a special case of Vibronic Boson Sampling. However, this does not necessarily mean that Vibronic Boson Sampling is more complex than Gaussian Boson Sampling. Here we develop a hierarchical structure to show how the initial correlation in Vibronic Boson Sampling can be absorbed in Gaussian Boson Sampling with ancillary modes and in a scattershot fashion. Since every Gaussian state is associated with a thermal state, our result implies that every sampling problem in molecular vibronic transitions, at any temperature, can be simulated by Gaussian Boson Sampling associated with a product of vacuum modes.
Boson sampling (BS) is a multimode linear optical problem that is expected to be intractable on classical computers. It was recently suggested that molecular vibronic spectroscopy (MVS) is computationally as complex as BS. In this review, we discuss the correspondence relation between BS and MVS and briefly introduce the experimental demonstrations of the molecular spectroscopic process using quantum devices. The similarity of the two theories results in another BS setup, which is called "vibronic BS". The hierarchical structure of vibronic BS, which includes the original BS and other Gaussian BS, is also explained.
Abstract Simulating vibronic spectra is a central task in physical chemistry, offering insight into important properties of molecules. Recently, it has been experimentally demonstrated that photonic platforms based on Gaussian boson sampling (GBS) are capable of performing these simulations. However, whether an actual GBS approach is required depends on the molecule under investigation. To develop a better understanding on the requirements for simulating vibronic spectra, we explore connections between theoretical approximations in physical chemistry and their photonic counterparts. Mapping these approximations into photonics, we show that for certain molecules the GBS approach is unnecessary. We place special emphasis on the linear coupling approximation, which in photonics corresponds to sampling from multiple coherent states. By implementing this approach in experiments, we demonstrate improved similarities over previously reported GBS results for formic acid and identify the particular attributes that a molecule must exhibit for this, and other approximations, to be valid. These results highlight the importance in forming deeper connections between traditional methods and photonic approaches.
Boson Sampling is a prominent candidate for the demonstration of quantum computational advantage but it remains unclear whether a large-scale boson sampler can find useful computational applications. The challenge is that to use a boson sampler to estimate, for example, a physical observable, it is necessary to coarse grain the outcome distribution, owing to the exponential size of the outcome space and the anti-concentration properties of the Boson Sampling distribution. In this work, we analyse the complexity of a specific type of coarse-graining of Boson Sampling distributions based on linear functions of the output photon occupation numbers, which we refer to as linear statistics. We present an efficient classical algorithm for approximating linear statistics of boson samplers within additive error for different kinds of input states, such as Fock states and squeezed states. This allows us to unify in the same framework recent results on efficient quantum-inspired classical algorithms for simulating molecular vibronic spectra, or efficient classical approximations of coarse-grained distributions based on detector binning. Additionally, we show how our algorithm can be used to classically evaluate a proposed one-way function based on Boson Sampling, while other proposals for cryptographic applications escape our classical simulation techniques. We leave open the question of classical simulability of non-linear statistics and connect it to the problem of computing transition amplitudes of linear-optical circuits with one layer of interactions.
The efficient simulation of quantum systems is a primary motivating factor for developing controllable quantum machines.For addressing systems with underlying bosonic structure, it is advantageous to utilize a naturally bosonic platform.Optical photons passing through linear networks may be configured to perform quantum simulation tasks, but the efficient preparation and detection of multiphoton quantum states of light in linear optical systems are challenging.Here, we experimentally implement a boson sampling protocol for simulating molecular vibronic spectra [J.Huh et al., Nat. Photonics 9, 615 (2015)] in a two-mode superconducting device.In addition to enacting the requisite set of Gaussian operations across both modes, we fulfill the scalability requirement by demonstrating, for the first time in any platform, a high-fidelity single-shot photon number resolving detection scheme capable of resolving up to 15 photons per mode.Furthermore, we exercise the capability of synthesizing non-Gaussian input states to simulate spectra of molecular ensembles in vibrational excited states.We show the reprogrammability of our implementation by extracting the spectra of photoelectron processes in H 2 O, O 3 , NO 2 , and SO 2 .The capabilities highlighted in this work establish the superconducting architecture as a promising platform for bosonic simulations, and by combining them with tools such as Kerr interactions and engineered dissipation, enable the simulation of a wider class of bosonic systems.
Abstract Electronic spectroscopy is today among the most powerful methods for studying chemical systems, and state-resolved (line-assigned) simulations are essential for attributing spectral features to specific vibrational excitations. The standard time-independent sum-over-states (SOS) route provides line assignments; while effective with truncation and prescreening, it can become computationally demanding as the number of modes increases. Vibronic boson sampling (VBS) offers an event-based alternative, but scaling photonic implementations remains challenging and the required vibronic inputs can be demanding for larger systems. Here we introduce coherent-state sampling (CSS), a sampling scheme for the Linear Coupling Model (LCM), where vibrational modes are independent. This enables a photonic architecture based on a single reconfigurable optical channel with essentially fixed hardware complexity; increasing system size is handled by additional measurement iterations rather than additional optical modes. Using pentacene as a test case, we demonstrate an end-to-end workflow—electronic-structure input, sampling strategy, hardware validation, and comparison to experiment—showing that both a laptop implementation and a superconducting-detector photonic implementation reproduce reference spectra with high fidelity and yield band shapes in good agreement with experiment. While not targeting quantum advantage, CSS provides a practically scalable, state-resolved tool for LCM vibronic spectroscopy and a controlled displacement-dominated complement to more general VBS schemes.