We present the computation of two-photon transition spectra between ro-vibrational states of the H2+ molecular ion, including the effects of hyperfine structure and excitation polarization. The reduced two-photon matrix elements are obtained by means of a variational method. We discuss the implications of our results for high-resolution spectroscopy of H2+.
Pulsed single-photon spectroscopy of an emitter with vibrational coupling
University of Warwick（华威大学）；University of Nottingham（诺丁汉大学）；Università di Napoli Federico II（那不勒斯费德里科二世大学）；Università di Parma（帕尔马大学）；INFN—Sezione di Milano-Bicocca（意大利国家核物理研究所米兰-比科卡分部）
We report measurements of electron spin echo envelope modulation (ESEEM) performed at millikelvin temperatures in a custom-built high-sensitivity spectrometer based on superconducting micro-resonators. The high quality factor and small mode volume (down to 0.2pL) of the resonator allow to probe a small number of spins, down to $5\cdot 10^2$. We measure 2-pulse ESEEM on two systems: erbium ions coupled to $^{183}$W nuclei in a natural-abundance $\text{CaWO}_4$ crystal, and bismuth donors coupled to residual $^{29}$Si nuclei in a silicon substrate that was isotopically enriched in the $^{28}$Si …
Measurements of hyperfine polarization quantum beats are used determine the magnetic dipole (A) and electric quadrupole (B) coupling constants in the excited atomic Cs 8p level. The experimental approach is a novel combination of pulsed optical pumping and time-delayed stimulated emission probing of the excited level. From the measured evolution of the atomic linear polarization degree as a function of probe delay time, we determine the hyperfine coupling constants A = 7.42(6) MHz and B = 0.14(29) MHz.
High-resolution Zeeman spectroscopy of electronic-nuclear hyperfine levels of ${^5\mathrm{I}_8}\rightarrow{^5\mathrm{I}_7}$ transitions in Ho$^{3+}$:Y$_2$SiO$_5$ is reported. Crystal-field parameters determined for the two $C_1$ symmetry sites in Er$^{3+}$:Y$_2$SiO$_5$ are successfully used to model the Zeeman-hyperfine data, including the prediction of avoided crossings between hyperfine levels under the influence of an external magnetic field. The two six- and seven-coordinate substitutional sites may be distinguished by comparing the spectra with crystal-field calculations.
Multi-dimensional spectroscopy represents a particularly insightful tool for investigating the interplay of nuclear and electronic dynamics, which plays an important role in a number of photophysical processes and photochemical reactions. Here we present a coherent state representation of the vibronic dynamics and of the resulting response functions for the widely used linearly displaced oscillator model. Analytical expressions are initially derived for the case of third-order response functions in an N-level system, with ground state initialization of the oscillator (zero-temperature limit). …
Vibrational spectroscopy of polar molecules with superradiance
本文研究了在高光学深度（OD）样品中极性分子光谱中振动跃迁的合作现象和超辐射。这种协同性来自于通过偶极-偶极相互作用建立的粒子间相干性，并导致衰变过程的加速。我们将我们的计算与最近的工作进行比较[Deiglmayr等人，EUR. J. D 65，99（2011）]，并且发现非常好的一致性，这表明超辐射效应需要包括在各种各样的超冷分子设置中，包括振动和旋转状态。
This review elaborates on the foundation, the advantages, and the prospects of tensor network representations for quantum states in vibrational spectroscopy. The focus is on the recently introduced matrix product state decomposition of nuclear quantum states and its optimization by the density matrix renormalization group algorithm.
Molecular polaritons have gained considerable attention due to their potential to control nanoscale molecular processes by harnessing electromagnetic coherence. Although recent experiments with liquid-phase vibrational polaritons have shown great promise for exploiting these effects, significant challenges remain in interpreting their spectroscopic signatures. In this letter, we develop a quantum-mechanical theory of pump-probe spectroscopy for this class of polaritons based on the quantum Langevin equations and the input-output theory. Comparison with recent experimental data shows good agree…
High precision spectroscopy of the $^1S_0$-to-${^1}D_2$ clock transition of $^{176}$Lu is reported. Measurements are performed with Hertz level precision with the accuracy of the hyperfine-averaged frequency limited by the calibration of an active hydrogen maser to the SI definition of the second via a GPS link. The measurements also provide accurate determination of the $^1D_2$ hyperfine structure. Hyperfine structure constants associated with the magnetic octupole and electric hexadecapole moments of the nucleus are considered, which includes a derivation of correction terms from third-order…
We report on spectroscopic results on the $^2S_{1/2} \rightarrow\,^2P_{3/2}$ transition in single trapped Yb$^+$ ions. We measure the isotope shifts for all stable Yb$^+$ isotopes except $^{173}$Yb$^+$, as well as the hyperfine splitting of the $^2P_{3/2}$ state in $^{171}$Yb$^+$. Our results are in agreement with previous measurements but are a factor of 5-9 more precise. For the hyperfine constant $A\left(^2P_{3/2}\right) = 875.4(10)$ MHz our results also agree with previous measurements but deviate significantly from theoretical predictions. We present experimental results on the branching …
Addressing intramolecular vibrational redistribution in a single molecule through pump and probe surface-enhanced vibrational spectroscopy
Centro de Física de Materiales (CFM-MPC), CSIC-EHU（材料物理中心）；Donostia International Physics Center (DIPC)（多诺西亚国际物理中心）；Department of Electricity and Electronics, FCT-ZTF, UPV-EHU（巴斯克国立大学电气与电子工程系）；Department of Polymers and Advanced Materials, Faculty of Chemistry, The University of the Basque Country, UPV/EHU（巴斯克国立大学化学学院高分子与先进材料系）；IKERBASQUE, Basque Foundation for Science（伊克尔巴斯基克科学基金会）
We study the collective behavior of molecules placed in an infrared (IR) microcavity, incorporating the local fluctuations, i.e., dynamical disorder. The cooperative feature in vibrational polaritons is shown to be dynamically eroded, due to intermolecule coherence. To further resolve such process, we develop a two-dimensional infrared spectroscopy (2D-IR) for molecules interacting with cavity modes. The cooperative feature in correspondence to the spectroscopic signal is specified. The results reveal the dark states by the cross peaks apart from the ones for polaritons, as a result of the bre…
Strong coupling of molecular vibrations to an infrared cavity mode affects their nature by creating dressed polariton states. We show how the single and double vibrational polariton manifolds may be controlled by varying the cavity coupling strength, and probed by a time domain 2DIR technique, Double Quantum Coherence (DQC). Applications are made to the amide-I ($CO$) and amide-II ($CN$) bond vibrations of $N-methylacetamide$ (NMA).
We report the first experimental two-dimensional infrared (2D IR) spectra of novel molecular photonic excitations - vibrational-polaritons. The application of advanced 2D IR spectroscopy onto novel vibrational-polariton challenges and advances our understanding in both fields. From spectroscopy aspect, 2D IR spectra of polaritons differ drastically from free uncoupled molecules; from vibrational-polariton aspects, 2D IR uniquely resolves hybrid light-matter polariton excitations and unexpected dark states in a state-selective manner and revealed hidden interactions between them. Moreover, 2D I…
Hyperfine spectroscopy and fast, all-optical arbitrary state initialization and readout of a single, ten-level ${}^{73}$Ge vacancy nuclear spin qudit in diamond
Determining the vibrational structure of a molecule is central to fundamental applications in several areas, from atmospheric science to catalysis, fuel combustion modeling, biochemical imaging, and astrochemistry. However, when significant anharmonicity and mode coupling are present, the problem is classically intractable for a molecule of just a few atoms. Here, we outline a set of quantum algorithms for solving the molecular vibrational structure problem for both near- and long-term quantum computers. There are previously unaddressed characteristics of this problem which require approaches …
A machine learning algorithm for partitioning the nuclear vibrational space into subspaces is introduced. The subdivision criterion is based on Liouville's theorem, i.e. best preservation of the unitary of the reduced dimensionality Jacobian determinant within each subspace along a probe full-dimensional classical trajectory. The algorithm is based on the idea of evolutionary selection and it is implemented through a probability graph representation of the vibrational space partitioning. We interface this customized version of genetic algorithms with our divide-and-conquer semiclassical initia…
We propose and experimentally demonstrate a scheme which effects hyperfine averaging during a Ramsey interrogation of a clock transition. The method eliminates the need to average over multiple optical transitions, reduces the sensitivity of the clock to its environment, and reduces inhomogeneous broadening in a multi-ion clock. The method is compatible with auto-balanced Ramsey spectroscopy, which facilitates elimination of residual shifts due to imperfect implementation and ac Stark shifts from the optical probe. We demonstrate the scheme using correlation spectroscopy of the $^1S_0$-to-$^3D…
