We consider the theory of the non-linear spectroscopy for a single molecule undergoing stochastic dynamics and interacting with a sequence of two laser pulses. General expressions for photon counting statistics are obtained, and an exact solution to the problem of the Kubo-Anderson process is found. In the limit of impulsive pulses the information on the photon statistics is contained in the molecule's dipole correlation function. The selective limit where temporal resolution is maintained, the semi-classical approximation and the fast modulation limit exhibit general behaviors of this new type of spectroscopy. We show how the design of the external field leads to rich insights on dynamics of individual molecules which are different than those found for an ensemble.
Single molecule spectroscopy aims at unveiling often hidden but potentially very important contributions of single entities to a system's ensemble response. Albeit contributing tremendously to our ever growing understanding of molecular processes the fundamental question of temporal evolution, or change, has thus far been inaccessible, resulting in a static picture of a dynamic world. Here, we finally resolve this dilemma by performing the first ultrafast time-resolved transient spectroscopy on a single molecule. By tracing the femtosecond evolution of excited electronic state spectra of singl…
Nonadiabatic dynamics around an avoid crossing or a conical intersection play a crucial role in the photoinduced processes of most polyatomic molecules. The present work shows that the topological phase in conical intersection makes the behavior of pump-probe high-order harmonic spectroscopy different from the case of avoid crossing. The coherence built up when the system crosses the avoid crossing will lead to the oscillatory behavior of the spectrum, while the geometric phase erodes these oscillations in the case of conical intersection. Additionally, the dynamical blueshift and the splittin…
High-order harmonic generation is a powerful and sensitive tool for probing atomic and molecular structures, combining in the same measurement an unprecedented attosecond temporal resolution with a high spatial resolution, of the order of the angstrom. Imaging of the outermost molecular orbital by high-order harmonic generation has been limited for a long time to very simple molecules, like nitrogen. Recently we demonstrated a technique that overcame several of the issues that have prevented the extension of molecular orbital tomography to more complex species, showing that molecular imaging c…
We report on two-photon photoassociation (PA) spectroscopy of ultracold heteronuclear LiRb molecules. This is used to determine the binding energies of the loosely bound levels of the electronic ground singlet and the lowest triplet states of LiRb. We observe strong two-photon PA lines with power broadened line widths greater than 20 GHz at relatively low laser intensity of 30 W/cm$^{2}$. The implication of this observation on direct atom to molecule conversion using stimulated Raman adiabatic passage (STIRAP) is discussed and the prospect for electronic ground state molecule production is the…
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）
Mid-infrared high-resolution spectroscopy has proven an invaluable tool for the study of the structure and dynamics of molecules in the gas phase. The advent of frequency combs advances the frontiers of precise molecular spectroscopy. Here we demonstrate, in the important 3-μm spectral region of the fundamental CH stretch in molecules, dual-comb spectroscopy with experimental coherence times between the combs that exceed half-an-hour. Mid-infrared Fourier transform spectroscopy using two frequency combs with self-calibration of the frequency scale, negligible contribution of the instrumental l…
In this research, we employ accurate time-dependent density functional calculations for ultrashort laser spectroscopy of nitrogen molecule. Laser pulses with different frequencies, intensities, and durations are applied to the molecule and the resulting photoelectron spectra are analyzed. It is argued that relative orientation of the molecule in the laser pulse significantly influence the orbital character of the emitted photoelectrons. Moreover, the duration of the laser pulse is also found to be very effective in controlling the orbital resolution and intensity of photoelectrons. Angular res…
We reported a detailed experimental study of the cold collision of Barium monofluoride (BaF) with buffer gas and the high-resolution spectroscopy relevant with direct laser cooling. BaF molecules are efficiently produced with laser ablation and buffer-gas cooled in a cryogenic apparatus. The laser cooling relevant transition $|X^2Σ, v=0, N=1\rangle$ to $|A^2Π, v'=0, J'=1/2\rangle$ is identified. The collision cross section with buffer gas is measured to be $1.4(7)\times10^{-14} cm^{-2}$, which is very suitable for buffer gas cooling. Both rotational and vibrational temperatures are effectively…
Infrared spectroscopy, especially for molecular vibrations in the fingerprint region between 600 and 1500 cm-1, is a powerful characterization method for bulk materials. However, molecular fingerprinting at the nanoscale level still remains a significant challenge, due to weak light-matter interaction between micron-wavelengthed infrared light and nano-sized molecules. Here, we demonstrate molecular fingerprinting at the nanoscale level using our specially designed graphene plasmonic structure on CaF2 nanofilm. This structure not only avoids the plasmon-phonon hybridization, but also provides …
Single-molecule approaches to biology offer a powerful new vision to elucidate the mechanisms that underpin the functioning of living cells. However, conventional optical single molecule spectroscopy techniques such as Förster fluorescence resonance energy transfer (FRET) or fluorescence correlation spectroscopy (FCS) are limited by diffraction to the nanomolar concentration range, far below the physiological micromolar concentration range where most biological reaction occur. To breach the diffraction limit, zero mode waveguides and plasmonic antennas exploit the surface plasmon resonances to…
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).
The emergence of confined structures and pattern formation are exceptional manifestations of concurring nonlinear interactions found in a variety of physical, chemical and biological systems[1]. Optical solitons are a hallmark of extreme spatial or temporal confinement enabled by a variety of nonlinearities. Such particle-like structures can assemble in complex stable arrangements, forming "soliton molecules"[2,3]. Recent works revealed oscillatory internal motions of these bound states, akin to molecular vibrations[4-8]. These observations beg the question as to how far the "molecular" analog…
Atomic-scale Stark-shift spectroscopy and microscopy of organic molecules
Centro de Física de Materiales (CFM-MPC), CSIC-EHU（材料物理中心（CFM-MPC），CSIC-EHU）；Department of Electricity and Electronics, FCT-ZTF, EHU（电气电子系，FCT-ZTF，EHU）；Institute of Physics, Czech Academy of Sciences（捷克科学院物理研究所）；Donostia International Physics Center（圣塞巴斯蒂安国际物理中心）；IKERBASQUE, Basque Foundation for Science（伊克尔巴斯基克，巴斯克科学基金会）
We theoretically study how time- and angle-resolved photoemission spectroscopy can be applied for imaging coherent electron dynamics in molecules. We consider a process in which a pump pulse triggers coherent electronic dynamics in a molecule by creating a valence electron hole. An ultrashort extreme ultraviolet (XUV) probe pulse creates a second electron hole in the molecule. Information about the electron dynamics is accessed by analyzing angular distributions of photoemission probabilities at a fixed photoelectron energy. We demonstrate that a rigorous theoretical analysis, which takes into…
Controlled Coherent Coupling in a Quantum Dot Molecule Revealed by Ultrafast Four-Wave Mixing Spectroscopy
Wrocław University of Science and Technology（弗罗茨瓦夫科技大学）；School of Physics, Trinity College Dublin（都柏林三一学院物理学院）；Technische Universität Berlin（柏林工业大学）；Ruhr-Universität Bochum（波鸿鲁尔大学）；Wrocław University of Technology（弗罗茨瓦夫理工大学）；Technische Universität München（慕尼黑工业大学）；Universität Paderborn（帕德博恩大学）；Université Grenoble Alpes（格勒诺布尔阿尔卑斯大学）
We report the most accurate measurement of the position of the weak quadrupole S(2) 2-0 line in D$_2$. The spectra were collected with a frequency-stabilized cavity ring-down spectrometer (FS-CRDS) with an ultra-high finesse optical cavity ($\mathcal{F}$ = 637 000) and operating in the frequency-agile, rapid scanning spectroscopy (FARS) mode. Despite working in the Doppler-limited regime, we reached 40 kHz of statistical uncertainty and 161 kHz of absolute accuracy, achieving the highest accuracy for homonuclear isotopologues of molecular hydrogen. The accuracy of our measurement corresponds t…
