We discuss semiempirical approaches and parametric methods developed for modeling molecular vibronic spectra. These methods, together with databases of molecular fragments, have proved efficient and flexible for solving various problems ranging from detailed interpretation of conventional vibronic spectra and calculation of radiative transition probabilities to direct simulations of dynamical (time-resolved) spectra and spectrochemical analysis of individual substances and mixtures. A number of specific examples and applications presented here show the potential of the semiempirical approach for predictive calculations of spectra and solution of inverse spectral problems. It is noteworthy that these advances provide computational insights into developing theories of photoinduced isomer transformations and nonradiative transitions in polyatomic molecules and molecular ensembles, theory of new methods for standardless quantitative spectral analysis.
The possibility of using time-resolved vibronic spectroscopy for spectral analysis of mixtures of chemical compounds with similar optical properties, when traditional methods are inefficient, is demonstrated by using the method of computer simulation. The analysis is carried out by the example of molecules of a series of polyenes (butadiene, hexatraene, octatetraene, decapentaene, and decatetraene), their various cis- and trans-rotational isomers, and phenyl-substituted polyenes. Ranges of relative concentrations of molecules similar in their spectral properties, where reliable interpretation …
Correlated driving-and-dissipation equation (CODDE) is an optimized complete second-order quantum dissipation approach, which is originally concerned with the reduced system dynamics only. However, one can actually extract the hybridized bath dynamics from CODDE with the aid of dissipaton-equation-of-motion theory, a statistical quasi-particle quantum dissipation formalism. Treated as an one{dissipaton theory, CODDE is successfully extended to deal with the Herzberg-Teller vibronic couplings in dipole-field interactions. Demonstrations will be carried out on the non-Condon spectroscopies of a …
The primary steps of photosynthesis rely on the generation, transport, and trapping of excitons in pigment-protein complexes (PPCs). Generically, PPCs possess highly structured vibrational spectra, combining many discrete intra-pigment modes and a quasi-continuous of protein modes, with vibrational and electronic couplings of comparable strength. The intricacy of the resulting vibronic dynamics poses significant challenges in establishing a quantitative connection between spectroscopic data and underlying microscopic models. Here we show how to address this challenge using numerically exact si…
We quantify the non-adiabatic contributions to the vibronic sidebands of equilibrium and explicitly time-resolved non-equilibrium photoelectron spectra for a vibronic model system of Trans-Polyacetylene. Using exact diagonalization, we directly evaluate the sum-over-states expressions for the linear-response photocurrent. We show that spurious peaks appear in the Born-Oppenheimer approximation for the vibronic spectral function, which are not present in the exact spectral function of the system. The effect can be traced back to the factorized nature of the Born-Oppenheimer initial and final ph…
Organic microcavities are photonic nanostructures that strongly confine the electromagnetic field, allowing exotic quantum regimes of light-matter interaction with disordered organic semiconductors. The unambiguous interpretation of the spectra of organic microcavities has been a long-standing challenge due to several competing effects involving electrons, vibrations and cavity photons. Here we present a theoretical framework that is able to describe the main spectroscopic features of organic microcavities consistently. We introduce a class of light-matter excitations called dark vibronic pola…
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…
We report the measurement of the 1$^{1}Σ\longrightarrow$ 2$^{1}Σ$ transition of CaH$^+$ by resonance-enhanced photodissociation of CaH$^+$ that is co-trapped with laser-cooled Ca$^+$ . We observe four resonances that we assign to transitions from the vibrational $v$=0 ground state to the $v'$=1-4 excited states based on theoretical predictions. A simple theoretical model that assumes instantaneous dissociation after resonant excitation yield results in good agreement with the observed spectral features except for the unobserved $v'$=0 peak. The resolution of our experiment is limited by the mo…
We observe vibronic transitions in CaD$^+$ between the 1$^{1}Σ$ and 2$^{1}Σ$ electronic states by resonance enhanced multiphoton photodissociation spectroscopy in a Coulomb crystal. The vibronic transitions are compared with previous measurements on CaH$^+$. The result is a revised assignment of the CaH$^+$ vibronic levels and a disagreement with CASPT2 theoretical calculations by approximately 700 cm$^{-1}$.
A general theory of electronic excitations in aggregates of molecules coupled to intramolecular vibrations and the harmonic environment is developed for simulation of the third-order nonlinear spectroscopy signals. The model is applied in studies of the time-resolved two-dimensional coherent spectra of four characteristic model systems: weakly / strongly vibronically coupled molecular dimers coupled to high / low frequency intramolecular vibrations. The results allow us to classify the typical spectroscopic features as well as to define the limiting cases, when the long-lived quantum coherence…
The prevalence of long-lasting oscillatory signals in the 2d echo-spectroscopy of light-harvesting complexes has led to a search for possible mechanisms. We investigate how two causes of oscillatory signals are intertwined: (i) electronic coherences supporting delocalized wave-like motion, and (ii) narrow bands in the vibronic spectral density. To disentangle the vibronic and electronic contributions we introduce a time-windowed Fourier transform of the signal amplitude. We find that 2d spectra can be dominated by excitations of pathways which are absent in excitonic energy transport. This lea…
We present derivation and implementation of the Multi-Configurational Strong-Field Approximation with Gaussian nuclear Wave Packets (MC-SFA-GWP) -- a version of the molecular strong-field approximation which treats all electronic and nuclear degrees of freedom, including their correlations, quantum-mechanically. The technique allows, for the first time, realistic simulation of high-harmonic emission in polyatomic molecules without invoking reduced-dimensionality models for the nuclear motion or the electronic structure. We use MC-SFA-GWP to model isotope effects in high-harmonics generation (H…
Natural and artificial light harvesting processes have recently gained new interest. Signatures of long lasting coherence in spectroscopic signals of biological systems have been repeatedly observed, albeit their origin is a matter of ongoing debate, as it is unclear how the loss of coherence due to interaction with the noisy environments in such systems is averted. Here we report experimental and theoretical verification of coherent exciton-vibrational (vibronic) coupling as the origin of long-lasting coherence in an artificial light harvester, a molecular J-aggregate. In this macroscopically…
Phase-modulated wave-packet interferometry is combined with mass-resolved photoion detection to investigate rubidium atoms attached to helium nanodroplets in a molecular beam experiment. The spectra of atomic Rb electronic states show a vastly enhanced sensitivity and spectral resolution when compared to conventional pump-probe wave-packet interferometry. Furthermore, the formation of Rb*He exciplex molecules is probed and for the first time a fully resolved vibrational spectrum for transitions between the lowest excited $5Π_{3/2}$ and the high-lying electronic states $2^2Π$, $4^2Δ$, $6^2Σ$ is…
In this work, we present a linear optical implementation for analog quantum simulation of molecular vibronic spectra, incorporating the non-Condon scattering operation with a quadratically small truncation error. Thus far, analog and digital quantum algorithms for achieving quantum speedup have been suggested only in the Condon regime, which refers to a transition dipole moment that is independent of nuclear coordinates. For analog quantum optical simulation beyond the Condon regime (i.e., non-Condon transitions) the resulting non-unitary scattering operations must be handled appropriately in …
The molecular ion ThF$^+$ is the species to be used in the next generation of search for the electron's Electric Dipole Moment (eEDM) at JILA. The measurement requires creating molecular ions in the eEDM sensitive state, the rovibronic ground state $^3Δ_1$, $v^+=0$, $J^+=1$. Survey spectroscopy of neutral ThF is required to identify an appropriate intermediate state for a Resonance Enhanced Multi-Photon Ionization (REMPI) scheme that will create ions in the required state. We perform broadband survey spectroscopy (from 13000 to 44000~cm$^{-1}$) of ThF using both Laser Induced Fluorescence (LIF…
We report a conceptually straightforward witness that isolates coherent electronic oscillations from their vibronic counterparts in nonlinear optical spectra of molecular aggregates: Coherent oscillations as a function of waiting time in broadband pump/broadband probe spectra correspond to coherent electronic oscillations. Oscillations in individual peaks of 2D electronic spectra do not necessarily yield this conclusion. Our witness is simpler to implement than quantum process tomography and potentially resolves a long-standing controversy on the character of oscillations in ultrafast spectra …
Laser-induced fluorescence excitation spectrum of NiS in the wavelength range of 450 - 560 nm has been recorded and analyzed. Thirty-five vibronic transition bands have been observed, 29 of which are reported for the first time. Rotational analyses indicated that all the observed bands can be attributable to the [Omega = 0] - X^3 Sigma^- transitions of ^58 NiS (and ^60 NiS). Twenty-five bands have been suggested to be grouped into four vibrational progressions. Furthermore, through dispersed fluorescence measurements we directly obtained the energies for the ground-state vibrational levels up …
We report absolute optical frequencies of electronic transitions from the $X\, ^2Π_{3/2},v''=0,J''=3/2$ rovibronic ground state to the 12 lowest levels of the $A\, ^2Σ^+,v'=0$ vibronic state in $^{16}$OH, as well as to the 16 lowest levels of the same vibronic state in $^{16}$OD. The absolute frequencies of these transitions have been determined with a relative uncertainty of a few parts in $10^{11}$, representing a $\sim$1000-fold improvement over previous measurements. To reach this level of precision, an optical frequency comb has been used to transfer the stability of a narrow-linewidth I$…
Rotationally resolved spectra of the C$^2Σ^+$-X$^2Π$ electronic system of the CH radical were measured using cavity ring-down spectroscopy in supersonically expanding, planar hydrocarbon plasma. The experimental conditions allowed the study of highly excited rotational levels starting from vibrationally excited states. Here we present some 200+ new or more accurately recorded transitions in the 0-0, 1-1 and 2-2 vibronic bands in the ultraviolet between 30900-32400 cm$^{-1}$ (324-309 nm). The resulting data, compared to earlier measurements, allows for the determination of more precise molecula…
The spectrum of electronic states at 30000--33000 cm$^{-1}$ in hafnium fluoride has been studied using (1+1) resonance-enhanced multi-photon ionization (REMPI) and (1+1$'$) REMPI. Six $Ω' = 3/2$ and ten $Π_{1/2}$ vibronic bands have been characterized. We report the molecular constants for these bands and estimate the electronic energies of the excited states using a correction derived from the observed isotope shifts. When either of two closely spaced $Π_{1/2}$ electronic states is used as an intermediate state to access autoionizing Rydberg levels, qualitatively distinct autoionization spect…
First results are presented obtained with an experimental setup developed to record IR spectra of rotationally state-selected ions. The method we use is a state-selective version of a method developed by S. Schlemmer, D. Gerlich and coworkers (Int. J. Mass. Spec. 185, 589 (1999); J. Chem. Phys. 117, 2068 (2002)) to record IR spectra of ions. Ions are produced in specific rotational levels using mass-analyzed-threshold-ionization spectroscopy. The state-selected ions generated by pulsed-field ionization of Rydberg states of high principal quantum number ($n\approx200$) are extracted toward an o…
We report the absorption profile of isolated Flavin Adenine Dinucleotide (FAD) mono-anions recorded using Photo-Induced Dissociation action spectroscopy. In this charge state, one of the phosphoric acid groups is deprotonated and the chromophore itself is in its neutral oxidized state. These measurements cover the first four optical transitions of FAD with excitation energies from 2.3 to 6.0~eV (210--550~nm). The $S_0\rightarrow S_2$ transition is strongly blue-shifted relative to aqueous solution, supporting the view that this transition has significant charge-transfer character. The remainin…
Conical Intersections Enable Ultrafast Molecular Spin Control in a Chromium Complex
Ningbo University（宁波大学）；Rosalind Franklin Institute（罗莎琳德·富兰克林研究所）；STFC Rutherford Appleton Laboratory（STFC鲁瑟福阿普尔顿实验室）；SLAC National Accelerator Laboratory（SLAC国家加速器实验室）；University of Toronto（多伦多大学）；University of Oxford（牛津大学）
Two-dimensional (2D) spectroscopy provides information about dissipative processes subsequent to electronic excitation, which play a functional role in energy harvesting materials and devices. This technique is particularly sensitive to electronic and vibronic coherence dynamics. While the theoretical treatment of relaxation in the context of 2D-spectroscopy is well-developed under the assumption of different timescales of population transfer and fluctuation dynamics, the interplay between both kinds of processes lacks a comprehensive description in terms of line shape functions. To bridge thi…
Vibrationally resolved electronic absorption spectra including the effect of vibrational pre-excitation are computed in order to interpret and predict vibronic transitions that are probed in the Vibrationally Promoted Electronic Resonance (VIPER) experiment [L. J. G. W. van Wilderen et al., Angew. Chem. Int. Ed. 53, 2667 (2014)]. To this end, we employ time-independent and time-dependent methods based on the evaluation of Franck-Condon overlap integrals and Fourier transformation of time-domain wavepacket autocorrelation functions, respectively. The time-independent approach uses a generalized…
Supercontinuum sources are all-fiber pulsed laser-driven systems that provide high power spectral densities within ultra-broadband spectral ranges. The tailored process of generating broadband, bright, and spectrally flat supercontinua -- through a complex interplay of linear and non-linear processes -- has been recently pushed further towards longer wavelengths and has evolved enough to enter the field of mid-infrared (mid-IR) spectroscopy. In this work, we review the current state and perspectives of this technology that offers laser-like emission properties and instantaneous broadband spect…
We describe an inexpensive instructional experiment that demonstrates the rotational energy levels of diatomic nitrogen, using the emission band spectrum of molecular nitrogen ionized by various processes in a commercial AC capillary discharge tube. The simple setup and analytical procedure is introduced as part of a sequence of educational experiments employed by a course of advanced atomic and molecular spectroscopy, where the study of rotational spectra is combined with the analysis of vibrational characteristics for a multifaceted picture of the quantum states of diatomic molecules.
Quantum technologies have seen a rapid developmental surge over the last couple of years. Though often overshadowed by quantum computation, quantum sensors show tremendous potential for widespread applications in chemistry and biology. One system stands out in particular: the nitrogen-vacancy (NV) center in diamond, an atomic-sized sensor allowing the detection of nuclear magnetic resonance (NMR) signals at unprecedented length scales down to a single proton. In this article, we review the fundamentals of NV center-based quantum sensing and its distinct impact on nano- to microscale NMR spectr…
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…
This review article discusses advances in the use of time-resolved photoelectron spectroscopy for the study of non-adiabatic processes in molecules. A theoretical treatment of the experiments is presented together with a number of experimental examples.
