Nonlinear Electronic Spectroscopy Research Articles

Investigating nonclassicality in nonlinear electronic spectroscopy

In this work, we establish a connection between nonlinear electronic spectroscopy and the protocol for the non-disturbance condition, the non-fullfilment of which is a witness of nonclassicality and can be related to the presence of coherence. Our approach permits us to express the nonclassicality witness condition in terms of common observables in the context of electronic spectroscopy experiments, such as the induced polarization. In this way, we provide the theoretical framework allowing one to infer nonclassicality from the detected signals in these experiments.

The highly excited-state manifold of guanine: calibration for nonlinear electronic spectroscopy simulations

A computational protocol based on the complete and restricted active space self-consistent field (CASSCF/RASSCF) methods and their second-order perturbation theory extensions (CASPT2/RASPT2) is employed to benchmark the highly excited-state manifold of the DNA/RNA canonical purine nucleobase guanine in vacuo. Several RASPT2 schemes are tested, displaying a steady convergence of electronic transition energies and dipole moments upon active space enlargement toward the reference values. The outcome allows calibrating and optimizing computational efforts by considering cheaper and more approximate RAS schemes that could enable the characterization of the excited-state manifolds of multi-chromophoric systems, such as DNA/RNA nucleobase dimers or multimers. Simulations of two-dimensional electronic spectra show similar trends to those observed on the other purine nucleobase adenine, deviating from this and other pyrimidine nucleobases in featuring its main excited-state absorption signal, embodied by sizable double HOMO to LUMO excitation contributions, in the UV probing window.

Semiclassical Path Integral Calculation of Nonlinear Optical Spectroscopy.

Computation of nonlinear optical response functions allows for an in-depth connection between theory and experiment. Experimentally recorded spectra provide a high density of information, but to objectively disentangle overlapping signals and to reach a detailed and reliable understanding of the system dynamics, measurements must be integrated with theoretical approaches. Here, we present a new, highly accurate and efficient trajectory-based semiclassical path integral method for computing higher order nonlinear optical response functions for non-Markovian open quantum systems. The approach is, in principle, applicable to general Hamiltonians and does not require any restrictions on the form of the intrasystem or system-bath couplings. This method is systematically improvable and is shown to be valid in parameter regimes where perturbation theory-based methods qualitatively breakdown. As a test of the methodology presented here, we study a system-bath model for a coupled dimer for which we compare against numerically exact results and standard approximate perturbation theory-based calculations. Additionally, we study a monomer with discrete vibronic states that serves as the starting point for future investigation of vibronic signatures in nonlinear electronic spectroscopy.

Development of Electronic Sum Frequency Generation Spectroscopies and Their Application to Liquid Interfaces

This feature article describes our recent work on the development of interface-selective second-order nonlinear electronic spectroscopies and their application to molecular structure and dynamics at liquid interfaces. We describe three methods that measure electronically resonant second-order nonlinear optical susceptibility (χ(2)) of interfacial molecules without contribution from the bulk: electronic sum-frequency generation (ESFG) provides high-quality interfacial electronic spectra by employing the combination of narrow-band and broad-band visible/near-infrared femtosecond pulses. Time-resolved ESFG (TR-ESFG) is the extension of ESFG to time-resolved measurements and provides femtosecond time-resolved electronic spectra at interfaces. Heterodyne-detected ESFG (HD-ESFG) is the ultimate second-order nonlinear electronic spectroscopy that directly provides the real and imaginary parts of χ(2). In particular, the imaginary χ(2) spectra obtained with HD-ESFG can be directly compared to the absorption spectra of bulk solution, and their signs contain information about the absolute orientation of the interfacial molecules. These interface-selective electronic spectroscopies enable rigorous comparison between the electronic spectra of liquid interfaces and those of bulk liquids, and the application to the following topics is discussed in this article: effective polarity at the air/water interface, interfacial ultrafast dynamics, absolute alignment of interfacial molecules, pH of the air/water interface, and the origin of nonresonant background. These studies reveal unique properties of molecules at air/liquid interfaces, which is markedly different from that in the bulk from a microscopic viewpoint.

Modeling the high-energy electronic state manifold of adenine: Calibration for nonlinear electronic spectroscopy.

Pump-probe electronic spectroscopy using femtosecond laser pulses has evolved into a standard tool for tracking ultrafast excited state dynamics. Its two-dimensional (2D) counterpart is becoming an increasingly available and promising technique for resolving many of the limitations of pump-probe caused by spectral congestion. The ability to simulate pump-probe and 2D spectra from ab initio computations would allow one to link mechanistic observables like molecular motions and the making/breaking of chemical bonds to experimental observables like excited state lifetimes and quantum yields. From a theoretical standpoint, the characterization of the electronic transitions in the visible (Vis)/ultraviolet (UV), which are excited via the interaction of a molecular system with the incoming pump/probe pulses, translates into the determination of a computationally challenging number of excited states (going over 100) even for small/medium sized systems. A protocol is therefore required to evaluate the fluctuations of spectral properties like transition energies and dipole moments as a function of the computational parameters and to estimate the effect of these fluctuations on the transient spectral appearance. In the present contribution such a protocol is presented within the framework of complete and restricted active space self-consistent field theory and its second-order perturbation theory extensions. The electronic excited states of adenine have been carefully characterized through a previously presented computational recipe [Nenov et al., Comput. Theor. Chem. 1040-1041, 295-303 (2014)]. A wise reduction of the level of theory has then been performed in order to obtain a computationally less demanding approach that is still able to reproduce the characteristic features of the reference data. Foreseeing the potentiality of 2D electronic spectroscopy to track polynucleotide ground and excited state dynamics, and in particular its expected ability to provide conformational dependent fingerprints in dimeric systems, the performances of the selected reduced level of calculations have been tested in the construction of 2D electronic spectra for the in vacuo adenine monomer and the unstacked adenine homodimer, thereby exciting the Lb/La transitions with the pump pulse pair and probing in the Vis to near ultraviolet spectral window.

Spectral lineshapes in nonlinear electronic spectroscopy.

We outline a computational approach for nonlinear electronic spectra, which accounts for the electronic energy fluctuations due to nuclear degrees of freedom and explicitly incorporates the fluctuations of higher excited states, induced by the dynamics in the photoactive state(s). This approach is based on mixed quantum-classical dynamics simulations. Tedious averaging over multiple trajectories is avoided by employing the linearly displaced Brownian harmonic oscillator to model the correlation functions. The present strategy couples accurate computations of the high-lying excited state manifold with dynamics simulations. The application is made to the two-dimensional electronic spectra of pyrene, a polycyclic aromatic hydrocarbon characterized by an ultrafast (few tens of femtoseconds) decay from the bright S2 state to the dark S1 state. The spectra for waiting times t2 = 0 and t2 = 1 ps demonstrate the ability of this approach to model electronic state fluctuations and realistic lineshapes. Comparison with experimental spectra [Krebs et al., New Journal of Physics, 2013, 15, 085016] shows excellent agreement and allows us to unambiguously assign the excited state absorption features.

Tracking conformational dynamics of polypeptides by nonlinear electronic spectroscopy of aromatic residues: a first-principles simulation study.

The ability of nonlinear electronic spectroscopy to track folding/unfolding processes of proteins in solution by monitoring aromatic interactions is investigated by first-principles simulations of two-dimensional (2D) electronic spectra of a model peptide. A dominant reaction pathway approach is employed to determine the unfolding pathway of a tetrapeptide, which connects the initial folded configuration with stacked aromatic side chains and the final unfolded state with distant noninteracting aromatic residues. The π-stacking and excitonic coupling effects are included through ab initio simulations based on multiconfigurational methods within a hybrid quantum mechanics/molecular mechanics scheme. It is shown that linear absorption spectroscopy in the ultraviolet (UV) region is unable to resolve the unstacking dynamics characterized by the three-step process: T-shaped→twisted offset stacking→unstacking. Conversely, pump-probe spectroscopy can be used to resolve aromatic interactions by probing in the visible region, the excited-state absorptions (ESAs) that involve charge-transfer states. 2D UV spectroscopy offers the highest sensitivity to the unfolding process, by providing the disentanglement of ESA signals belonging to different aromatic chromophores and high correlation between the conformational dynamics and the quartic splitting.

Vibronic models for nonlinear spectroscopy simulations.

It is already well established that the high-frequency intramolecular vibrations are responsible for many observed dynamic phenomena in linear and nonlinear electronic spectroscopy such as the spectral lineshape formation, the transition dipole moment, the lifetime borrowing, andvibrational and mixed coherence beats. All these implications together with the vibronic enhancement of the energy and charge transfer can be explained by the vibronic molecular exciton theory and are highly relevant for the description of the spectral dynamics in photosynthetic pigment-protein complexes. In this paper, a few critical points of the vibronic theory application to linear and nonlinear signals are discussed. Models, which differ in the selection and truncation of molecular basis, are compared by analyzing the energy spectrum and exciton-vibrational dynamics in the presence of the energetic disorder. The limits of the widely used one-particle approximation are defined.

On the linear and non-linear electronic spectroscopy of chlorophylls: a computational study

A theoretical analysis of linear and non-linear (two-photon absorption) electronic spectroscopy of all known porphyrinic pigments has been performed using linear and quadratic density functional response theory, with the long-range corrected CAM-B3LYP functional. We found that higher Soret transitions often contain non-Gouterman contributions and that each chlorophyll has the possibility for resonance enhanced TPA in the Soret region, although there is also significant TPA in the Q region.