Exploring electronic resonances in pyridine: Insights from orbital stabilization techniques.

Electron attachment to pyridine results in electronic resonances, metastable states that can decay through electronic or nuclear degrees of freedom. This study uses orbital stabilization techniques combined with bound electronic structure methods, based on equation of motion coupled cluster or multi-reference methods, to calculate positions and widths of electronic resonances in pyridine that exist below 10 eV. We report four 2B1 and four 2A2 resonances, including one 2B1 not previously reported experimentally and two 2A2 resonances not reported at all in the literature. The two lower energy resonances are one-particle shape resonances, while the remaining are mixed or primarily core-excited resonances. Multi-reference perturbation theory provides the best description of these resonances, especially when their character is mixed. We describe the character of these resonances qualitatively and calculate Dyson orbitals, which provide information about their decay channels.

Modeling the effect of substituents on the electronically excited states of indole derivatives.

A proper understanding of excited state properties of indole derivatives can lead to rational design of efficient fluorescent probes. The optically active L a $$ {L}_a $$ and L b $$ {L}_b $$ excited states of a series of substituted indoles, where a substituent was placed on position four, were calculated using equation of motion coupled cluster and time dependent density functional theory. The results indicate that most substituted indoles have a brighter second excited state corresponding to experimental absorption maxima, but a few with electron withdrawing substituents absorb more on the first excited state. Absorption on the first excited state may increase their fluorescence quantum yield, making them better probes. Electronic structure methods were found to predict the energies of the systems with electron withdrawing substituents more accurately than those with electron donating substituents. The excited states of both states correlated well with electrophilicity, similar to the experimental trends for the absorption maxima. Overall, these computational studies indicate that theory can be used to predict excited state properties of substituted indoles, when the substituent is an electron withdrawing group.

Molecular Dynamical and Quantum Mechanical Exploration of the Site-Specific Dynamics of Cy3 Dimers Internally Linked to dsDNA.

Performing spectroscopic measurements on biomolecules labeled with fluorescent probes is a powerful approach to locating the molecular behavior and dynamics of large systems at specific sites within their local environments. The indocarbocyanine dye Cy3 has emerged as one of the most commonly used chromophores. The incorporation of Cy3 dimers into DNA enhances experimental resolution owing to the spectral characteristics influenced by the geometric orientation of excitonically coupled monomeric units. Various theoretical models and simulations have been utilized to aid in the interpretation of the experimental spectra. In this study, we employ all-atom molecular dynamics simulations to study the structural dynamics of Cy3 dimers internally linked to the dsDNA backbone. We used quantum mechanical calculations to derive insights from both the linear absorption spectra and the circular dichroism data. Furthermore, we explore potential limitations within a commonly used force field for cyanine dyes. The molecular dynamics simulations suggest the presence of four possible Cy3 dimeric populations. The spectral simulations on the four populations show one of them to agree better with the experimental signatures, suggesting it to be the dominant population. The relative orientation of Cy3 in this population compares very well with previous predictions from the Holstein-Frenkel Hamiltonian model.

Spectroscopic approaches for studies of site-specific DNA base and backbone 'breathing' using exciton-coupled dimer-labeled DNA.

DNA regulation and repair processes require direct interactions between proteins and DNA at specific sites. Local fluctuations of the sugar-phosphate backbones and bases of DNA (a form of DNA 'breathing') play a central role in such processes. Here we review the development and application of novel spectroscopic methods and analyses - both at the ensemble and single-molecule levels - to study structural and dynamic properties of exciton-coupled cyanine and fluorescent nucleobase analogue dimer-labeled DNA constructs at key positions involved in protein-DNA complex assembly and function. The exciton-coupled dimer probes act as 'sensors' of the local conformations adopted by the sugar-phosphate backbones and bases immediately surrounding the dimer probes. These methods can be used to study the mechanisms of protein binding and function at these sites.

Excited state hydrogen or proton transfer pathways in microsolvated n-cyanoindole fluorescent probes.

The sensitivity of the fluorescence properties of n-cyanoindole (n-CNI) fluorescent probes to the microenvironment makes them potential reporters of protein conformation and hydration. The fluorescence intensity of 5-CNI, 6-CNI, and 7-CNI is quenched when exposed to water solvent whereas substitution on position 4 of indoles dramatically increases it. A potential mechanism for this sensitivity to water may be similar to that found in indole. The fluorescence of indole is found to be quenched when interacting with water and ammonia solvent molecules via radiationless decay through an S1 (πσ*)/S0 conical intersection caused by excited state proton or hydrogen transfer to the solvent molecules. In this study we examine this fluorescence quenching mechanism along the N-H bond stretch of n-CNI probes using water cluster models and quantum mechanical calculations of the excited states. We find that n-CNI-(H2O)1-2 clusters form cyclic or non-cyclic structures via hydrogen bonds which lead to different photochemical reaction paths that can potentially quench the fluorescence by undergoing internal conversion from S1 to S0. However, the existence of a high energy barrier along the potential energy surface of the S1 state in most cases prevents this from occurring. We show that substitution on position 4 leads to the highest energy barrier that prevents the fluorophore from accessing these non-radiative channels, in agreement with its high intensity. We also find that the energy barrier in the S1 state of non-cyclic 5-CNI-(H2O)1-2 excited complexes decreases as the number of water molecules increases, which suggests great sensitivity of the fluorescence quenching on the aqueous environment.

Using transition density models to interpret experimental optical spectra of exciton-coupled cyanine (iCy3)2 dimer probes of local DNA conformations at or near functional protein binding sites.

Exciton-coupled chromophore dimers are an emerging class of optical probes for studies of site-specific biomolecular interactions. Applying accurate theoretical models for the electrostatic coupling of a molecular dimer probe is a key step for simulating its optical properties and analyzing spectroscopic data. In this work, we compare experimental absorbance and circular dichroism (CD) spectra of 'internally-labeled' (iCy3)2 dimer probes inserted site-specifically into DNA fork constructs to theoretical calculations of the structure and geometry of these exciton-coupled dimers. We compare transition density models of varying levels of approximation to determine conformational parameters of the (iCy3)2 dimer-labeled DNA fork constructs. By applying an atomistically detailed transition charge (TQ) model, we can distinguish between dimer conformations in which the stacking and tilt angles between planar iCy3 monomers are varied. A major strength of this approach is that the local conformations of the (iCy3)2 dimer probes that we determined can be used to infer information about the structures of the DNA framework immediately surrounding the probes at various positions within the constructs, both deep in the duplex DNA sequences and at sites at or near the DNA fork junctions where protein complexes bind to discharge their biological functions.

Unravelling the Origin of the Vibronic Spectral Signatures in an Excitonically Coupled Indocarbocyanine Cy3 Dimer.

The indocarbocyanine Cy3 dye is widely used to probe the dynamics of proteins and DNA. Excitonically coupled Cy3 dimers exhibit very unique spectral signatures that depend on the interchromophoric geometrical orientation induced by the environment, making them powerful tools to infer the dynamics of their surroundings. Understanding the origin of the dimeric spectral signatures is a necessity for an accurate interpretation of the experimental results. In this work, we simulate the vibronic spectrum of an experimentally well-studied Cy3 dimer, and we explain the origin of the experimental signatures present in its linear absorption spectrum. The Franck-Condon harmonic approximations, among other tests, are used to probe the factors contributing to the spectrum. It is found that the first peak in the absorption spectrum originates from the lower energy excitonic state, while the next two peaks are vibrational progressions of the higher energy excitonic state. The polar solvent plays a crucial role in the appearance of the spectrum, being responsible for the localized S1 minimum, which results in an increased intensity of the first peak.

Excited-state dynamics of o-nitrophenol studied with UV pump-VUV probe time-resolved photoelectron and photoion spectroscopy.

Time-resolved photoionization measurements were performed on o-nitrophenol pumped with UV laser pulses at a central wavelength of 255 nm (4.9 eV) and probed with vacuum ultraviolet (VUV) pulses at 153 nm (8.1 eV). The photoelectron spectrum and time of flight mass spectrum for ions were recorded at each pump-probe delay. The measurements are interpreted with the aid of electronic structure calculations for both the neutral and ionic states. Evidence is found for the formation of a bicyclic intermediate followed by NO dissociation through a process of internal conversion and intersystem crossing. The combination of photoelectron and photoion spectroscopy, together with computational results, provides strong evidence of intersystem crossing that is difficult to establish with only a single technique.

Mechanistic Aspects of the Effect of Flanking Nucleotide Sequence on CPD Formation and CPD Self-Repair in DNA.

A cyclobutane pyrimidine dimer (CPD) is a photolesion which is produced by a cycloaddition reaction between two stacked pyrimidine bases upon UV light absorption. Because of its harmful effect on important cellular processes involving DNA and especially its relevance to skin cancer, the mechanisms of how a CPD is formed or repaired have been studied extensively, and it has been demonstrated that flanking nucleotide sequences play a crucial role in CPD formation or self-repair. Understanding the mechanisms behind this sequence dependence of CPD formation or self-repair is of great importance because it can give us valuable information on which sequence will be vulnerable to this DNA photodamage. This Perspective focuses on the mechanisms of how flanking nucleotide sequences affect CPD formation or self-repair, especially highlighting the role of computational studies in this field.

Effective Fragment Potentials for Microsolvated Excited and Anionic States.

The effective fragment potential (EFP) approach is a sophisticated hybrid approach that allows the inclusion of solvation effects when describing properties and reactivity in the condensed phase, without using empirical parameters. This work examines the performance of the EFP method when describing microsolvation in electronically excited states of neutrals and anions. The examples selected include both localized valence states, as well as diffuse nonvalence states, which represent greater challenges to conventional electronic structure methods. The equation-of-motion coupled cluster with singles and doubles (EOM-XX-CCSD) methodology has been used to provide the quantum chemical description of both the full microsolvated clusters, and the chromophoric moiety in mixed quantum/EFP calculations. We find that, when averaging over multiple configurations of microsolvated clusters, the differences between QM/EFP and full quantum results are minimal, although individual configurations often have larger errors. As expected, diffuse states have somewhat larger errors, although not significantly so. The close proximity of states leading to mixing can make QM/EFP less accurate because a change of ordering of states can occur. Other properties, such as photoelectron images and lifetimes of metastable states, are very well described for the monohydrated clusters investigated.

Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances.

The positions and widths of the optically allowed electronic states of the tetracene radical anion located above the detachment threshold energy (i.e anion resonances) are mapped out using total photodetachment yield spectroscopy of cryogenically cooled ions. The presence of these states is detected via the sharp increase in the photodetachment yield compared to that of the monotonic nonresonant direct photodetachment background. The resolution of the resulting spectrum is limited by the ∼5 cm-1 line width of the tunable laser and thus provides a stringent benchmark for computations of the energies and autodetachment lifetimes of these resonance states. The experimental results are compared to high-level electronic structure computations and line width modeling using the orbital stabilization method. These theoretical results are found to be in near quantitative agreement with the experimental data, highlighting their capability to accurately describe the energies and lifetimes of anion resonances for relatively large molecules.

Strong Field Double Ionization of Formaldehyde Investigated Using Momentum Resolved Covariance Imaging and Trajectory Surface Hopping.

We use covariance velocity map imaging of fragment ions from the strong field double ionization of formaldehyde in conjunction with trajectory surface hopping calculations to determine the ionization yields to different singlet and triplet states of the dication. The calculated kinetic energy release for trajectories initiated on different electronic states is compared with the experimental values based on momentum resolved covariance measurements. We determine the state resolved double ionization yields as a function of laser intensity and pulse duration down to 6 fs (two optical cycles).

Nonadiabatic Excited State Dynamics of Organic Chromophores: Take-Home Messages.

Nonadiabatic excited state dynamics are important in a variety of processes. Theoretical and experimental developments have allowed for a great progress in this area, while combining the two is often necessary and the best approach to obtain insight into the photophysical behavior of molecules. In this Feature Article we use examples of our recent work combining time-resolved photoelectron spectroscopy with theoretical nonadiabatic dynamics to highlight important lessons we learned. We compare the nonadiabatic excited state dynamics of three different organic molecules with the aim of elucidating connections between structure and dynamics. Calculations and measurements are compared for uracil, 1,3-cyclooctadiene, and 1,3-cyclohexadiene. The comparison highlights the role of rigidity in influencing the dynamics and the difficulty of capturing the dynamics accurately with calculations.

Modeling the Electronic Absorption Spectra of the Indocarbocyanine Cy3.

Accurate modeling of optical spectra requires careful treatment of the molecular structures and vibronic, environmental, and thermal contributions. The accuracy of the computational methods used to simulate absorption spectra is limited by their ability to account for all the factors that affect the spectral shapes and energetics. The ensemble-based approaches are widely used to model the absorption spectra of molecules in the condensed-phase, and their performance is system dependent. The Franck-Condon approach is suitable for simulating high resolution spectra of rigid systems, and its accuracy is limited mainly by the harmonic approximation. In this work, the absorption spectrum of the widely used cyanine Cy3 is simulated using the ensemble approach via classical and quantum sampling, as well as, the Franck-Condon approach. The factors limiting the ensemble approaches, including the sampling and force field effects, are tested, while the vertical and adiabatic harmonic approximations of the Franck-Condon approach are also systematically examined. Our results show that all the vertical methods, including the ensemble approach, are not suitable to model the absorption spectrum of Cy3, and recommend the adiabatic methods as suitable approaches for the modeling of spectra with strong vibronic contributions. We find that the thermal effects, the low frequency modes, and the simultaneous vibrational excitations have prominent contributions to the Cy3 spectrum. The inclusion of the solvent stabilizes the energetics significantly, while its negligible effect on the spectral shapes aligns well with the experimental observations.

Stable excited dication: trapping on the S1 state of formaldehyde dication after strong field ionization.

Combined theoretical and experimental work examines the dynamics of dication formaldehyde produced by strong field ionization. Trajectory surface hopping dynamics on the first several singlet electronic states of the formaldehyde dication are used to examine the relaxation pathways and dissociation channels, while kinetic energy distributions after strong field ionization of formaldehyde and deuterated formaldehyde are used to confirm the theoretical predictions. We find that the first excited state of the formaldehyde dication is stable, neither decays to the ground state nor dissociates, even though the ground state and higher lying states are directly dissociative. The stability of the first excited state is explained by its symmetry which does not allow for radiative or nonradiative transitions to the ground state and by large barriers to dissociate on the excited state surface.

Projected Complex Absorbing Potential Multireference Configuration Interaction Approach for Shape and Feshbach Resonances.

Anion resonances are formed as metastable intermediates in low-energy electron-induced reactions. Due to the finite lifetimes of resonances, applying standard Hermitian formalism for their characterization presents a vexing problem for computational chemists. Numerous modifications to conventional quantum chemical methods have enabled satisfactory characterization of resonances, but specific issues remain, especially in describing two-particle one-hole (2p-1h) resonances. An accurate description of these resonances and their coupling with single-particle resonances requires a multireference approach. We propose a projected complex absorbing potential (CAP) implementation within the multireference configuration interaction (MRCI) framework to characterize single-particle and 2p-1h resonances. As a first application, we use the projected-CAP-MRCI approach to characterize and benchmark the 2Πg shape resonance in N2-. We test its performance as a function of the size of the subspace and other parameters, and we compute the complex potential energy surface of the 2Πg shape resonance to show that a smooth curve is obtained. One key benefit of MRCI is that it can describe Feshbach resonances (most common examples of 2p-1h resonances) at the same footing as shape resonances. Therefore, it is uniquely positioned to describe mixing between the different channels. To test these additional capabilities, we compute Feshbach resonances in H2O- and anions of dicyanoethylene isomers. We find that CAP-MRCI can efficiently capture the mixing between the Feshbach and shape resonances in dicyanoethylene isomers, which has significant consequences for their lifetimes.

Conformer-Specific Dissociation Dynamics in Dimethyl Methylphosphonate Radical Cation.

The dynamics of the dimethyl methylphosphonate (DMMP) radical cation after production by strong field adiabatic ionization have been investigated. Pump-probe experiments using strong field 1300 nm pulses to adiabatically ionize DMMP and a 800 nm non-ionizing probe induce coherent oscillations of the parent ion yield with a period of about 45 fs. The yields of two fragments, PO2C2H7+ and PO2CH4+, oscillate approximately out of phase with the parent ion, but with a slight phase shift relative to each other. We use electronic structure theory and nonadiabatic surface hopping dynamics to understand the underlying dynamics. The results show that while the cation oscillates on the ground state along the P=O bond stretch coordinate, the probe excites population to higher electronic states that can lead to fragments PO2C2H7+ and PO2CH4+. The computational results combined with the experimental observations indicate that the two conformers of DMMP that are populated under experimental conditions exhibit different dynamics after being excited to the higher electronic states of the cation leading to different dissociation products. These results highlight the potential usefulness of these pump-probe measurements as a tool to study conformer-specific dynamics in molecules of biological interest.

A Unique QP Partitioning and Siegert Width Using Real-Valued Continuum-Remover Potential.

A simple, practical quantum chemical procedure is presented for computing the energy position and the decay width of autoionization resonances. It combines the L2-stabilized resonance wave function obtained using the real-valued continuum-remover (CR) potential [Y. Sajeev Chem. Phys. Lett. 2013, 587, 105-112] and the Feshbach projection operator (FPO) partitioning technique. Unlike the conventional FPO partitioning of the total wave function into its resonant Q space and background P space components, an explicit partitioning of the total wave function into its interaction region and noninteraction region components is obtained with the help of real-valued continuum-remover potential. The molecular system is initially confined inside a CR potential which removes the electronic continuum of the molecular system in which its resonance state is embedded and, thus, unravels the Q space component of the resonance wave function as a bound, localized eigenstate of the confined system. The eigenfunctions of the molecular Hamiltonian represented in the {1-Q} space constitute a complementary, orthogonal P space. A unique QP partition is obtained when the level-shift of the Q space function due to its coupling with the P space is zero, and the resonance width is computed using these unique partitioned spaces. This new procedure, which we refer to as CR-FPO formalism, is formally very simple and straightforward to implement, yet its applications to the resonance state of a model Hamiltonian and to the doubly excited resonance states of atomic and molecular systems at the full-CI level are very accurate as compared to the alternative, very precise L2 methods. In addition, the CR-FPO formalism is implemented in the multireference configuration interaction (MRCI) method, and uses it for calculating the energy position and the autionization decay width of 2Πg shape resonance in N2-.

Exact-Factorization-Based Surface Hopping for Multistate Dynamics.

A surface-hopping algorithm recently derived from the exact factorization approach, SHXF [Ha et al. J. Phys. Chem. Lett. 2018, 9, 1097], introduces an additional term in the electronic equation of surface hopping that couples electronic states through the quantum momentum. This term not only provides a first-principles description of decoherence, but here we show it is crucial to accurately capture nonadiabatic dynamics when more than two states are occupied at any given time. Using a vibronic coupling model of the uracil cation, we show that the lack of this term in traditional surface-hopping methods, including those with decoherence corrections, leads to failure to predict the dynamics through a three-state intersection, while SHXF performs similarly to the multiconfiguration time-dependent Hartree quantum dynamics benchmark.