Time-resolved Infrared Spectroscopy Research Articles

Modus Operandi of a Pedalo-Type Molecular Switch: Insight from Dynamics and Theoretical Spectroscopy.

Molecular switches which can be triggered by light to interconvert between two or more well-defined conformation differing in their chemical or physical properties are fundamental for the development of materials with on-demand functionalities. Recently, a novel molecular switch based on a the azodicarboxamide core has been reported. It exhibits a volume-conserving conformational change upon excitation, making it a promising candidate for embedding in confined environments. In order to rationally implement and efficiently utilize the azodicarboxamide molecular switch, detailed insight into the coordinates governing the excited-state dynamics is needed. Here, we report a detailed comparative picture of the molecular motion at the atomic level in the presence and absence of explicit solvent. Our hybrid quantum mechanics/molecular mechanics (QM/MM) excited state simulations reveal that, although the energy landscape is slightly modulated by the solvation, the light-induced motion is dominated by a bending-assisted pedalo-type motion independent of the solvation. To support the predicted mechanism, we simulate time-resolved IR spectroscopy from first principles, thereby resolving fingerprints of the light-induced switching process. Our calculated time-resolved data are in good agreement with previously reported measured spectra.

Investigating the Photodissociation Dynamics of CF2BrCF2I in CCl4 through Femtosecond Time-Resolved Infrared Spectroscopy

The photodissociation dynamics of CF2BrCF2I in CCl4 at 280 ± 2 K were investigated by probing the C-F stretching mode from 300 fs to 10 μs after excitation at 267 nm using time-resolved infrared spectroscopy. The excitation led to the dissociation of I or Br atoms within 300 fs, producing the CF2BrCF2 or CF2ICF2 radicals, respectively. All nascent CF2ICF2 underwent further dissociation of I, producing CF2CF2 with a time constant of 56 ± 5 ns. All nascent g-CF2BrCF2 isomerized into the more stable a-CF2BrCF2 with a time constant of 47 ± 5 ps. Furthermore, a-CF2BrCF2 underwent a bimolecular reaction with either itself (producing CF2BrCF2Br and CF2CF2) or Br in the CCl4 solution (producing CF2BrCF2Br) at a diffusion-limited rate. The secondary dissociation of Br from a-CF2BrCF2 was significantly slow to compete with the bimolecular reactions. Overall, approximately half of the excited CF2BrCF2I at 267 nm produced CF2BrCF2Br, whereas the other half produced CF2CF2. The excess energies in the nascent radicals were thermalized much faster than the secondary dissociation of I from CF2ICF2 and the observed bimolecular reactions, implying that the secondary reactions proceeded under thermal conditions. This study further demonstrates that structure-sensitive time-resolved infrared spectroscopy can be used to study various reaction dynamics in solution in real time.

Trapping of a Mononitrosyl Nonheme Intermediate of Nitric Oxide Reductase by Cryo-Photolysis of Caged Nitric Oxide.

Characterization of short-lived reaction intermediates is essential for elucidating the mechanism of the reaction catalyzed by metalloenzymes. Here, we demonstrated that the photolysis of a caged compound under cryogenic temperature followed by thermal annealing is an invaluable technique for trapping of short-lived reaction intermediates of metalloenzymes through the study of membrane-integrated nitric oxide reductase (NOR) that catalyzes reductive coupling of two NO molecules to N2O at its heme/nonheme FeB binuclear center. Although NO produced by the photolysis of caged NO did not react with NOR under cryogenic temperature, annealing to ∼160 K allowed NO to diffuse and react with NOR, which was evident from the appearance of EPR signals assignable to the S = 3/2 state. This indicates that the nonheme FeB-NO species can be trapped as the intermediate. Time-resolved IR spectroscopy with the use of the photolysis of caged NO as a reaction trigger showed that the intermediate formed at 10 μs gave the NO stretching frequency at 1683 cm-1 typical of nonheme Fe-NO, confirming that the combination of the cryo-photolysis of caged NO and annealing enabled us to trap the reaction intermediate. Thus, the cryo-photolysis of the caged compound has great potential for the characterization of short-lived reaction intermediates.

Molecular Photothermal Effects on Time-Resolved IR Spectroscopy: Solute-Solvent Intermolecular Energy Transfer.

Time-resolved IR pump-probe (IR-PP) and two-dimensional IR (2D-IR) spectroscopy are valuable tools for studying ultrafast chemical and biological processes in solutions. However, the corresponding signals at long times are obscured by the molecular photothermal effects resulting from the heat dissipation of vibrationally photoexcited molecules to the surroundings. Recently, a phenomenology model was used to describe molecular photothermal effects on IR-PP signals and the diagonal and cross-peaks of 2D-IR spectra at long pump-probe delay times. Here, we consider the thermal diffusion equation with a time-dependent heat source term to describe the solute-solvent energy transfer process. An approximate solution to the nonhomogeneous differential equation shows that the molecular photothermal effect is determined by the mean intermolecular distance between IR-absorbing molecules. We show that the time profile of heat dissipation from a vibrationally excited molecule to the surroundings, which provides information about the mechanisms involved in the solute-solvent intermolecular energy transfer process in solutions, can be directly measured by analyzing the molecular photothermal IR-PP and 2D-IR signals. We anticipate that the present work can be used to interpret local heating-induced time-resolved IR spectroscopic signals and understand the rate of and the mechanisms involved in the conversion from high-frequency molecular vibrational energy to solvent kinetic energy in condensed phases.

Dynamics of hydrogen bond reorganization in the S1(ππ*) state of 9-Anthracenecarboxaldehyde

Effect of solvent polarity and hydrogen bonding interaction on the excited state dynamics of 9-Anthracenecarboxaldehyde (9-ACD) have been investigated using steady state and time-resolved electronic and vibrational spectroscopic techniques. Photophysical properties and dynamics of the excited states are seen to be more sensitive to intermolecular hydrogen bonding ability of the solvent, rather than its polarity. FTIR studies reveal formation of complexes with the protic solvents via formation of conventional hydrogen bond at the carbonyl site of 9-ACD molecule. In strong hydrogen bond donating solvents, namely, 2, 2, 2-trifuoroethanol (TFE) and 1, 1, 1, 3, 3, 3-hexafluoroisopropanol (HFIP), nearly all the molecules of 9-ACD in solution remain engaged in complex formation leaving insignificant number of molecules remaining free in solution. In aprotic solvents, the S1 state is short-lived (the lifetime is only a few tens of ps) and intersystem crossing (ISC) is the major deactivation pathway (the triplet yield is near unity). However, in strong hydrogen bond donating solvents, the S1 state lifetime is long (a few ns) because the deactivation pathway for the S1 state via the triplet manifold is blocked. Both the ultrafast time-resolved electronic and vibrational spectroscopy studies in TFE and HFIP reveal that hydrogen bond reorganization process following photoexcitation of the hydrogen bonded complex is the only relaxation process undergone by the S1 state in sub-100 ps time domain. However, the time-resolved IR (TRIR) spectroscopy studies further reveal the possibility of formation of aromatic π- hydrogen bonding and reorganization of the hydrogen bond at this site makes the major contribution towards the S1 state relaxation process in strong hydrogen bond donating solvents.

Processing helix–coil transition data: Account of chain length and solvent effects

Numerous nanobiotechnologies include manipulations of short polypeptide chains. The conformational properties of these polypeptides are studied in vitro by circular dichroism and time-resolved infrared spectroscopy. To find out the interaction parameters, the measured temperature dependence of normalized helicity degree needs to be further processed by fitting to a model. Using recent advances in the Hamiltonian formulation of the classical Zimm and Bragg model, we explicitly include chain length and solvent effects in the theoretical description. The expression for the helicity degree we suggest successfully fits the experimental data and provides hydrogen bonding energies and nucleation parameter values within the standards in the field.

Reduction of aerobic metabolism and increased microvascular perfusion during pressure-adjusted static compression as underlying mechanism with potential of preventing chemotherapy-induced neuropathy

Abstract Chemotherapy (CTX)-induced neuropathy [CIPN] limits the maximal applicable dose. Static compression for prevention of CIPN is recommended by guidelines. The postulated underlying effect of reduced microvascular perfusion (MP), however, contradicts current knowledge of elegant in vivo studies. We, thus tested the hypothesis of increased MP combined with reduction of aerobic metabolism in response to pressure-adjusted static compression (PSC) in CTX-induced endothelial damage (CIED). Metabolic oxygen demand (dh), tissue oxygenation (StO2), oxygen supply (O2h) and microvascular perfusion (th) were measured with quantitative time-resolved near infra-red spectroscopy (NIRS) and temperature with thermography on upper extremities following standard procedures in healthy volunteers (n=12, 6 female; age 22±2), peripheral arterial disease patients (n=17, PAD; 75% male, age 68±9 years, 42%, positive controls) and CTX (n=22) with and without clinical CIPN (n=11 each, 46% male; age 64±11 years). Endothelial microvascular function was quantified during post-ischaemic reactive hyperaemia (PIRH). Resting muscle metabolism was quantified by dh during minute 1 of arterial occlusion. Perfusion was quantified by th during venous occlusion. PSC was applied with commercially available compression products and patented palmar pads for up to 90 minutes under standardised and controlled conditions. PSC induces instant and constant fall of temperature (−4.8±0.8°C, p<0.05) and oxygen demand (−3.4±5.2μM, p<0.05). PSC lead to further reduction of tissue metabolism (O2h: −27±38%, dh: −27±38.2%, PIRH-AUC: −20±27%, p<0,05 each compared to without PSC). Oxygen supply increased time-dependently (O2h: 3.0±1.3 μM, p<0.001) as consequence of locally increased perfusion (19±45%, p<0.05) with subsequent rise of tissue oxygenation (StO2: 9.1±4.2, p<0.01) that continued beyond the PSC-duration, indicating a rather metabolic mechanism. This effect is accompanied by a significant similar, albeit lesser reaction on the control hand (p<0.05). PIRH was reduced in controls in response to PSC as a sign for reduced metabolism. In PAD, reaction to PSC was less pronounced and non-significant, reflecting effects of endothelial dysfunction. Patients with CTX with CIPN showed significant endothelial dysfunction compared to controls (StO2 downslope −7±2%, T95 (s) 13±5, PIRH-AUC 9±6, p<0.05 each) and to CTX without CIPN (p<0.05 each), like PAD. For the first time, CIED as result of CTX comparable to atherosclerotic disease is shown. In contrast to previous assumptions of clinicians propagating compression therapy for prevention of CIPN, the results presented prove that not constriction of the products, but rather a combination of increased local perfusion and oxygen delivery in combination with mechanical effects on the low pressure system and reduced metabolism is induced by PSC. These findings open the field for well-designed RCTs to develop novel treatment options for CIPN targeting CIED. Funding Acknowledgement Type of funding sources: Private company. Main funding source(s): MEDIACC GmbH

Molecular photothermal effects on time-resolved IR spectroscopy.

Time-resolved IR pump-probe (IR-PP) and two-dimensional IR (2D-IR) spectroscopy are valuable techniques for studying various ultrafast chemical and biological processes in solutions. The time-dependent changes of nonlinear IR signals reflecting fast molecular processes such as vibrational energy transfer and chemical exchange provide invaluable information on the rates and mechanisms of solvation dynamics and structural transitions of multispecies vibrationally interacting molecular systems. However, due to the intrinsic difficulties in distinguishing the contributions of molecule-specific processes to the time-resolved IR signals from those resulting from local heating, it becomes challenging to interpret time-resolved IR-PP and 2D-IR spectra exhibiting transient growing-in spectral components and cross-peaks unambiguously. Here, theoretical considerations of various effects of vibrational coupling, energy transfer, chemical exchange, the generation of hot ground states, molecular photothermal process, and their combinations on the line shapes and time-dependent intensities of IR-PP spectra and 2D-IR diagonal peaks and cross-peaks are presented. We anticipate that the present work will help researchers using IR pump-probe and 2D-IR techniques to distinguish local heating-induced photothermal signals from genuine nonlinear IR signals.

Unraveling the Photoactivation Mechanism of a Light-Activated Adenylyl Cyclase Using Ultrafast Spectroscopy Coupled with Unnatural Amino Acid Mutagenesis.

The hydrogen bonding network that surrounds the flavin in blue light using flavin adenine dinucleotide (BLUF) photoreceptors plays a crucial role in sensing and communicating the changes in the electronic structure of the flavin to the protein matrix upon light absorption. Using time-resolved infrared spectroscopy (TRIR) and unnatural amino acid incorporation, we investigated the photoactivation mechanism and the role of the conserved tyrosine (Y6) in the forward reaction of the photoactivated adenylyl cyclase from Oscillatoria acuminata (OaPAC). Our work elucidates the direct connection between BLUF photoactivation and the structural and functional implications on the partner protein for the first time. The TRIR results demonstrate the formation of the neutral flavin radical as an intermediate species on the photoactivation pathway which decays to form the signaling state. Using fluorotyrosine analogues to modulate the physical properties of Y6, the TRIR data reveal that a change in the pKa and/or reduction potential of Y6 has a profound effect on the forward reaction, consistent with a mechanism involving proton transfer or proton-coupled electron transfer from Y6 to the electronically excited FAD. Decreasing the pKa from 9.9 to <7.2 and/or increasing the reduction potential by 200 mV of Y6 prevents proton transfer to the flavin and halts the photocycle at FAD•-. The lack of protonation of the anionic flavin radical can be directly linked to photoactivation of the adenylyl cyclase (AC) domain. While the 3F-Y6 and 2,3-F2Y6 variants undergo the complete photocycle and catalyze the conversion of ATP into cAMP, enzyme activity is abolished in the 3,5-F2Y6 and 2,3,5-F3Y6 variants where the photocycle is halted at FAD•-. Our results thus show that proton transfer plays an essential role in initiating the structural reorganization of the AC domain that results in AC activity.

IR-Supported Thermogravimetric Analysis of Water in Hydrogels

Isothermal thermogravimetry in a kinetic mode and time-resolved infrared spectroscopy was used to characterize water and its binding in hydrogels formed by interactions between hyaluronan and micelles of Septonex, an oppositely charged surfactant. Thermogravimetry provided detailed insight into the dehydration kinetics of the gel and thus brought indirect information on the strength of water binding in the hydrogel network. Infrared (IR) spectroscopy complemented the study with a direct analysis of structural changes occurring in the gel during its dehydration. IR spectroscopy thus contributed to understanding the processes which were observed in thermogravimetry, qualitatively, on the molecular level. This study can contribute to a broader application of the combined thermogravimetry–IR approach in the study of hydrogel materials and the development of their applications, especially in bio-related areas where water is among the key players.

Direct Observation of the Dynamics of Ylide Solvation by Hydrogen-bond Donors Using Time-Resolved Infrared Spectroscopy.

The photoexcitation of α-diazocarbonyl compounds produces singlet carbene intermediates that react with nucleophilic solvent molecules to form ylides. The zwitterionic nature of these newly formed ylides induces rapid changes in their interactions with the surrounding solvent. Here, ultrafast time-resolved infrared absorption spectroscopy is used to study the ylide-forming reactions of singlet carbene intermediates from the 270 nm photoexcitation of ethyl diazoacetate in various solvents and the changes in the subsequent ylide–solvent interactions. The results provide direct spectroscopic observation of the competition between ylide formation and C–H insertion in reactions of the singlet carbene with nucleophilic solvent molecules. We further report the specific solvation dynamics of the tetrahydrofuran (THF)-derived ylide (with a characteristic IR absorption band at 1636 cm–1) by various hydrogen-bond donors and the coordination by lithium cations. Hydrogen-bonded ylide bands shift to a lower wavenumber by −19 cm–1 for interactions with ethanol, −14 cm–1 for chloroform, −10 cm–1 for dichloromethane, −9 cm–1 for acetonitrile or cyclohexane, and −16 cm–1 for Li+ coordination, allowing the time evolution of the ylide–solvent interactions to be tracked. The hydrogen-bonded ylide bands grow with rate coefficients that are close to the diffusional limit. We further characterize the specific interactions of ethanol with the THF-derived ylide using quantum chemical (MP2) calculations and DFT-based atom-centered density matrix propagation trajectories, which show preferential coordination to the α-carbonyl group. This coordination alters the hybridization character of the ylidic carbon atom, with the greatest change toward sp2 character found for lithium-ion coordination.

Time-resolved infrared absorption spectroscopy applied to photoinduced reactions: how and why.

Time-resolved infrared (IR)spectroscopy is a widely used technique in the investigation of photoinduced reactions, given its capabilities of providing structural information about the presence of intermediates and the reaction mechanism. Despite the fact that it is used in several fields since the '80s, the communication between the different scientific communities (photochemists, photobiologists, etc.) has been to date quite limited. In some cases, this lack of communication happened-and still happens-even inside the same scientific community (for instance between specialists in ultrafast ps/fs IR and those in "fast" ns/µs/ms IR). Even more surprising is the difficulty of non-specialists to understand the potential of time-resolved IR spectroscopy, despite the fact that IR spectroscopy is normally taught to all chemistry and material science students, and to several biology and physics students. This tutorial review aims at helping to solve these issues, first by providing a comprehensive but reader-friendly overview of the different techniques, and second, by focusing on five "case studies" (from photobiology, gas-phase photocatalysis, photochemistry, semiconductors and metal-carbonyl complexes). We are confident that this approach can help the reader-whichever is its background-to understand the capabilities of time-resolved IR spectroscopy to study the mechanism of photoinduced reactions.

Time-Resolved Infrared Spectroscopy with Multivariate Analysis on Photoinduced Proton Transfer in Aromatic Urea-Acetate Anion Complexes.

1-Anthracen-2-yl-3-phenylurea (2PUA) is an aromatic urea compound, which forms a hydrogen-bonded complex with an acetate anion (AcO-), 2PUA-AcO- complex. We investigated the photoinduced reaction of the 2PUA-AcO- complex in dimethyl sulfoxide (DMSO) by nanosecond time-resolved infrared (TR-IR) spectroscopy. TR-IR spectra obtained after the photoexcitation of 2PUA with the equal concentration of AcO- were consistently explained by a photoinduced proton transfer model. The spectral and temporal profiles of the TR-IR spectra largely depended on concentration conditions of 2PUA and AcO-. Under the condition where excessive amounts of AcO- existed, the TR-IR spectra contained an unexpected signal whose amplitude was related to the concentration of free AcO- in the solution. Using singular value decomposition analysis of the concentration-dependent TR-IR spectra, we extracted the spectral component that reflects the photoinduced reaction of the 2PUA-AcO- complex. The extracted spectrum resembled the TR-IR spectrum obtained under the equal concentration condition, indicating that the same proton transfer occurs during the photoinduced reaction of the 2PUA-AcO- complex irrespective of the concentration conditions. Comparing the steady-state and transient IR spectra of the 2PUA with AcO- in DMSO with density functional theory calculations suggests that both 2PUA-AcO- complex and tautomer species interact with solvent DMSO molecules in their electronic ground states to a large extent.

Selective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes

The ability to control photoinduced charge transfer within molecules represents a major challenge requiring precise control of the relative positioning and orientation of donor and acceptor groups. Here we show that such photoinduced charge transfer processes within homo- and hetero-rotaxanes can be controlled through organisation of the components of the mechanically interlocked molecules, introducing alternative pathways for electron donation. Specifically, studies of two rotaxanes are described: a homo[3]rotaxane, built from a perylenediimide diimidazolium rod that threads two pillar[5]arene macrocycles, and a hetero[4]rotaxane in which an additional bis(1,5-naphtho)-38-crown-10 (BN38C10) macrocycle encircles the central perylenediimide. The two rotaxanes are characterised by a combination of techniques including electron diffraction crystallography in the case of the hetero[4]rotaxane. Cyclic voltammetry, spectroelectrochemistry, and EPR spectroscopy are employed to establish the behaviour of the redox states of both rotaxanes and these data are used to inform photophysical studies using time-resolved infra-red (TRIR) and transient absorption (TA) spectroscopies. The latter studies illustrate the formation of a symmetry-breaking charge-separated state in the case of the homo[3]rotaxane in which charge transfer between the pillar[5]arene and perylenediimide is observed involving only one of the two macrocyclic components. In the case of the hetero[4]rotaxane charge separation is observed involving only the BN38C10 macrocycle and the perylenediimide leaving the pillar[5]arene components unperturbed.

Time-resolved infra-red studies of photo-excited porphyrins in the presence of nucleic acids and in HeLa tumour cells: insights into binding site and electron transfer dynamics.

Cationic porphyrins based on the 5,10,15,20-meso-(tetrakis-4-N-methylpyridyl) core (TMPyP4) have been studied extensively over many years due to their strong interactions with a variety of nucleic acid structures, and their potential use as photodynamic therapeutic agents and telomerase inhibitors. In this paper, the interactions of metal-free TMPyP4 and Pt(II)TMPyP4 with guanine-containing nucleic acids are studied for the first time using time-resolved infrared spectroscopy (TRIR). In D2O solution (where the metal-free form exists as D2TMPyP4) both compounds yielded similar TRIR spectra (between 1450-1750 cm-1) following pulsed laser excitation in their Soret B-absorption bands. Density functional theory calculations reveal that vibrations centred on the methylpyridinium groups are responsible for the dominant feature at ca. 1640 cm-1. TRIR spectra of D2TMPyP4 or PtTMPyP4 in the presence of guanosine 5'-monophosphate (GMP), double-stranded {d(GC)5}2 or {d(CGCAAATTTGCG)}2 contain negative-going signals, 'bleaches', indicative of binding close to guanine. TRIR signals for D2TMPyP4 or PtTMPyP bound to the quadruplex-forming cMYC sequence {d(TAGGGAGGG)}2T indicate that binding occurs on the stacked guanines. For D2TMPyP4 bound to guanine-containing systems, the TRIR signal at ca. 1640 cm-1 decays on the picosecond timescale, consistent with electron transfer from guanine to the singlet excited state of D2TMPyP4, although IR marker bands for the reduced porphyrin/oxidised guanine were not observed. When PtTMPyP is incorporated into HeLa tumour cells, TRIR studies show protein binding with time-dependent ps/ns changes in the amide absorptions demonstrating TRIR's potential for studying light-activated molecular processes not only with nucleic acids in solution but also in biological cells.

Charge carrier dynamics and reaction intermediates in heterogeneous photocatalysis by time-resolved spectroscopies.

Sunlight as the most abundant renewable energy holds the promise to make our society sustainable. However, due to its low power density and intermittence, efficient conversion and storage of solar energy as a clean fuel are crucial. Apart from solar fuel synthesis, sunlight can also be used to drive other reactions including organic conversion and air/water purification. Given such potential of photocatalysis, the past few decades have seen a surge in the discovery of photocatalysts. However, the current photocatalytic efficiency is still very moderate. To address this challenge, it is important to understand fundamental factors that dominate the efficiency of a photocatalytic process to enable the rational design and development of photocatalytic systems. Many recent studies highlighted transient absorption spectroscopy (TAS) and time-resolved infrared (TRIR) spectroscopy as powerful approaches to characterise charge carrier dynamics and reaction pathways to elucidate the reasons behind low photocatalytic efficiencies, and to rationalise photocatalytic activities exhibited by closely related materials. Accordingly, as a fast-moving area, the past decade has witnessed an explosion in reports on charge carrier dynamics and reaction mechanisms on a wide range of photocatalytic materials. This critical review will discuss the application of TAS and TRIR in a wide range of heterogeneous photocatalytic systems, demonstrating the variety of ways in which these techniques can be used to understand the correlation between materials design, charge carrier behaviour, and photocatalytic activity. Finally, it provides a comprehensive outlook for potential developments in the area of time-resolved spectroscopies with an aim to provide design strategies for photocatalysts.

Real-time observation of photoionization-induced water migration dynamics in 4-methylformanilide-water by picosecond time-resolved infrared spectroscopy and ab initio molecular dynamics simulations.

A novel time-resolved pump-probe spectroscopic approach that enables to keep high resolution in both the time and energy domain, nanosecond excitation-picosecond ionization-picosecond infrared probe (ns-ps-ps TRIR) spectroscopy, has been applied to the trans-4-methylformanilide-water (4MetFA-W) cluster. Water migration dynamics from the CO to the NH binding site in a peptide linkage triggered by photoionization of 4MetFA-W is directly monitored by the ps time evolution of IR spectra, and the presence of an intermediate state is revealed. The time evolution is analyzed by rate equations based on a four-state model of the migration dynamics. Time constants for the initial to the intermediate and hot product and to the final product are obtained. The acceleration of the dynamics by methyl substitution and the strong contribution of intracluster vibrational energy redistribution in the termination of the solvation dynamics is suggested. This picture is well confirmed by the ab initio on-the-fly molecular dynamics simulations. Vibrational assignments of 4MetFA and 4MetFA-W in the neutral (S0 and S1) and ionic (D0) electronic states measured by ns IR dip and electron-impact IR photodissociation spectroscopy are also discussed prior to the results of time-resolved spectroscopy.

Characterization of Acetonitrile Isotopologues as Vibrational Probes of Electrolytes.

Acetonitrile has emerged as a solvent candidate for novel electrolyte formulations in metal-ion batteries and supercapacitors. It features a bright local C≡N stretch vibrational mode whose infrared (IR) signature is sensitive to battery-relevant cations (Li+, Mg2+, Zn2+, Ca2+) both in pure form and in the presence of water admixture across a full possible range of concentrations from the dilute to the superconcentrated regime. Stationary and time-resolved IR spectroscopy thus emerges as a natural tool to study site-specific intermolecular interactions from the solvent perspective without introducing an extrinsic probe that perturbs solution morphology and may not represent the intrinsic dynamics in these electrolytes. The metal-coordinated acetonitrile, water-separated metal–acetonitrile pair, and free solvent each have a distinct vibrational signature that allows their unambiguous differentiation. The IR band frequency of the metal-coordinated acetonitrile depends on the ion charge density. To study the ion transport dynamics, it is necessary to differentiate energy-transfer processes from structural interconversions in these electrolytes. Isotope labeling the solvent is a necessary prerequisite to separate these processes. We discuss the design principles and choice of the CD313CN label and characterize its vibrational spectroscopy in these electrolytes. The Fermi resonance between 13C≡N and C–D stretches complicates the spectral response but does not prevent its effective utilization. Time-resolved two-dimensional (2D) IR spectroscopy can be performed on a mixture of acetonitrile isotopologues and much can be learned about the structural dynamics of various species in these formulations.

Solvent-Dependent Excited-State Evolution of Prodan Dyes.

Excited-state character and dynamics of two 6-(dimethylamino)-2-acylnaphthalene dyes (Prodan and Badan-SCH2CH2OH) were studied by picosecond time-resolved IR spectroscopy (TRIR) in solvents of different polarity and relaxation times: hexane, CD3OD, and glycerol-d8. In all these solvents, near-UV excitation initially produced the same S1(ππ*) excited state characterized by a broad TRIR signal. A very fast decay (3, ∼100 ps) followed in hexane, whereas conversion to a distinct IR spectrum with a ν(C═O) band downshifted by 76 cm-1 occurred in polar/H-bonding solvents, slowing down on going from CD3OD (1, 23 ps) to glycerol-d8 (5.5, 51, 330 ps). The final relaxed excited state was assigned as planar Me2N → C═O intramolecular charge transfer S1(ICT) by comparing experimental and TDDFT-calculated spectra. TRIR conversion kinetics are comparable to those of early stages of multiexponential fluorescence decay and dynamic fluorescence red-shift. This work presents a strong evidence that Prodan-type dyes undergo solvation-driven charge separation in their S1 state, which is responsible for the dynamic fluorescence Stokes shift observed in polar/H-bonding solvents. The time evolution of the optically prepared S1(ππ*) state to the S1(ICT) final state reflects environment relaxation and solvation dynamics. This finding rationalizes the widespread use of Prodan-type dyes as probes of environment dynamics and polarity.

Isomer-Selective Spectroscopy and Dynamics of Phenol-Arn (n ≤ 5) Clusters.

Structures and ionization-induced solvation dynamics of phenol-(argon)n clusters, PhOH-Arn (n ≤ 5), were studied by using a variety of isomer-selective photoionization and vibrational spectroscopic techniques. Several higher-energy isomers were found and assigned for the first time by systematically controlling the experimental conditions of the supersonic expansion. This behavior is also confirmed for the PhOH-Kr2 cluster. Solvation structures are elucidated by evaluating systematic shifts in the S1 ← S0 origin and ionization energies obtained by resonance-enhanced photoionization, in addition to the OH stretching frequency obtained by IR photodissociation. Isomer-selective picosecond time-resolved IR spectroscopy for the n = 2 clusters revealed that the dynamics for the ionization-induced intermolecular π → H site-switching reaction strongly depends on the initial isomeric structure. In particular, the reaction time for the (1|1) isomer is 7 ps, while that for (2|0) is <3 ps. This difference shows that the switching time is determined by the distance of the reaction coordinate between the initial π-site and the final OH-site.