Electronic Relaxation Research Articles

The comprehensive investigation of barrier layers on power loss mechanisms in AlGaN/GaN HEMT structures

The electron relaxation mechanism of the electrons in the pseudo triangle quantum well located in the Al0.3Ga0.7N/GaN heterostructure interface grown by the Molecular Beam Epitaxy (MBE) is studied by Shubnikov de-Haas (SdH) oscillations. Four different sample types were used in the experiments; the carrier density in the quantum well is the same for all samples, whereas the top layer structures are different. The effects of a spacer layer placed between the barrier layer and the quantum well layer, a doped barrier layer placed behind the undoped barrier layer, and a passivation layer placed as a top layer on the energy relaxation processes of the carriers in the quantum well were investigated. The SdH oscillation measurements were carried out under a magnetic field of up to 11 T at a temperature range of 1.8–20 K. The electron temperatures and energy relaxation mechanisms are obtained by comparing the change in the relative amplitude of SdH oscillations in different applied electric fields and lattice temperatures. It is deduced that the samples with a passivation layer and doped barrier layer have higher electron temperatures at lower applied electric fields. The hot electrons relax with acoustic phonon scattering for these samples, including deformation and piezoelectric interactions in the low-temperature region determined theoretically. However, the hot electrons relax with acoustic phonon scattering for samples with spacer layer and spacer/passivation layers in the high-temperature region determined theoretically. Furthermore, it was observed that the spacer and passivation layers lead to faster relaxation of hot electrons.

TD-DFT analysis of the photo-ring-opening reaction of the flav-3-en-2-ol in acetonitrile solution: Functional choice and effect of solvated hydrogen bond

Of the forty hybrid functionals supported by Gaussian 16, only fourteen functionals with small contributions from the exact Hartree-Fock exchange demonstrated the breaking of the C2-O1 bond of flav-3-en-2-ol: TPSSh, O3LYP, τHCTHhyb, B3LYP, B3P86, B3PW91, B971, B972, X3LYP, B98, APF, APFD, mPW1LYP, and mPW3PBE. TPSSh and O3LYP gave rise to a cis-2-hydroxychalcone transition accompanied by ground-state intramolecular proton transfer (GSIPT), and the remaining twelve functionals selected showed a return to the flav-3-en-2-ol with the recovery of the C2-O1 bond. The strong H-bond of acetonitrile with flav-3-en-2-ol has a striking effect on the consequences of the excitation in comparison with a single flav-3-en-2-ol molecule: optimization of the S1 excited state of the solvated complex leads to the breaking of the C2-O1 bond by O3LYP functional only. However, upon relaxation of the excited enol form, this bond was recovered, and a return to the flav-3-en-2-ol occurred. Nevertheless, the O3LYP functional gives a theoretical model consistent with the experiment: the H-bond of flav-3-en-2-ol with the acetonitrile molecule is a switch in the reaction path. If this H-bond is present at the excitation moment, then the flav-3-en-2-ol molecule undergoes a C2-O1 bond cleavage but recovers upon relaxation. If this H-bond is absent, then the flav-3-en-2-ol molecule transforms into the enol form which goes further into cis-2-hydroxychalcone. The excitation of the solvated complex causes a pronounced strengthening of this intermolecular H-bond. GSIPT is caused by a change in the polarization of the enol form during its electronic relaxation, as a result of which the proton begins to experience a stronger attraction to the opposite part of the molecule.

Tensile Strain-Dependent Ultrafast Electron Transfer and Relaxation Dynamics in Flexible WSe2/MoS2 Heterostructures.

Understanding and controlling carrier dynamics in two-dimensional (2D) van der Waals heterostructures through strain are crucial for their flexible applications. Here, femtosecond transient absorption spectroscopy is employed to elucidate the interlayer electron transfer and relaxation dynamics under external tensile strains in a WSe2/MoS2 heterostructure. The results show that a modest ∼1% tensile strain can significantly alter the lifetimes of electron transfer and nonradiative electron-hole recombination by >30%. Ab initio non-adiabatic molecular dynamics simulations suggest that tensile strain weakens the electron-phonon coupling, thereby suppressing the transfer and recombination dynamics. Theoretical predictions indicate that strain-induced energy difference increases along the electron transfer path could contribute to the prolongation of the transfer lifetime. A subpicosecond decay process, related to hot-electron cooling, remains almost unaffected by strain. This study demonstrates the potential of tuning interlayer carrier dynamics through external strains, offering insights into flexible optoelectronic device design with 2D materials.

Electronic relaxation mechanism of 9-methyl-2,6-diaminopurine and 2,6-diaminopurine-2'-deoxyribose in solution.

Prolonged ultraviolet exposure results in the formation of cyclobutane pyrimidine dimers (CPDs) in RNA. Consequently, prebiotic photolesion repair mechanisms should have played an important role in the maintenance of the structural integrity of primitive nucleic acids. 2,6-Diaminopurine is a prebiotic nucleobase that repairs CPDs with high efficiency when incorporated into polymers. We investigate the electronic deactivation pathways of 2,6-diaminopurine-2'-deoxyribose and 9-methyl-2,6-diaminopurine in acetonitrile and aqueous solution to shed light on the photophysical and excited state properties of the 2,6-diaminopurine chromophore. Evidence is presented that both are photostable compounds exhibiting similar deactivation mechanisms upon the population of the S1 (ππ* La ) state at 290 nm. The mechanism involves deactivation through the C2- and C6-reaction coordinates and >99% of the excited state population decays through nonradiative pathways involving two conical intersections with the ground state. The radiative and nonradiative lifetimes are longer in aqueous solution compared to acetonitrile. While τ1 is similar in both derivatives, τ2 is ca. 1.5-fold longer in 2,6-diaminopurine-2'-deoxyribose due to a more efficient trapping in the S1 (ππ* La ) minimum. Therefore, 2,6-diaminopurine could have accumulated in significant quantities during prebiotic times to be incorporated into non-canonical RNA and play a significant role in its photoprotection.

The solid effect of dynamic nuclear polarization in liquids - accounting for g-tensor anisotropy at high magnetic fields.

In spite of its name, the solid effect of dynamic nuclear polarization (DNP) is also operative in viscous liquids, where the dipolar interaction between the polarized nuclear spins and the polarizing electrons is not completely averaged out by molecular diffusion on the timescale of the electronic spin-spin relaxation time. Under such slow-motional conditions, it is likely that the tumbling of the polarizing agent is similarly too slow to efficiently average the anisotropies of its magnetic tensors on the timescale of the electronic . Here we extend our previous analysis of the solid effect in liquids to account for the effect of -tensor anisotropy at high magnetic fields. Building directly on the mathematical treatment of slow tumbling in electron spin resonance , we calculate solid-effect DNP enhancements in the presence of both translational diffusion of the liquid molecules and rotational diffusion of the polarizing agent. To illustrate the formalism, we analyze high-field (9.4 T) DNP enhancement profiles from nitroxide-labeled lipids in fluid lipid bilayers. By properly accounting for power broadening and motional broadening, we successfully decompose the measured DNP enhancements into their separate contributions from the solid and Overhauser effects.

Few-femtosecond electronic and structural rearrangements of driven by the Jahn-Teller effect.

The Jahn-Teller effect (JTE) is central to the understanding of the physical and chemical properties of a broad variety of molecules and materials. Whereas the manifestations of the JTE in stationary properties of matter are relatively well studied, the study of JTE-induced dynamics is still in its infancy, largely owing to its ultrafast and non-adiabatic nature. For example, the time scales reported for the distortion of from the initial geometry to a nominal relaxed structure range from 1.85 fs over 10 ± 2 fs to 20 ± 7 fs. Here, by combining element-specific attosecond transient-absorption spectroscopy and quantum-dynamics simulations, we show that the initial electronic relaxation occurs within 5 fs and that the subsequent nuclear dynamics are dominated by the Q2 scissoring and Q1 symmetric stretching modes, which dephase in 41 ± 10 fs and 13 ± 3 fs, respectively. Significant structural relaxation is found to take place only along the e-symmetry Q2 mode. These results demonstrate that created by ionization of is best thought of as a highly fluxional species that possesses a long-time-averaged vibrational distribution centered around a structure. The methods demonstrated in our work provide guidelines for the understanding of Jahn-Teller driven non-adiabatic dynamics in other more complex systems.

Defects and plasma Ag co-modified S-scheme Ag/NVs-CN/Bi2O2-δCO3 heterojunction with multilevel charge transfer channels for boosting full-spectrum-driven degradation of antibiotics

The optimization of the photogenerated carriers’ relaxation dynamics process is critical for the improvement of photocatalytic performance. Herein, a ternary heterojunction with multilevel charge transfer channels was constructed by coupling plasma Ag, nitrogen vacancies carbon nitride (NVs-CN) and Bi2O2-δCO3. Ag/NVs-CN/Bi2O2-δCO3 heterojunction showed the S-scheme mechanism, which not only promoted the interfacial charge transfer, but also enhanced the driving force for redox reactions. The defect states induced by nitrogen vacancies and oxygen vacancies provided an additional energy level platforms for hot electrons relaxation of plasma Ag, resulting in the improved separation efficiency and utilization rate of the high-energy hot carriers. Hence, the prepared Ag/NVs-CN/Bi2-δO2CO3 heterojunction exhibited the markedly boosted full-spectrum driven catalytic activity for antibiotics degradation. 80.5% and 83.8% of tetracycline and ciprofloxacin could be mineralized into H2O and CO2 by the optimal heterojunction under visible light irradiation, and the corresponding mineralization efficiencies could reach 81.7% and 81.5% under NIR light irradiation. The proposed multichannel charge transfer mechanism provided a new insight into the design and preparation of high-active full-spectrum responsive heterojunction photocatalysts.

Multi-Spectroscopic and TD-DFT Studies on Chromogenic and Fluorogenic Detection of Cyanide in an Aqueous Solution.

Different spectroscopic techniques and Density Functional Theory (DFT)/Time-Dependent Density Functional Theory (TDDFT) calculations have been employed to investigate the dual channel CN- detection behaviour of the developed chemo-dosimeter (AK3). The CN- with AK3 reaction triggered a colour change from pale yellow to colourless and enhanced fluorescence. UV-Vis, fluorescence, 1H & 13C NMR and mass techniques coupled with theoretical calculations (Mulliken charges, dihedral angles) revealed that the CN- sensing process mechanism involves deprotonation of the N-H group followed by nucleophilic addition reaction. Detailed TD-DFT calculations showed that the relaxation of excited electrons from LUMO and to two different ground states is responsible for the weak/moderate fluorescence of AK3. Nucleophilic addition of CN- to the C-atom of the CH = CH bridge terminated the π-conjugation between donor and acceptor regions, reduced the coplanarity, decreased the ICT transition and consequently enhanced the fluorescence of the probe. The practical utility of the probe was demonstrated by detecting cyanide in food materials and determining CN- in environmental water samples.

Holmium (III)-doped multifunctional nanotheranostic agent for ultra-high-field magnetic resonance imaging-guided chemo-photothermal tumor therapy

Ultra-high-field (UHF) MRI has shown great advantages over low-field magnetic resonance imaging (MRI). Despite being the most commonly used MRI contrast agents, gadolinium chelates perform poorly in high magnetic fields, which significantly weakens their T1 intensity. In comparison, the rare element Holmium (Ho)-based nanoparticles (NPs) have demonstrated great potential as T2-weighted MRI contrast agents in UHF MRI due to their extremely short electron relaxation times (∼ 10−13s). In this study, a multifunctional nanotherapeutic probe was designed for UHF MRI-guided chemotherapy and photothermal therapy. The Ho (III)-doped mesoporous polydopamine (Ho-MPDA, HM) nanosphere was loaded with the chemotherapeutic drug mitoxantrone (MTO) and then coated with 4T1 cell membranes to enhance active targeting delivery to breast cancer. The prepared nanotherapeutic probe MTO@HMM@4T1 (HMM@T) exhibited good biocompatibility, high drug-loading capability and great potential as Ho (III)-based UHF MRI contrast agents. Moreover, the biodegradation of HMM@T in response to the intratumor pH and glutathione (GSH) promotes MTO release. Near-infrared (NIR) light irradiation of HM induced photothermal therapy and further enhanced drug release. Consequently, HMM@T effectively acted as an MRI-guided tumor-targeting chemo-photothermal therapy against 4T1 breast cancer. Statement of significanceUltra-high-field (UHF) MRI has shown great advantages over low-field magnetic resonance imaging (MRI). Although gadolinium chelates are the most commonly used MRI contrast agents in clinical practice, they exhibit a significantly decreased T1 relaxivity at UHF. Holmium exhibits outstanding UHF magnetic resonance capabilities in comparison with gadolinium chelates currently used in clinic. Herein, a theranostic nanodrug (HMM@T) was designed for UHF MRI-guided chemo-photothermal therapy. The nanodrug possessed remarkable UHF T2 MRI properties (r2 = 152.13 mM−1s−1) and high drug loading capability of 18.4 %. The biodegradation of HMM@T NPs under triple stimulations of pH, GSH, and NIR led to an efficient release of MTO in tumor microenvironment. Our results revealed the potential of a novel UHF MRI-guided multifunctional nanosystem in cancer treatment.

Significantly enhanced performance and conductivity mechanism in Nb/Mn co-doped CaBi4Ti4O15 ferroelectrics

With the rapid development of high-end industries, the demand for high-temperature piezoelectric materials is significantly increasing. However, realizing the ultra-high performance to meet more applications still faces major scientific and engineering challenges of our time. Here, a new Nb/Mn co-doped CaBi4Ti4O15 (CBT) high-temperature piezoelectric material system of CaBi4Ti4-x(Nb2/3Mn1/3)xO15 was synthesized by the conventional solid-state sintering method. The results show that the addition of the dopants tends to break the long-range ferroelectric chain and soften the flexibility of polarization, resulting in more distorted crystal structure and better ferroelectric properties of CBT ceramics. The ultra-high piezoelectric constant (d33 = 26.8 pC/N) is thus attained in CBT-based ceramics with x = 0.12, which is about several times larger than that of pure CBT ceramics. Moreover, numerous nano-sized layered domain structures that lie on the lateral plane of grains are observed in ceramics, with lower domain wall energy and better dynamic features under electric fields, mainly responsible for the origin of enhanced performance. Besides, excess dopants could make the conductivity mechanism of CBT ceramics transform from p-type to n-type, and also result in a shift of conduction relaxation mechanism from defect dipole rotation polarization to electron relaxation polarization. The work not only provides a promising candidate for high-temperature piezoelectric materials, but also opens a window for optimizing performance by tailoring domain structures using chemical modification.

Reveal Ultrafast Electron Relaxation across Sub-bands of Tellurium by Time- and Energy-Resolved Photoemission Microscopy.

Exploring ultrafast carrier dynamics is crucial for the materials' fundamental properties and device design. In this work, we employ time- and energy-resolved photoemission electron microscopy with tunable pump wavelengths from visible to near-infrared to reveal the ultrafast carrier dynamics of the elemental semiconductor tellurium. We find that two discrete sub-bands around the Γ point of the conduction band are involved in excited-state electron ultrafast relaxation and reveal that hot electrons first go through ultrafast intra sub-band cooling on a time scale of about 0.3 ps and then transfer from the higher sub-band to the lower one on a time scale of approximately 1 ps. Additionally, theoretical calculations reveal that the lower one has flat-band characteristics, possessing a large density of states and a long electron lifetime. Our work demonstrates that TR- and ER-PEEM with broad tunable pump wavelengths are powerful techniques in revealing the details of ultrafast carrier dynamics in time and energy domains.

Efficient electroluminescence in doped-GaAs via terahertz metamaterials

We investigate the highly efficient terahertz nonlinearity exhibited by n-type GaAs crystals under metallic metamaterials. An intense THz field applied to the metamaterials leads to impact ionization in the GaAs substrate, which emits electroluminescence in the near-infrared region. Even for a similar THz field strength, n-type GaAs emits near-infrared photons more efficiently than semi-insulating GaAs. We analyzed the luminescence lineshapes and intensity as a function of the excitation field strength, using Fermi–Dirac statistics and the density of states in the conduction band to quantify electron density and locate the Fermi level after the relaxation of excited hot electrons.

Relaxation of relativistic pair plasma in a massive photon field

The relaxation of relativistic hot electron–positron plasma is investigated by incorporating the effect of non-zero photon mass, and a quadruple Beltrami (QB) relaxed state for the magnetic vector potential is derived. The QB state is a linear superposition of four single force-free fields and is characterized by four self-organized structures of different length scales. The analysis of QB states shows that for certain values of generalized helicities at lower relativistic temperatures, plasma shows diamagnetic behaviour. It is also noteworthy that the inclusion of non-zero photon mass naturally provides the possibility of multiscale structure formation in the relaxed state. In this scenario, one of the field structures is significantly larger than the Compton wavelength of photons, while the other three structures are on the scale of the electron skin depth. The potential implications of this QB state for astrophysical environments are also discussed.

Dynamical Phonons Following Electron Relaxation Stages in Photoexcited Graphene.

Ultrafast electron-phonon relaxation dynamics in graphene hides many distinct phenomena, such as hot phonon generation, dynamical Kohn anomalies, and phonon decoupling, yet it still remains largely unexplored. Here, we unravel intricate mechanisms governing the vibrational relaxation and phonon dressing in graphene at a highly nonequilibrium state by means of first-principles techniques. We calculate dynamical phonon spectral functions and momentum-resolved line widths for various stages of electron relaxation and find photoinduced phonon hardening, overall increase of relaxation rate and nonadiabaticity, as well as phonon gain. Namely, the initial stage of photoexcitation is found to be governed by strong phonon anomalies of finite-momentum optical modes along with incoherent phonon production. The population inversion state, on the other hand, allows the production of coherent and strongly coupled phonon modes. Our research provides vital insights into the electron-phonon coupling phenomena in graphene and serves as a foundation for exploring nonequilibrium phonon dressing in materials where ordered states and phase transitions can be induced by photoexcitation.

Field- and Temperature-Dependent Paramagnetic Relaxation Enhancements in Co(II) Trispyrazolylmethanes.

A comprehensive field- and temperature-dependent examination of nuclear magnetic resonance paramagnetic relaxation enhancements (PREs) for the constitutive protons of [Co(Tpm)2][BF4]2 is presented. Data for an apically substituted derivative clearly establish that bis-Tpm complexes of Co(II) undergo Jahn-Teller dynamics about the molecular threefold axis. PREs from the parent Tpm complex were used to numerically extract the electron relaxation times (T1e). The Tpm complex showed field-dependent behavior, with an approximately 40% higher activation barrier than the related trispyrazolylborate (Tp) complex, based on fits to the T1e vs T, B0 data. Analysis of the field-dependent line widths revealed a surprisingly large contribution from susceptibility (Curie) relaxation (20-35% at the highest field), and a molecular radius (9.5 Å) that is consistent with a tightly associated counterion slowing rotation in solution. Density functional theory showed a shared vibration that is consistent with the Jahn-Teller and appears proportionately higher in energy in [Co(Tpm)2]2+. Complete active-space self-consistent field calculations support ascribing electron relaxation to enhanced mixing of the two Eg orbital sets that accompanies the tetragonal distortion and the differences in electron correlation times to the higher Jahn-Teller activation barrier in [Co(Tpm)2]2+.

Redox enhanced slow ion kinetics in oxide ceramics

AbstractThere is a growing interest in field‐assisted fast ceramic processing and long‐term service of electrochemical devices under harsh operation conditions. These extreme redox conditions can make some conventionally thought slow ions highly mobile in electrochemical materials and devices and greatly accelerate the microstructural evolution. Experimental observations for enhanced slow ion diffusion that controls mass transport include accelerated grain growth in zirconia and ceria under atmospheric and electrochemical reduction above 1000°C and lattice cavitation of high‐voltage Li‐rich layered cathodes of lithium‐ion batteries at room temperature. These observations cannot be explained by altered defect concentrations under defect chemistry arguments. Instead, they support hugely enhanced slow ion mobility. My colleagues and I recently proposed a new mechanism resulted from strong electron–phonon interactions and dynamic electronic relaxations at the saddle point of an ion hopping event, which significantly lowers the ion migration barrier. In this perspective article, the theory and its experimental and computational supports shall be discussed. Such an electronic effect holds even in nominally ionic ceramic materials with wide bandgaps and is expected to be general in many transition metal oxides. It rationalizes a variety of intriguing experimental observations and offers an electronic perspective on the redox enhancement of slow ion kinetics in structural, functional, and energy ceramics.

All-in-one self-floating porous foams as robust heat-blocking layers for efficient photothermal conversion and solar desalination

Solar-driven interfacial evaporation is a highly efficient and ecofriendly technology for producing freshwater. Herein, self-floating plasmon Ag/black TiO2/carbon porous layered foams (Ag-BTCFs) were demonstrated as efficient solar-thermal convectors using freeze-drying cast-molding and high-temperature surface hydrogenation strategies. This all-in-one three-dimensional (3D) cross-linked self-floating porous layered foam material with full-spectrum absorption can fully harvest sunlight (∼95.45%) and effectively block heat transfer to its sublayer. The synergy of sufficient utilization of absorbed ultraviolet radiation by black TiO2 (b-TiO2), visible light absorption by Ag nanoparticles (Ag NPs) via localized surface plasmon resonance, and near-infrared absorption by layered-amorphous carbon can achieve full-solar-spectrum absorption to concentrate thermal energy. In addition to their synergistic effect, they are conducive to the relaxation of hot electrons when utilizing photogenerated holes to degrade pollutants in domestic wastewater. The steam generation efficiency of Ag-BTCFs is up to 1.79 kg m−2h−1 due to their solar energy conversion efficiency of 81.74% under 1 sun irradiation, which is five times higher than the evaporation rate of pure water. Notably, the material’s efficient ion removal rate of 99.80% for solar desalination indicates its high potential for various applications. This strategy provides new insights for fabricating recyclable heat-blocking layer systems against thermal loss to enhance solar steam generation.

Size and crystallinity effect on the ultrafast optical response of chemically synthesized silver nanoparticles

The excited localized surface plasmon (LSP) in metallic nanoparticles is known to relax through several processes such as electron-electron scattering, electron-phonon coupling, and phonon-phonon scattering. In the current research, the ultrafast electron-phonon (e-ph) coupling relaxation processes for different average sizes and crystallinity of chemically synthesized silver nanoparticles were evaluated utilizing transient absorption spectroscopy. The nanoparticle size and crystallinity of similar linear dimension polycrystalline spherical and monocrystalline cubic nanoparticles ranging from ca. 30–60 nm was related to their electron relaxation time constants and revealed very different dependencies. For the monocrystalline nanocubes, the electron-phonon coupling was not dependent on the cube edge length, while for the polycrystalline nanospheres, it was linearly decreasing with diameter. We demonstrate that the e-ph coupling time constant could be used to evaluate crystallinity and crystallite size in plasmonic metal nanoparticles when the size (surface area) of the nanoparticle is known.

In-Situ-Grown Cu Dendrites Plasmonically Enhance Electrocatalytic Hydrogen Evolution on Facet-Engineered Cu2 O.

Herein, facet-engineered Cu2 O nanostructures are synthesized by wet chemical methods for electrocatalytic HER, and it is found that the octahedral Cu2 O nanostructures with exposed crystal planes of (111) (O-Cu2 O) has the best hydrogen evolution performance. Operando Raman spectroscopy and ex-situ characterization techniques showed that Cu2 O is reduced during HER, in which Cu dendrites are grown on the surface of the Cu2 O nanostructures, resulting in the better HER performance of O-Cu2 O after HER (O-Cu2 O-A) compared with that of the as-prepared O-Cu2 O. Under illumination, the onset potential of O-Cu2 O-A is ca. 52 mV positive than that of O-Cu2 O, which is induced by the plasmon-activated electrochemical system consisting of Cu2 O and the in-situ generated Cu dendrites. Incident photon-to-current efficiency (IPCE) measurements and the simulated UV-Vis spectrum demonstrate the hot electron injection (HEI) from Cu dendrites to Cu2 O. Ab initio nonadiabatic molecular dynamics (NAMD) simulations revealed the transfer of photogenerated electrons (27 fs) from Cu dendrites to Cu2 O nanostructures is faster than electron relaxation (170 fs), enhancing its surface plasmons activity, and the HEI of Cu dendrites increases the charge density of Cu2 O. These make the energy level of the catalyst be closer to that of H+ /H2 , evidenced by the plasmon-enhanced HER electrocatalytic activity.

Ultrafast Proton Transfer and Contact Ion-Pair Formation in Formic Acid Clusters.

The ultrafast proton transfer dynamics of homogeneous formic acid clusters (FA)n, n < 10, are investigated with femtosecond time-resolved mass spectrometry. We monitor the proton transfer pathway following Rydberg state electronic relaxation and find that successful ion pair formation increases logarithmically with cluster size. Ab initio calculations demonstrate similar excitation/relaxation behavior for each cluster, revealing a contact ion pair forms between two molecules composing the cluster before finally a formate anion (HCOO-) is dissociated by the probe pulse. The sub-ps time scale for rearrangement and proton transfer increases almost linearly with cluster size, requiring ∼67 fs per additional formic acid molecule and ranging from 213 ± 51 fs for the trimer to 667 ± 116 fs for FA9. The near-linear trends measured for both rearrangement lifetime and ion pair formation suggest that proton transfer is unlikely in the formic acid dimer but becomes prominent in small clusters.