Excited state dynamics of normal dithienylethene molecules either isolated or deposited on an argon cluster.

Real-time dynamics of the electronically excited open-ring isomer of 1,2-bis(2-methylbenzo[b]thiophen-3-yl)perfluorocyclopentene (BTF6) and 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene (PTF6) molecules was investigated using a set-up that associates a molecular beam, femtosecond lasers and velocity map imaging. The molecules were either free in the gas phase or bound to an argon cluster. DFT and TDDFT calculations were performed on BTF6. The calculated vertical excitation energies indicate an excitation by the pump laser towards a superposition of S5 and S6 states. The free molecule dynamics was found to follow a three wavepacket model. One describes the parallel conformer (P) of these molecules. It is unreactive with respect to the ring closure reaction which is responsible for the photochromic property of these molecules. It has no observable decay at the experiment time scale (up to 350 ps). The other two wavepackets describe the reactive antiparallel conformer (AP). They are formed by an early splitting of the wavepacket that was launched initially by the pump laser. They can be considered as generated by excitation of different, essentially uncoupled, deformation modes. They subsequently evolve along independent pathways. One is directed ballistically towards a conical intersection (CI) and decays through the CI to a potential energy surface where it can no longer be detected. The other fraction of the wavepacket decays also towards undetected states but in this case the driving mechanism is a non-adiabatic electronic relaxation within a potential well of the energy surfaces where it was launched. When BTF6 and PTF6 molecules are bound to an argon cluster, the same three wavepacket model applies. The vibronic relaxation timespan is enhanced by a factor 5 and a larger fraction of AP conformers follows this pathway. In contrast, the time constant associated with the ballistic movement is enhanced by only a factor of 2.

Consistent characterization of the electronic ground state of iron(II) phthalocyanine from valence and core-shell electron spectroscopy.

We studied the iron(II) phthalocyanine molecule in the gas-phase. It is a complex transition organometallic compound, for which, the characterization of its electronic ground state is still debated more than 50 years after the first published study. Here, we show that to determine its electronic ground state, one needs a large corpus of data sets and a consistent theoretical methodology to simulate them. By simulating valence and core-shell electron spectra, we determined that the ground state is a 3Eg and that the ligand-to-metal charge transfer has a large influence on the spectra.

Time-Resolved Observation of the Solvation Dynamics of a Rydberg Excited Molecule Deposited on an Argon Cluster. II. DABCO☆ at Long Time Delays.

The real-time dynamics of DABCO-argon clusters is investigated in a femtosecond pump-probe experiment where the pump excites DABCO to the S1 state within the argon cluster. The probe operates by photoionization and documents the energy and angular distributions of the resulting photoelectrons. The present work complements a previous work from our group [Awali Phys. Chem. Chem. Phys., 2014, 16, 516-526] where this dynamics was probed at short time, up to 4 ps after the pump pulse. Here, the dynamics is followed up to 500 ps. A multiscale dynamics is observed. It includes a jump between two solvation sites (time scale 0.27 ps) followed by the relaxation of the solvation cage excess vibrational energy (time scale 14 ps) and then by that of DABCO (time scale >150 ps). Polarization anisotropy, double polarization, and angular anisotropy effects are reported also. They are interpreted (quantitatively for the former effect) in terms of decoherence of rotational alignment, driven by the overall rotation of the DABCO-argon clusters. A tomographic view of the DABCO excited orbital, provided by the double anisotropy effect, is discussed on a qualitative basis.

Water binding to FeIII hemes studied in a cooled ion trap: characterization of a strong 'weak' ligand.

The interaction of a water molecule with ferric heme-iron protoporphyrin ([PP FeIII]+) has been investigated in the gas phase in an ion trap and studied theoretically by density functional theory. It is found that the interaction of water with ferric heme leads to a stable [PP-FeIII-H2O]+ complex in the intermediate spin state (S = 3/2), in the same state as its unligated [PP-FeIII]+ homologue, without spin crossing during water attachment. Using the Van't Hoff equation, the reaction enthalpy for the formation of a Fe-OH2 bond has been determined for [PP-FeIII-H2O]+ and [PP-FeIII-(H2O)2]+. The corrected binding energy for a single Fe-H2O bond is -12.2 ± 0.6 kcal mol-1, while DFT calculations at the OPBE level yield -11.7 kcal mol-1. The binding energy of the second ligation yielding a six coordinated FeIII atom is decreased with a bond energy of -9 ± 0.9 kcal mol-1, well reproduced by calculations as -7.1 kcal mol-1. However, calculations reveal features of a weaker bond type, such as a rather long Fe-O bond with 2.28 Å for the [PP-FeIII-H2O]+ complex and the absence of a spin change by complexation. Thus despite a strong bond with H2O, the FeIII atom does not show, through theoretical modelling, a strong acceptor character in its half filled 3dz2 orbital. It is also observed that the binding properties of H2O to hemes seem strikingly specific to ferric heme and we have shown, experimentally and theoretically, that the affinity of H2O for protonated heme [H PP-Fe]+, an intermediate between FeIII and FeII, is strongly reduced compared to that for ferric heme.

Energetics and ionization dynamics of two diarylketone molecules: benzophenone and fluorenone.

Single photon ionization and subsequent unimolecular ion decomposition were studied on jet-cooled benzophenone and fluorenone separately, using VUV synchrotron radiation in a photoion/photoelectron coincidence setup. Slow PhotoElectron Spectra (SPES) were recorded in coincidence with either the parent or the fragment ions for hν < 12.5 eV. Dissociative ionization is observed for benzophenone only. The full interpretation of the measurements, including the identification of the neutral and ionic species when dissociative ionization is at play, benefits from high level ab initio computations for determining the equilibrium structures and the energetics of the neutral and ionized molecules and of their fragments. Electronically excited states of the parent molecular ions were calculated also. From this analysis, an accurate experimental determination of the energetics of the benzophenone and fluorenone ions and of their fragmentation channels is available: adiabatic ionization energies of benzophenone at 8.923 ± 0.005 eV and of fluorenone at 8.356 ± 0.007 eV; and appearance energies of benzophenone fragment ions at 11.04 ± 0.02 eV (loss of C6H5), 11.28 ± 0.02 eV (loss of H) and 11.45 ± 0.02 eV (loss of CO). The corresponding fragmentation mechanisms are explored, showing likely concerted bonds rearrangement. Possible pre-ionizing fragmentation is discussed in light of the spectra presented. The structural rigidity of fluorenone diarylketone seems to be the origin of the inhibition of the fragmentation of its cation.

The dramatic effect of N-methylimidazole on trans axial ligand binding to ferric heme: experiment and theory.

The binding energy of CO, O2 and NO to isolated ferric heme, [FeIIIP]+, was studied in the presence and absence of a σ donor (N-methylimidazole and histidine) as the trans axial ligand. This study combines the experimental determination of binding enthalpies by equilibrium measurements in a low temperature ion trap using the van't Hoff equation and high level DFT calculations. It was found that the presence of N-methylimidazole as the axial ligand on the [FeIIIP]+ porphyrin dramatically weakens the [FeIIIP-ligand]+ bond with an up to sevenfold decrease in binding energy owing to the σ donation by N-methylimidazole to the FeIII(3d) orbitals. This trans σ donor effect is characteristic of ligation to iron in hemes in both ferrous and ferric redox forms; however, to date, this has not been observed for ferric heme.

Large amplitude motion within acetylene-rare gas complexes hosted in helium droplets.

Near-infrared spectroscopy of the C2H2-Ar, Kr complexes was performed in the spectral region overlapping the ν3/ν2 + ν4 + ν5 Fermi-type resonance of C2H2. The experiment was conducted along the HElium NanoDroplet Isolation (HENDI) technique in order to study the coupling dynamics between a floppy molecular system (C2H2-Ar and C2H2-Kr) and a mesoscopic quantum liquid (the droplet). Calculations were performed using a spectral element based close-coupling program and state-of-the-art 2-dimensional potential energy surfaces to determine the bound states of the C2H2-Ar and C2H2-Kr complexes and simulate the observed spectra. This furnished a quantitative basis to unravel how the superfluid and non-superfluid components of the droplet affect the rotation and the deformation dynamics of the hosted complex.

The surprisingly high ligation energy of CO to ruthenium porphyrins.

A combined theoretical and experimental approach has been used to investigate the binding energy of a ruthenium metalloporphyrin ligated with CO, ruthenium tetraphenylporphyrin [RuII TPP], in the RuII oxidation degree. Measurements performed with VUV ionization using the DESIRS beamline at Synchrotron SOLEIL led to adiabatic ionization energies of [RuII TPP] and its complex with CO, [RuII TPP-CO], of 6.48 ± 0.03 eV and 6.60 ± 0.03 eV, respectively, while the ion dissociation threshold of [RuII TPP-CO]+ is measured to be 8.36 ± 0.03 eV using the ground-state neutral complex. These experimental data are used to derive the binding energies of the CO ligand in neutral and cationic complexes (1.88 ± 0.06 eV and 1.76 ± 0.06 eV, respectively) using a Born-Haber cycle. Density functional theory calculations, in very satisfactory agreement with the experimental results, help to get insights into the metal-ligand bond. Notably, the high ligation energies can be rationalized in terms of the ruthenium orbital structure, which is singular compared to that of the iron atom. Thus, beyond indications of a strengthening of the Ru-CO bond due to the decrease in the CO vibrational frequency in the complex as compared to the Fe-CO bond, high-level calculations are essential to accurately describe the metal ligand (CO) bond and show that the Ru-CO bond energy is strongly affected by the splitting of triplet and singlet spin states in uncomplexed [Ru TPP].

Self-trapping relaxation decay investigated by time-resolved photoelectron spectroscopy.

The present work combines time-resolved photoelectron spectroscopy on isolated species with high-level data processing to address an issue which usually pertains to materials science: the electronic relaxation dynamics towards the formation of a self-trapped exciton (STE). Such excitons are common excited states in ionic crystals, silica and rare gas matrices. They are associated with a strong local deformation of the matrix. Argon clusters were taken as a model. They are excited initially to a Wannier exciton at 14 eV and their evolution towards the formation of an STE has showed an unusual type of vibronic relaxation where the electronic excitation of the cluster decreases linearly as a function of time with a 0.59 ± 0.06 eV ps-1 rate. The decay was followed for 3.0 ps, and the STE formation occurred in ∼5.1 ± 0.7 ps.

Dioxygen Binding to Protonated Heme in the Gas Phase, an Intermediate Between Ferric and Ferrous Heme.

With a view to characterizing the influence of the electronic structure of the Fe atom on the nature of its bond with dioxygen (O2 ) in heme compounds, a study of the UV/Vis action spectra and binding energies of heme-O2 molecules has been undertaken in the gas phase. The binding reaction of protonated ferrous heme [FeII -hemeH]+ with O2 has been studied in the gas phase by determining the equilibrium of complexed [FeII -hemeH(O2 )]+ with uncomplexed protonated heme in an ion trap at controlled temperatures. The binding energy of O2 to the Fe atom of protonated ferrous heme was obtained from a van't Hoff plot. Surprisingly, this energy (1540±170 cm-1 , 18.4±2 kJ mol-1 ) is intermediate between those of ferric heme and ferrous heme. This result is interpreted in terms of a delocalization of the positive charge over the porphyrin cycle, such that the Fe atom bears a fractional positive charge. The resulting electron distribution on the Fe atom differs notably from that of a purely low-spin ferrous heme [FeII -heme(O2 )] complex, as deduced from its absorption spectrum. It also differs from that of ferric heme [FeIII -heme(O2 )]+ , as evidenced by the absorption spectra. Protonated heme creates a specific bond that cannot accommodate strong σ donation.

Direct observation of slow intersystem crossing in an aromatic ketone, fluorenone.

Direct measurements of Single vibronic Level InterSystem Crossing (SLISC) have been performed on the fluorenone molecule in the gas phase, by time resolved photoelectron and photoion spectroscopy. Vibronic transitions above the S1 nπ* origin were excited in the 432-420 nm region and the decay of S1 and growth of T1(3)ππ* could be observed within a 10 ns time domain. The ionization potential is measured as 8.33 ± 0.04 eV. The energy of the first excited triplet state of fluorenone, T1 has been characterized directly at 18 640 ± 250 cm(-1). The internal conversion of S1 to S0 is found to amount to ∼15% of the population decay, thus ISC is the dominant electronic relaxation process. ISC, although favored by the S1(1)nπ*-T1(3)ππ* coupling scheme, is 3 orders of magnitude less efficient than in the similar molecule benzophenone. Thus, the planarity of the fluorenone molecule disfavors the exploration of the configuration space where surface crossings would create high ISC probability, which occurs in benzophenone through surface crossings. The time evolution of S1 fluorenone is well accounted for by the statistical decay of individual levels into a quasi-continuum of T1 vibronic levels.

Structure of cobalt protoporphyrin chloride and its dimer, observation and DFT modeling.

In this article we present a joint study by time-of-flight mass spectroscopy and density functional theory of cobalt protoporphyrin dimer complexes. The main novelty of the experimental part is to reveal the formation of porphyrin dimers that eventually include a chlorine atom. Density functional theory calculations have been performed to shed light on the structural and electronic properties of monomers and dimers that may be formed experimentally. Various geometries of the monomers are analyzed in the two lowest spin states. The electronic structures are examined by means of population analysis relying on the iterative Hirshfeld scheme and the topological analyses of the electron localization function. It is shown that the cobalt ligand bond is purely ionic in the triplet states but shows a noticeable covalent character in the singlet state. Ionization potential of Co-protoporphyrin and binding energies of the chlorine ligand are also reported. Concerning the dimers, several association patterns are investigated for the chlorinated and non-chlorinated complexes. It is found that the structures of the most stable complexes involve four hydrogen bonds between the carboxylic acid moieties of the protoporphyrins. However other association modes are likely to be possible in the experiments.

Bonding of heme Fe(III) with dioxygen: observation and characterization of an incipient bond.

While ferrous heme (Fe(II)) within hemoproteins binds dioxygen efficiently, it has not yet been possible to observe the analog complex with ferric heme (Fe(III)). We present the first observation and characterization of the latter complex in a cooled ion trap. The bond formation enthalpy of ferric heme-O2 has been derived from the Van't Hoff equation by means of temperature dependent measurements. The binding energy of the [heme Fe(III)-O2](+) ionic complex is rather strong as compared to that of [heme Fe(III)-N2](+), showing the formation of an incipient Fe-O bond, which is confirmed by the electronic absorption spectra of the two complexes. This first observation of the [heme Fe(III)-O2](+) complex lays the basis for the precise description of its electronic states.

Photoionization of Benzophenone in the Gas Phase: Theory and Experiment.

We report on the single photoionization of jet-cooled benzophenone using a tunable source of VUV synchrotron radiation coupled with a photoion/photoelectron coincidence acquisition device. The assignment and the interpretation of the spectra are based on a characterization by ab initio and density functional theory calculations of the geometry and of the electronic states of the cation. The absence of structures in the slow photoelectron spectrum is explained by a congestion of the spectrum due to the dense vibrational progressions of the very low frequency torsional mode in the cation either in pure form or in combination bands. Also a high density of electronic states has been found in the cation. Presently, we estimate the experimental adiabatic and vertical ionization energy of benzophenone at 8.80 ± 0.01 and 8.878 ± 0.005 eV, respectively. The ionization energy as well as the energies of the excited states are compared to the calculated ones.

Observation in the gas phase of the ligation of 1-methylimidazole to hemoprotein mimics.

Hemoprotein mimics, cobalt picket fence porphyrins have been prepared in the gas phase as neutral molecules for the first time. Their ligation properties have been studied with 1-methylimidazole and compared with those of other cobalt porphyrins, tetraphenyl porphyrin, and cobalt protoporphyrin IX chloride, in view of studying the sterical properties of the ligation. It is shown that the cobalt picket fence porphyrin can only accept one 1-methylimidazole ligand in contrast to less sterically crowded porphyrins like cobalt tetraphenylporphyrin that present two accessible ligation sites. The femtosecond dynamics of these ligated systems have been studied after excitation at 400 nm, in comparison with the unligated ones. The observed transients are formed in much shorter times, 30 fs for the ligated species, as compared to free species (100 fs), supporting the porphyrin to metal charge transfer nature of these transients. The similar decays of the ligated transients <1 ps reveal the absence of photodissociation of the cobalt-1-methylimidazole bond at this step of evolution.

Competitive direct vs. indirect photochromism dynamics of constrained inverse dithienylethene molecules.

State-of-the-art experimental and theoretical tools were used to investigate the gas-phase relaxation dynamics of various photoexcited photochromic dithienylethene molecules in situations where several relaxation channels are simultaneously at play. Unconstrained and constrained dynamics were addressed by considering unbridged and bridged molecules with a polyether bridge of various sizes (from 2 to 4 units). Time-resolved ultrafast ionization spectroscopy techniques were used to probe the dynamics. This revealed the existence of several relaxation pathways from the first excited state to the ground-state. Characteristic times were determined for each process. These channels compete at an early stage of the dynamics only when the initial wavepacket splits into two parts. A striking excited state wavepacket oscillation is observed in bridged molecules. A general reaction mechanism is proposed which rationalizes the carbon-carbon distance rule which is widely used as an empirical tool to predict the photoactivity of photochromic molecules in crystals.

Gas phase dynamics of triplet formation in benzophenone.

Benzophenone is a prototype molecule for photochemistry in the triplet state through its high triplet yield and reactivity. We have investigated its dynamics of triplet formation under the isolated gas phase conditions via femtosecond and nanosecond time resolved photoelectron spectroscopy. This represents the complete evolution from the excitation in S2 to the final decay of T1 to the ground state S0. We have found that the triplet formation can be described almost as a direct process in preparing T1, the lowest reacting triplet state, from the S1 state after S2 → S1 internal conversion. The molecule was also deposited by a pick-up technique on cold argon clusters providing a soft relaxation medium without evaporation of the molecule and the mechanism was identical. This cluster technique is a model for medium influenced electronic relaxation and provides a continuous transition from the isolated gas phase to the relaxation dynamics in solution.

Time resolved observation of the solvation dynamics of a Rydberg excited molecule deposited on an argon cluster-I: DABCO* at short times.

This paper is a joint experimental and theoretical approach concerning a molecule deposited on a large argon cluster. The spectroscopy and the dynamics of the deposited molecule are measured using the photoelectron spectroscopy. The absorption spectrum of the deposited molecule shows two solvation sites populated in the ground state. The combined dynamics reveals that the population ratio of the two sites is reversed when the molecule is electronically excited. This work provides the timescale of the corresponding solvation dynamics. Theoretical calculation supports the interpretation. More generally, close examination of the short time dynamics (0-6 ps) of DABCO···Ar(n) gives insights into the ultrafast relaxation dynamics of molecules deposited at interfaces and provides hence the time scale for deposited molecules to adapt to their neighborhoods.

A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine.

How much time does it take for a wavepacket to roam on a multidimensional potential energy surface? This combined theoretical and pump-probe femtosecond time experiment on 2-hydroxypyridine proposes an answer. Bypassing the well-established transition state and conical intersection relaxation pathways, this molecular system undergoes relaxation into the S1 excited state: the central ring is destabilized by the electronic excitation, within ~100 fs after absorption of the pump photon, then the H-atom bound to oxygen undergoes a roaming behavior when it couples to other degrees of freedom of the molecule. The timescale of the latter process is measured to be ~1.3 ps. Further evolution of the wavepacket is either an oscillation onto the S1 potential or a conversion into the triplet state for timescale larger than ~110 ps. Our work introduces a new tool for the understanding of time-resolved relaxation dynamics applied to large molecules through the roaming dynamics characterized by its strongly delocalized wavepacket on flat molecular potential energy surfaces.