Spectroscopic Characterization of Hydrogen-Bonded 2,7-Diazaindole Water Complex Isolated in the Gas Phase.

We present a systematic experimental analysis of the 1:1 complex of 2,7-diazaindole (27DAI) with water in the gas phase. The complex was characterized by using two-color-resonant two-photon ionization (R2PI), laser-induced fluorescence (LIF), single vibronic level fluorescence (SVLF), and photoionization efficiency (PIE) spectroscopic methods. The 000 band of the S1←S0 electronic transition of the 27DAI-H2O complex was observed at 33,074 cm-1, largely red-shifted by 836 cm-1 compared to that of the bare 27DAI. From the R2PI spectrum, the detected modes at 141 (ν'Tx), 169 (ν'Ty), and 194 (ν'Ry) cm-1 were identified as the internal motions of the H2O molecule in the complex. However, these modes were detected at 115 (ν″Tx), 152 (ν″Ty), and 190 (ν″Ry) cm-1 in the ground state, which suggested a stronger hydrogen bonding interaction in the photo-excited state. The structural determination was aided by the detection of νNH and νOH values in the ground and excited state complexes using the FDIR and IDIR spectroscopies. The detection of νNH at 3414 and νOH at 3447 cm-1 in 27DAI-H2O has shown an excellent correlation with the most stable structure consisting of N(1)-H···O and OH···N(7) hydrogen-bonded bridging water molecule in the ground state. The structure of the complex in the electronic excited state (S1) was confirmed by the corresponding bands at 3210 (νNH) and 3265 cm-1 (νOH). The IR-UV hole-burning spectroscopy confirmed the presence of only one isomer in the molecular beam. The ionization energy (IE) of the 27DAI-H2O complex was obtained as 8.789 ± 0.002 eV, which was significantly higher than the 7AI-H2O complex. The higher IE values of N-rich molecules suggest a higher resistivity of such molecules against photodamage. The obtained structure of the 27DAI-H2O complex has explicitly shown the formation of a cyclic one-solvent bridge incorporating N(1)-H···O and O-H···N(7) hydrogen bonds upon microsolvation. The lower excitation and higher ionization energies of the 27DAI-H2O complex compared to 7AI-H2O established higher stabilization of N-rich molecules. The solvent clusters forming a linear bridge between the hydrogen/proton acceptor and donor sites in the complex can be considered as a stepping stone to investigate the photoinduced deactivation mechanisms in nitrogen containing biologically relevant molecules.

Origin of unique hyper-Raman signals of trifluoroethanol.

We report the hyper-Raman (HR) spectrum of trifluoroethanol, excited with 532 nm light, in an aqueous solution at basic pH. The HR spectrum exhibits a distinct spectral pattern that diverges entirely from the infrared and Raman spectra of trifluoroethanol. This observed unique HR signal was attributed to the products of photoinduced radical reactions in the aqueous solution. This result exemplifies the exceptional capabilities of HR spectroscopy based on resonance conditions.

Competing Excited-State Hydrogen and Proton-Transfer Processes in 6-Azaindole-S3,4 and 2,6-Diazaindole-S3,4 Clusters (S=H2 O, NH3 ).

Excited state hydrogen (ESHT) and proton (ESPT) transfer reaction pathways in the three and four solvent clusters of 6-azaindole (6AI-S3,4 ) and 2,6-diazaindole (26DAI-S3,4 )(S=H2 O, NH3 ) were computationally investigated to understand the fate of photo-excited biomolecules. The ESHT energy barriers in (H2 O)3 complexes (39.6-41.3 kJmol-1 ) were decreased in (H2 O)4 complexes (23.1-20.2 kJmol-1 ). Lengthening the solvent chain lowered the barrier because of the relaxed transition states geometries with reduced angular strains. Replacing the water molecule with ammonia drastically decreased the energy barriers to 21.4-21.3 kJmol-1 in (NH3 )3 complexes and 8.1-9.5 kJ mol-1 in (NH3 )4 complexes. The transition states were identified as Ha atom attached to the first solvent molecule. The formation of stronger hydrogen bonds in (NH3 )3,4 complexes resulted in facile ESHT reaction than that in the (H2 O)3,4 complexes. The ESPT energy barriers in 6AI-S3,4 and 26DAI-S3,4 were found to range between 40-73 kJmol-1 . The above values were significantly higher than that of the ESHT processes and hence are considered as a minor channel in the process. The effect of N(2) insertion was explored for the very first time in the isolated solvent clusters using local vibrational mode analysis. In DAI-S4 , the higher Ka (Ha ⋯Sa ) values depicted the increased photoacidity of the N(1)-Ha group which may facilitate the hydrogen transfer reaction. However, the increased N(6)⋯Hb bond length elevated the reaction barriers. Therefore, in the ESHT reaction channel, the co-existence of two competing factors led to a marginal/no change in the overall energy barriers due to the N(2) insertion. In the ESPT reaction pathway, the energy barriers showed notable increase upon N(2) insertion because of the increased N(6)⋯Hb bond length.

Laser spectroscopic characterization of supersonic jet cooled 2,7-diazaindole.

We report the first gas phase comprehensive study of the electronic spectroscopy of 2,7-diazaindole molecule in the ground and excited states. Single vibronic level fluorescence spectroscopy (SVLF) was performed to determine the ground state vibrations of the molecule, which depicted a large Franck-Condon activity beyond 2600 cm-1. For the excited state characterization, laser-induced fluorescence (LIF) and two-color resonant two-photon ionization spectroscopy (2C-R2PI) were performed. The band origin (000) for S1 ← S0 transition appeared at 33910 ± 1 cm-1 which was red shifted by 718 cm-1 and 1322 cm-1 compared to that of 7-azaindole and indole respectively. The Franck-Condon active vibrational modes in the spectra were seen till the (000) + 1600 cm-1 region. The IR-UV hole burning spectroscopy confirmed the absence of any other isomeric species in the molecular beam. The ionization energy (IE) of the molecule was measured as 8.921 ± 0.001 eV, recorded using photoionization efficiency spectroscopy. The above IE value was significantly higher than that of the related indole derivatives, suggesting the higher photostability of the 27DAI molecule due to N(2) insertion. The ground and excited state N-H stretching frequencies of the molecule were determined using fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR), and the values are 3523 and 3467 cm-1, respectively. The lower value of νNH in the electronic excited state implied the increased photoacidity of the group. A comparative analysis of the experimental LIF/2C-R2PI spectra was done against Franck-Condon simulated spectra at three different levels of theory. The vibrational frequencies calculated at B3LYP-D4/def2-TZVPP showed the most accurate prediction in comparison with the experimentally detected symmetric modes in the ground state. However, in the excited state, the lower energy asymmetric modes simulated at the B3LYP/def-SVP level of theory provided the best agreement with the experiment. This is most probably due to the distortion observed at the pyrazolyl ring leading to the appearance of asymmetric vibrational modes. The above study highlights the possibility to appropriately tune the excitation wavelengths as well as alter the photostability of the organic chromophores via additional N-insertion in the molecular systems.

A combined spectroscopic and computational investigation on the solvent-to-chromophore excited-state proton transfer in the 2,2'-pyridylbenzimidazole-methanol complex.

This article demonstrates experimental proof of excited state 'solvent-to-chromophore' proton transfer (ESPT) in the isolated gas phase PBI (2,2'-pyridylbenzimidazole)-CH3OH complex, aided by computational calculations. The binary complexes of PBI with CH3OH/CH3OD were produced in a supersonic jet-cooled molecular beam and the energy barrier of the photo-excited process was determined using resonant two-colour two-photon ionization spectroscopy (R2PI). The ESPT process in the PBI-CH3OH complex was confirmed by the disappearance of the Franck-Condon active vibrational transitions above 000 + 390 cm-1. In the PBI-CH3OD complex, the reappearance of the Franck-Condon transitions till 000 + 800 cm-1 confirmed the elevation of the ESPT barrier upon isotopic substitution due to the lowering of the zero-point vibrational energy. The ESPT energy barrier in PBI-CH3OH was bracketed as 410 ± 20 cm-1 (4.91 ± 0.23 kJ mol-1) by comparing the spectra of PBI-CH3OH and PBI-CH3OD. The solvent-to-chromophore proton transfer was confirmed based on the significantly decreased quantum tunnelling of the solvent proton in the PBI-CH3OD complex. The computational investigation resulted in an energy barrier of 6.0 kJ mol-1 for the ESPT reaction in the PBI-CH3OH complex, showing excellent agreement with the experimental value. Overall, the excited state reaction progressed through an intersection of ππ* and nπ* states before being deactivated to the ground state via internal conversion. The present investigation reveals a novel reaction pathway for the deactivation mechanism of the photo-excited N-containing biomolecules in the presence of protic-solvents.

Excited-state deactivation via solvent-to-chromophore proton transfer in an isolated 1 : 1 molecular complex: experimental validation by measuring the energy barrier and kinetic isotope effect.

We have experimentally demonstrated conclusive evidence of solvent-to-chromophore excited-state proton transfer (ESPT) as a deactivation mechanism in a binary complex isolated in the gas phase. This was achieved by determining the energy barrier of the ESPT processes, qualitatively analysing the quantum tunnelling rates and evaluating the kinetic isotope effect. The 1 : 1 complexes of 2,2'-pyridylbenzimidazole (PBI) with H2O, D2O and NH3, produced in supersonic jet-cooled molecular beam, were characterised spectroscopically. The vibrational frequencies of the complexes in the S1 electronic state were recorded using a resonant two-colour two-photon ionization method coupled to a time-of-flight mass spectrometer set-up. In PBI-H2O, the ESPT energy barrier of 431 ± 10 cm-1 was measured using UV-UV hole-burning spectroscopy. The exact reaction pathway was experimentally determined via the isotopic substitution of the tunnelling-proton (in PBI-D2O) and by increasing the width of the proton-transfer barrier (in PBI-NH3). In both cases, the energy barriers were significantly increased to >1030 cm-1 in PBI-D2O and to >868 cm-1 in PBI-NH3. The heavy atom in PBI-D2O decreased the zero-point energy in the S1 state significantly, resulting in elevation of the energy barrier. Secondly, the solvent-to-chromophore proton tunnelling was found to decrease drastically upon deuterium substitution. In the PBI-NH3 complex, the solvent molecule formed preferential hydrogen bonding with the acidic (PBI)N-H group. This led to the formation of weak hydrogen bonding between ammonia and the pyridyl-N atom, thus increasing the proton-transfer barrier width (H2N-H⋯Npyridyl(PBI)). The above resulted in an increased barrier height and a decreased quantum tunnelling rate in the excited state. The experimental investigation, aided by computational investigations, demonstrated conclusive evidence of a novel deactivation channel for an electronically excited biologically relevant system. The variation observed for the energy barrier and the quantum tunnelling rate by substituting NH3 in place of H2O can be directly correlated with the drastically different photochemical and photophysical reactions of biomolecules under various microenvironments.

Accurate measurement of sequential Ar desorption energies from the dispersion-dominated Ar1-3 complexes of aromatic molecules.

We present experimental determination of the energies associated with the gradual desorption of Ar atoms from the aromatic molecular surface. Non-covalently bound 2,2'-pyridylbenzimidazole-Ar1-3 complexes were produced in the gas phase and characterized using resonant two-photon ionization (R2PI) spectroscopy. The single Ar desorption from the PBI-Ar, PBI-Ar2 and PBI-Ar3 complexes were measured as 581 ± 18, 656 ± 30 and 537 ± 31 cm-1, respectively. The energies were bracketed between the last observed band in the respective R2PI spectra and the disappeared intramolecular modes of PBI. The Arn dissociation energies in the S1 state were measured as 581 ± 18, 1237 ± 48 and 1774 ± 79 cm-1, respectively, for n = 1, 2 and 3. The calculated dissociation energies of the respective complexes, obtained using three computational methods, show excellent agreement with the experimental data. The ground state dissociation energies were estimated by subtracting the Δν shift of the origin band, and the respective values are 541 ± 18, 1160 ± 48 and 1634 ± 79 cm-1. Overall, the calculated values resulted in scaling factors ranging from 0.956 to 1.017, which depict the predictive power of the methods to determine dispersion energies. The current investigation describes a unique methodology to accurately determine the dissociation and desorption energies of Ar atoms from the surfaces of bio-relevant aromatic molecules.

A combined experimental and computational study on the deactivation of a photo-excited 2,2'-pyridylbenzimidazole-water complex via excited-state proton transfer.

In this report, we present solvent assisted excited-state proton transfer coupled to the deactivation of a photo-excited 2,2'-pyridylbenzimidazole bound to a single water molecule. Experimentally, the mass-selected 1 : 1 complex was probed using two-colour resonant two-photon ionization (2C-R2PI) and UV-UV hole-burning (HB) spectroscopy in a supersonically jet-cooled molecular beam. Computationally, three structural isomers were identified as the normal, the tautomer and the proton transfer product of the PBI-H2O complex in the excited S1 state using B3LYP-D4/def2-TZVPP and ADC(2) (MP2)/cc-pVDZ levels of theory. The most stable form in the ground state, i.e., the normal form, was identified using the excitation spectrum in the 30 544 to 30 936 cm-1 region. The 2C-R2PI spectrum showed a sudden break-off above the 000 + 392 cm-1 region, even though the Frack-Condon activity of the S1 ← S0 transition was measured beyond 000 + 1000 cm-1 in the HB spectrum. The intensity of the bands associated with the excited state intermolecular vibrational modes near the break-off region was found to be drastically decreased, which indicates efficient quantum mechanical tunnelling along the hydrogen transfer coordinate. The sudden disappearance of the intermolecular vibrational modes in the spectrum revealed the existence of a deactivation channel in the PBI-H2O complex near 392-450 cm-1 above the 000 transition. The computational investigation predicted that the deactivation of the excited-state occurred via the intersection between the S1 and S0 states, which was associated with the proton transfer from the H2O to the PBI molecule along the O(3)-H(4)→N(5) coordinate. The highest energy structure was identified as the point of intersection between the nπ* (S2) and ππ* (S1) states. The associated barrier height was experimentally determined to be 392-450 cm-1, which showed a reasonable agreement with the calculated excited-state proton transfer barrier. Competing reaction channels such as dissociation and tautomerization were found to be highly energetically inaccessible.

Solvent assisted excited-state deactivation pathways in isolated 2,7-diazaindole-S1-3 (S = Water and Ammonia) complexes.

The role of solvent molecules in the deactivation of photo-excited 2,7-diazaindole (DAI) - (H2O)1-3 and DAI - (NH3)1-3 complexes were computationally investigated. An excited-state proton transfer (ESPT) path from the solvent to the DAI molecule was followed using the TD-DFT-D4 (B3LYP) level of theory. The computed potential energy profile of ESPT process has shown intersection between ππ* and nπ* states facilitated via relative stabilization of the nπ* state with decreasing N(7)-Hb bond length. The ESPT process, starting from the DAI-Sn (ππ*) state, crosses through a barrier ranging from 27 to 36 kJmol-1 for water complexes and 26-30 kJmol-1 for ammonia complexes. The energy of the excited state was rapidly decreased with a shorter N(7)-Hb bond length. Subsequently, a significant trend of finding a second intersection between the ground and the excited state was observed for all the complexes. The results firmly suggested a significant deactivation channel of excited azaindole derivatives. In the present system, two competing channels, ESPT and ESHT, were found to be energetically accessible. The energy barriers associated with the ESPT barriers for DAI-(H2O)1-3 complexes are similar to the ESHT barrier, depicting equal dominance of both processes. The increased basicity of the N(7) atom in the excited state resulted a facile ESPT process from the water to N(7) of the DAI molecule. However, DAI-(NH3)1-3 complexes show clear preference for ESHT over ESPT process owing to its higher gas-phase pKa value making it a poor proton donor. The above systems can be used as a model to computationally and experimentally investigate the competing radiative and deactivation pathways of photo-excited solvated complexes of N-H-bearing bio-relevant molecules via proton and hydrogen transfer reactions.

Excited state hydrogen atom transfer pathways in 2,7-diazaindole - S1-3 (S = H2O and NH3) clusters.

The photoinduced tautomerization reactions via hydrogen atom transfer in the excited electronic state (ESHT) have been computationally investigated in 2,7-diazaindole (27DAI) - (H2O)1-3 and 27DAI - (NH3)1-3 isolated clusters to understand the role of various solvent wires. Two competing ESHT reaction pathways originating from the N(1)-H group to the neighbouring N(7) (R(1H-Sn-7H)) and N(2) (R(1H-Sn-2H)) atoms were rigorously examined for each system. Both one- and two-dimensional potential energy surfaces have been calculated in the excited state to investigate the pathways. The R(1H-Sn-7H) was found to be the dominant route with reaction barriers ranging from 26-40 kJmol-1 for water clusters, and 14-26 kJmol-1 for ammonia clusters. The barrier heights for ammonia clusters were found to be nearly half of the that observed for the water systems. The lengthening of the solvent chain up to two molecules resulted in a drastic decrease in the barrier heights for R(1H-Sn-7H). The barriers of the competing reaction channel R(1H-Sn-2H) were found to be significantly higher (31-127 kJmol-1) but were observed to be decreasing with the lengthening of the solvent wire as in the R(1H-Sn-7H) pathway. In both the reactions, the angle strain present in the transition state structures was dependent upon the solvent chain's length and was most likely the governing factor for the barrier heights in each solvent cluster. The results have also affirmed that the ammonia molecule is a better candidate for hydrogen transfer than water because of its higher gas-phase basicity. The results delineated from this investigation can pave the way to unravel the excited-state hydrogen atom transfer pathways in novel N-H bearing molecules.

A combined spectroscopic and computational investigation on dispersion-controlled docking of Ar atoms on 2-(2'-pyridyl)benzimidazole.

The dispersion-controlled docking of inert Ar atoms on the face of polycyclic 2-(2'-pyridyl)-benzimidazole (PBI) was studied experimentally aided by computational findings. The PBI-Arn (n = 1-3) complexes were produced in a supersonically jet-cooled molecular beam and probed using resonant two-photon ionization coupled with a time-of-flight mass spectrometric detection scheme and laser-induced fluorescence spectroscopy. The ground state vibrational frequencies were obtained from single vibronic level fluorescence spectroscopy. The formation of multiple isomers was verified using UV-UV hole-burning spectroscopy. The geometries of PBI-Arn (n = 1-3) complexes were derived by mutual agreement between experimental findings and computational results such as vibrational frequencies in the ground and excited electronic states, Franck-Condon factors and spectral shift of the S1← S0 transitions. All the above analyses provided good agreement between the experimental and simulated spectrum with the most stable PBI-Arn (n = 1-3) clusters. The highest intermolecular interaction between PBI and Ar was obtained with the Ar atom positioned above the imidazolyl ring. A second Ar atom was preferably docking on the other side of the imidazolyl ring than the pyridyl ring. The subsequent addition of the third Ar atom preferred the position above the pyridyl ring. The current investigation can be useful to investigate the preferential docking of dispersion-controlled interacting partners in multifunctional aromatic side chains present in biological systems.

Intermolecular dissociation energies of 1-naphthol·n-alkane complexes.

Using the stimulated-emission-pumping/resonant 2-photon ionization (SEP-R2PI) method, we have determined accurate intermolecular dissociation energies D0 of supersonic jet-cooled intermolecular complexes of 1-naphthol (1NpOH) with alkanes, 1NpOH·S, with S = methane, ethane, propane, and n-butane. Experimentally, the smaller alkanes form a single minimum-energy structure, while 1-naphthol·n-butane forms three different isomers. The ground-state dissociation energies D0(S0) for the complexes with propane and n-butane (isomers A and B) were bracketed within ±0.5%, being 16.71 ± 0.08 kJ/mol for S = propane and 20.5 ± 0.1 kJ/mol for isomer A and 20.2 ± 0.1 kJ/mol for isomer B of n-butane. All 1NpOH·S complexes measured previously exhibit a clear dissociation threshold in their hot-band detected SEP-R2PI spectra, but weak SEP-R2PI bands are observed above the putative dissociation onset for the methane and ethane complexes. We attribute these bands to long-lived complexes that retain energy in rotation-type intermolecular vibrations, which couple only weakly to the dissociation coordinates. Accounting for this, we find dissociation energies of D0(S0) = 7.98 ± 0.55 kJ/mol (±7%) for S = methane and 14.5 ± 0.28 kJ/mol (±2%) for S = ethane. The D0 values increase by only 1% upon S0 → S1 excitation of 1-naphthol. The dispersion-corrected density functional theory methods B97-D3, B3LYP-D3, and ωB97X-D predict that the n-alkanes bind dispersively to the naphthalene "Face." The assignment of the complexes to Face structures is supported by the small spectral shifts of the S0 → S1 electronic origins, which range from +0.5 to -15 cm-1. Agreement with the calculated dissociation energies D0(S0) is quite uneven, the B97-D3 values agree within 5% for propane and n-butane, but differ by up to 20% for methane and ethane. The ωB97X-D method shows good agreement for methane and ethane but overestimates the D0(S0) values for the larger n-alkanes by up to 20%. The agreement of the B3LYP-D3 D0 values is intermediate between the other two methods.

Measuring Intermolecular Binding Energies by Laser Spectroscopy.

The ground-state dissociation energy, D0(S0), of isolated intermolecular complexes in the gas phase is a fundamental measure of the interaction strength between the molecules. We have developed a three-laser, triply resonant pump-dump-probe technique to measure dissociation energies of jet-cooled M•S complexes, where M is an aromatic chromophore and S is a closed-shell 'solvent' molecule. Stimulated emission pumping (SEP) via the S0→S1 electronic transition is used to precisely 'warm' the complex by populating high vibrational levels v" of the S0 state. If the deposited energy E(v") is less than D0(S0), the complex remains intact, and is then mass- and isomer-selectively detected by resonant two-photon ionization (R2PI) with a third (probe) laser. If the pumped level is above D0(S0), the hot complex dissociates and the probe signal disappears. Combining the fluorescence or SEP spectrum of the cold complex with the SEP breakoff of the hot complex brackets D0(S0). The UV chromophores 1-naphthol and carbazole were employed; these bind either dispersively via the aromatic rings, or form a hydrogen bond via the -OH or -NH group. Dissociation energies have been measured for dispersively bound complexes with noble gases (Ne, Kr, Ar, Xe), diatomics (N2, CO), alkanes (methane to n-butane), cycloalkanes (cyclopropane to cycloheptane), and unsaturated compounds (ethene, benzene). Hydrogen-bond dissociation energies have been measured for H2O, D2O, methanol, ethanol, ethers (oxirane, oxetane), NH3 and ND3.

Accurate dissociation energies of two isomers of the 1-naphthol⋠cyclopropane complex.

The 1-naphthol⋅cyclopropane intermolecular complex is formed in a supersonic jet and investigated by resonant two-photon ionization (R2PI) spectroscopy, UV holeburning, and stimulated emission pumping (SEP)-R2PI spectroscopy. Two very different structure types are inferred from the vibronic spectra and calculations. In the "edge" isomer, the OH group of 1-naphthol is directed towards a C-C bond of cyclopropane, the two ring planes are perpendicular. In the "face" isomer, the cyclopropane is adsorbed on one of the π-aromatic faces of the 1-naphthol moiety, the ring planes are nearly parallel. Accurate ground-state intermolecular dissociation energies D0 were measured with the SEP-R2PI technique. The D0(S0) of the edge isomer is bracketed as 15.35 ± 0.03 kJ/mol, while that of the face isomer is 16.96 ± 0.12 kJ/mol. The corresponding excited-state dissociation energies D0(S1) were evaluated using the respective electronic spectral shifts. Despite the D0(S0) difference of 1.6 kJ/mol, both isomers are observed in the jet in similar concentrations, so they must be separated by substantial potential energy barriers. Intermolecular binding energies, De, and dissociation energies, D0, calculated with correlated wave function methods and two dispersion-corrected density-functional methods are evaluated in the context of these results. The density functional calculations suggest that the face isomer is bound solely by dispersion interactions. Binding of the edge isomer is also dominated by dispersion, which makes up two thirds of the total binding energy.

Intermolecular dissociation energies of dispersively bound 1-naphthol⋠cycloalkane complexes.

Intermolecular dissociation energies D0(S0) of the supersonic jet-cooled complexes of 1-naphthol (1NpOH) with cyclopentane, cyclohexane, and cycloheptane were determined to within <0.5% using the stimulated-emission pumping resonant two-photon ionization method. The ground state D0(S0) values are bracketed as 20.23±0.07 kJ/mol for 1NpOH⋅cyclopentane, 20.34±0.04 kJ/mol for 1NpOH⋅cyclohexane, and 22.07±0.10 kJ/mol for two isomers of 1NpOH⋅cycloheptane. Upon S0→S1 excitation of the 1-naphthol chromophore, the dissociation energies of the 1NpOH⋅cycloalkane complexes increase from 0.1% to 3%. Three dispersion-corrected density functional theory (DFT) methods predict that the cycloalkane moieties are dispersively bound to the naphthol face via London-type interactions, similar to the "face" isomer of the 1-naphthol⋅cyclopropane complex [S. Maity et al., J. Chem. Phys. 145, 164304 (2016)]. The experimental and calculated D0(S0) values of the cyclohexane and cyclopentane complexes are practically identical, although the polarizability of cyclohexane is ∼20% larger than that of cyclopentane. Investigation of the calculated pairwise atomic contributions to the D2 dispersion energy reveals that this is due to subtle details of the binding geometries of the cycloalkanes relative to the 1-naphthol ring. The B97-D3 DFT method predicts dissociation energies within about ±1% of experiment, including the cyclopropane face complex. The B3LYP-D3 and ωB97X-D calculated dissociation energies are 7-9 and 13-20% higher than the experimental D0(S0) values. Without dispersion correction, all the complexes are calculated to be unbound.

Gas Phase Detection of Benzocyclopropenyl.

The gas phase detection of benzocyclopropenyl is reported. In this aromatic resonance stabilized radical, a large angular strain is present due to a three-membered ring annelated to a benzene. The resonant two-color two-photon ionization technique is used to record the D1((2)A2) ← D0((2)B1) electronic transition of this radical after the in situ synthesis in a discharge source. The spectrum features absorptions up to 3300 cm(-1) above the origin band at 19,305 cm(-1). Benzocyclopropenyl is possibly the major product of the bimolecular reaction of benzene and an atomic carbon at low temperatures.

Electronic spectra of linear HC5H and cumulene carbene H2C5.

The 1(3)Σu (-)←X(3)Σg (-) transition of linear HC5H (A) has been observed in a neon matrix and gas phase. The assignment is based on mass-selective experiments, extrapolation of previous results of the longer HC2n+1H homologues, and density functional and multi-state CASPT2 theoretical methods. Another band system starting at 303 nm in neon is assigned as the 1(1)A1←X˜(1)A1 transition of the cumulene carbene pentatetraenylidene H2C5 (B).

Electronic Spectroscopy of Resonantly Stabilized Aromatic Radicals: 1-Indanyl and Methyl Substituted Analogues.

The gas-phase electronic spectra of two resonantly stabilized radicals, 1-indanyl (C9H9) and 1-methyl-1-indanyl (C10H11), have been recorded in the visible region using a resonant two-color two-photon ionization (R2C2PI) scheme. The D1(A″) ← D0(A″) origin bands of 1-indanyl and 1-methyl-1-indanyl radicals are observed at 21157 and 20565 cm(­1), respectively. The excitation of a' vibrations in the D1 state is observed up to ∼1500 cm(­1) above the origin band in both cases. The experimental assignments are in agreement with DFT and TD-DFT calculations. The R2C2PI spectrum recorded at m/z = 131 amu (C10H11) features three additional electronic transitions at 21433, 21369, and 17989 cm(­1), which are assigned to the origin bands of 7-methyl-1-indanyl, 2,3,4-trihydronaphthyl, and methyl-4-ethenylbenzyl radicals, respectively.

Combined crossed molecular beam and ab initio investigation of the reaction of boron monoxide (BO; X(2)Σ(+)) with 1,3-butadiene (CH2CHCHCH2; X(1)Ag) and its deuterated counterparts.

The reactions of the boron monoxide ((11)BO; X(2)Σ(+)) radical with 1,3-butadiene (CH2CHCHCH2; X(1)Ag) and its partially deuterated counterparts, 1,3-butadiene-d2 (CH2CDCDCH2; X(1)Ag) and 1,3-butadiene-d4 (CD2CHCHCD2; X(1)Ag), were investigated under single collision conditions exploiting a crossed molecular beams machine. The experimental data were combined with the state-of-the-art ab initio electronic structure calculations and statistical RRKM calculations to investigate the underlying chemical reaction dynamics and reaction mechanisms computationally. Our investigations revealed that the reaction followed indirect scattering dynamics through the formation of (11)BOC4H6 doublet radical intermediates via the barrierless addition of the (11)BO radical to the terminal carbon atom (C1/C4) and/or the central carbon atom (C2/C3) of 1,3-butadiene. The resulting long-lived (11)BOC4H6 intermediate(s) underwent isomerization and/or unimolecular decomposition involving eventually at least two distinct atomic hydrogen loss pathways to 1,3-butadienyl-1-oxoboranes (CH2CHCHCH(11)BO) and 1,3-butadienyl-2-oxoboranes (CH2C ((11)BO)CHCH2) in overall exoergic reactions via tight exit transition states. Utilizing partially deuterated 1,3-butadiene-d2 and -d4, we revealed that the hydrogen loss from the methylene moiety (CH2) dominated with 70 ± 10% compared to an atomic hydrogen loss from the methylidyne group (CH) of only 30 ± 10%; these data agree nicely with the theoretically predicted branching ratio of 80% versus 19%.

Synthesis of prebiotic glycerol in interstellar ices.

Contemporary mechanisms for the spontaneous formation of glycerol have not been able to explain its existence on early Earth. The exogenous origin and delivery of organic molecules to early Earth presents an alternative route to their terrestrial in situ formation since biorelevant molecules like amino acids, carboxylic acids, and alkylphosphonic acids have been recovered from carbonaceous chondrites. Reported herein is the first in situ identification of glycerol, the key building block of all cellular membranes, formed by exposure of methanol-based - interstellar model ices to ionizing radiation in the form of energetic electrons. These results provide compelling evidence that the radiation-induced formation of glycerol in low-temperature interstellar model ices is facile. Synthesized on interstellar grains and eventually incorporated into the "building material" of solar systems, biorelevant molecules such as glycerol could have been dispensed to habitable planets such as early Earth by comets and meteorites.