Aimable Kalume

Characterization of iso-CF2I2 in frequency and ultrafast time domains

The photolysis of diiododifluoromethane (CF(2)I(2)) in condensed phases was studied by a combination of matrix isolation and ultrafast time-resolved spectroscopy, in concert with ab initio calculations. Photolysis at wavelengths of 355 or 266 nm of CF(2)I(2):Ar samples (1:5000) held at approximately 8 K yielded iso-CF(2)I(2) (F(2)C-I-I), a metastable isomer of CF(2)I(2), characterized here for the first time. The infrared (IR) spectra of this isomer were recorded in matrix experiments, and the derived positions of the C-F stretching modes are in very good agreement with the predictions of high level ab initio calculations, which show that the iso-form is a minimum on the CF(2)I(2) ground state potential energy surface. The formation of this isomer following 350 nm excitation of CF(2)I(2) in room temperature CCl(4) solutions was monitored through its intense C-F stretching mode by means of ultrafast time-resolved IR absorption. Together, matrix isolation and ultrafast IR absorption experiments suggest that the formation of iso-CF(2)I(2) occurs via recombination of CF(2)I radical and I atom. Ultrafast IR experiments detect a delayed rise of iso-CF(2)I-I absorption, placing an upper limit of 400 fs for the C-I bond dissociation and primary geminate recombination processes. The product absorption spectrum recorded 1 ns after 350 nm excitation of CF(2)I(2) in solution is virtually identical to the visible absorption spectrum of iso-CF(2)I(2) trapped in matrix isolation experiments [with subtracted I(2)(X) absorption]. The formation of this isomer in solution at room temperature has direct dynamic implications for the ultrafast production of molecular iodine from electronically excited CF(2)I(2).

Spectroscopic and computational studies of matrix-isolated iso-CHBr3: Structure, properties, and photochemistry of iso-bromoform

Iso-polyhalomethanes are known reactive intermediates that play a pivotal role in the photochemistry of halomethanes in condensed phases. In this work, iso-bromoform (iso-CHBr(3)) and its deuterated isotopomer were characterized by matrix isolation infrared and UV/visible spectroscopy, supported by ab initio and density functional theory calculations, to further probe the structure, spectroscopy, and photochemistry of this important intermediate. Selected wavelength laser irradiation of CHBr(3) isolated in Ar or Ne matrices at ~5 K yielded iso-CHBr(3); the observed infrared and UV/visible absorptions are in excellent agreement with computational predictions, and the energies of various stationary points on the CHBr(3) potential energy surface were characterized computationally using high-level methods in combination with correlation consistent basis sets. These calculations show that, while the corresponding minima lie ~200 kJ/mol above the global CHBr(3) minimum, the isomer is bound by some 60 kJ/mol in the gas phase with respect to the CHBr(2) + Br asymptote. The photochemistry of iso-CHBr(3) was investigated by selected wavelength laser irradiation into the intense S(0) → S(3) transition, which resulted in back photoisomerization to CHBr(3). Intrinsic reaction coordinate calculations confirmed the existence of a first-order saddle point connecting the two isomers, which lies energetically below the threshold of the radical channel. Subsequently, natural bond orbital analysis and natural resonance theory were used to characterize the important resonance structures of the isomer and related stationary points, which demonstrate that the isomerization transition state represents a crossover from dominantly covalent to dominantly ionic bonding. In condensed phases, the ion-pair dominated isomerization transition state structure is preferentially stabilized, so that the barrier to isomerization is lowered.

Formation and relaxation dynamics of iso-CH2Cl–I in cryogenic matrices

Photolysis of chloroiodomethane (CH(2)ClI) in cryogenic matrices followed by recombination of the nascent radical pair produces an isomer (CH(2)Cl-I) that features a halogen-halogen (Cl-I) bond. Using ultrafast laser pulses, it is possible to follow the formation of this isomer by transient electronic absorption in low-temperature matrices of N(2), CH(4), and Ar. Frequency-domain measurements provide vibrational and electronic spectra, and electronic structure calculations give the structures of the isomers and the minimum energy path that connects them. The ultrafast experiments cleave the C-I bond with a 267-nm photolysis pulse and probe the formation of the isomer at wavelengths between 435 nm and 510 nm. The longest wavelengths preferentially interrogate vibrationally excited molecules, and their transient absorption shows that the highly vibrationally excited isomer appears within 1 to 2 ps, depending on the matrix, likely reflecting the loss of 2000 cm(-1) or more of energy in a strong, inelastic collision of the fragments with the matrix. The subsequent relaxation of the vibrationally excited isomer occurs in 20 to 40 ps, a time that is comparable to those observed for halomethane molecules and their isomers in liquids and in supercritical CO(2). These observations suggest that the formation and initial relaxation of the isomer in dense media do not depend strongly on the identity of the surroundings.

Spectroscopic And Computational Studies Of The Laser Photolysis Of Matrix Isolated 1,2-dibromoethanes: Formation And Fate Of The Bromoethyl Radicals

We report experimental and computational studies of the photolysis of atmospherically important 1,2-dibromoethanes (1,2-C(2)X(4)Br(2); X = H, F) in Ar matrixes at 5 K. Using the pulsed deposition method, we find that significant conformational relaxation occurs for 1,2-C(2)H(4)Br(2) (EDB; observed anti/gauche ratio =30:1) but not for 1,2-C(2)F(4)Br(2) (TFEDB; anti/gauche = 3:1), which is traced to a larger barrier to rotation about the C-C bond in the latter. Laser photolysis of matrix-isolated EDB at 220 nm reveals the growth of infrared bands assigned to the gauche conformer and C(2)H(4)-Br(2) charge transfer complex (both as major products), and the C(2)H(4)Br radical and C(2)H(3)Br-HBr complex as minor (trace) products. The presence of the C(2)H(4)-Br(2) complex is confirmed in the UV/visible spectrum, which shows an intense charge transfer band at 237 nm that grows in intensity upon annealing. In contrast to previous reports, our experimental and computational results do not support a bridged structure for the C(2)H(4)Br radical in either the gas phase or matrix environments. We also report on the laser photolysis of matrix-isolated TFEDB at 220 nm. Here, the dominant photoproducts are the anti and gauche conformers of the C(2)F(4)Br radical, the vibrational and electronic spectra of which are characterized here for the first time. The increase in yield of radical for TFEDB vs EDB is consistent with the stronger C-Br bond in the fluoro-substituted radical species. The photochemistry of the C(2)F(4)Br radical following excitation at 266 nm was investigated and found to lead C-Br bond cleavage and formation of C(2)F(4). The implications of this work for the atmospheric and condensed phase photochemistry of the alkyl halides is emphasized.

Matrix isolation and computational study of isodifluorodibromomethane (F2CBr–Br): A route to Br2 formation in CF2Br2 photolysis

The photolysis products of dibromodifluoromethane (CF(2)Br(2)) were characterized by matrix isolation infrared and UV/Visible spectroscopy, supported by ab initio calculations. Photolysis at wavelengths of 240 and 266 nm of CF(2)Br(2):Ar samples (approximately 1:5000) held at approximately 5 K yielded iso-CF(2)Br(2) (F(2)CBrBr), a weakly bound isomer of CF(2)Br(2), which is characterized here for the first time. The observed infrared and UV/Visible absorptions of iso-CF(2)Br(2) are in excellent agreement with computational predictions at the B3LYP/aug-cc-pVTZ level. Single point energy calculations at the CCSD(T)/aug-cc-pVDZ level on the B3LYP optimized geometries suggest that the isoform is a minimum on the CF(2)Br(2) potential energy surface, lying some 55 kcal/mol above the CF(2)Br(2) ground state. The energies of various stationary points on the CF(2)Br(2) potential energy surface were characterized computationally; taken with our experimental results, these show that iso-CF(2)Br(2) is an intermediate in the Br+CF(2)Br-->CF(2)+Br(2) reaction. The photochemistry of the isoform was also investigated; excitation into the intense 359 nm absorption band resulted in isomerization to CF(2)Br(2). Our results are discussed in view of the rich literature on the gas-phase photochemistry of CF(2)Br(2), particularly with respect to the existence of a roaming atom pathway leading to molecular products.

Reactive pathways in the chlorobenzene-ammonia dimer cation radical: new insights from experiment and theory.

Building upon our recent studies of noncovalent interactions in chlorobenzene and bromobenzene clusters, in this work we focus on interactions of chlorobenzene (PhCl) with a prototypical N atom donor, ammonia (NH3). Thus, we have obtained electronic spectra of PhCl···(NH3)n (n = 1-3) complexes in the region of the PhCl monomer S0 -S1 (ππ*) transition using resonant 2-photon ionization (R2PI) methods combined with time-of-flight mass analysis. Consistent with previous studies, we find that upon ionization the PhCl···NH3 dimer cation radical reacts primarily via Cl atom loss. A second channel, HCl loss, is identified for the first time in R2PI studies of the 1:1 complex, and a third channel, H atom loss, is identified for the first time. While prior studies have assumed the dominance of a π-type complex, we find that the reactive complex corresponds instead to an in-plane σ-type complex. This is supported by electronic structure calculations using density functional theory and post-Hartree-Fock methods and Franck-Condon analysis. The reactive pathways in this system were extensively characterized computationally, and consistent with results from previous calculations, we find two nearly isoenergetic arenium ions (Wheland intermediates; denoted WH1, WH2), which lie energetically below the initially formed dimer cation radical complex. At the energy of our experiment, intermediate WH1, produced from ipso-addition, is not stable with respect to Cl or HCl loss, and the relative branching between these channels observed in our experiment is well reproduced by microcanonical transition state theory calculations based upon the calculated parameters. Intermediate WH2, where NH3 adds ortho to the halogen, decomposes over a large barrier via H atom loss to form protonated o-chloroaniline. This channel is not open at the (2-photon) energy of our experiments, and it is suggested that photodissociation of a long-lived (i.e., several ns) WH2 intermediate leads to the observed products.

PULSED JET DISCHARGE MATRIX ISOLATION AND COMPUTATIONAL STUDY OF HALOGEN ATOM COMPLEXES: Br--BrCH

Halogen atoms are important reactive radicals in the atmosphere. In this work, pulsed jet discharge matrix isolation spectroscopy and computational methods were used to characterize prereactive complexes of halogen atoms with simple halons. Our experiments combined matrix isolation techniques with a pulsed DC discharge nozzle, where a dilute CH(2)XBr (X = H, Cl, Br)/rare gas sample was gently discharged and the products were deposited onto a cold KBr window. The Br···BrCH(2)X (X = H, Cl, Br) complexes were characterized by infrared and electronic spectroscopy, supported by ab initio and density functional theory (DFT) calculations, which shed light on the structure of, bonding in, and binding energy of the complexes. The correlation of charge-transfer energy with donor ionization potential (Mulliken correlation) was examined, and the charge-transfer photochemistry of the complexes was explored.

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Building upon our recent studies of radical addition pathways following excitation of the I2 chromophore in the donor-acceptor complex of ethylene and I2 (C2H4···I2), in this article, we extend our studies to examine photoinduced electron transfer. Thus, irradiation into the intense charge-transfer band of the complex (λmax = 247 nm) gave rise to a band at 366 nm that is assigned to the bridged ethylene-I radical complex on the basis of our prior work. The formation of the radical complex is explained by a mechanism that involves rapid back electron transfer leading to I-I bond fission. Excitation into the charge-transfer band of the radical complex led to regeneration of the parent complex and the formation of the final photoproduct, anti- and gauche-1,2-diiodoethane, which confirms that the reaction proceeds ultimately by a radical addition mechanism. This finding is contrasted with our previous study of the C2H4···Br2 complex, where CT excitation led to only one product, anti-1,2-dibromoethane, a result explained by a single electron-transfer mechanism proceeding via a bridged bromonium ion intermediate. For the I2 complex, the breakup of the photolytically generated I2(-•) anion radical is apparently sufficiently slow to render it uncompetitive with back electron transfer. Finally, we report a detailed computational examination of the parent and radical complexes of both bromine and iodine, using high-level single- and multireference methods, which provide insight into the different behaviors of the charge-transfer states of the two radicals and the role of spin-orbit coupling.

X (X=H,Cl,Br)

We report an experimental and computational study of the photodecomposition pathways of a prototypical gem-dihalide, 1,1-dibromoethane (1,1-EDB), in the condensed phase. Following photolysis of the matrix isolated parent compound in Ar at 5 K, photoproducts are observed corresponding to Br2 elimination (+ C2H4 or C2H2) and HBr elimination (+ vinyl bromide). The elimination products are observed in the matrix as complexes. In contrast to our recent studies of the photolysis of matrix isolated polyhalomethanes, no evidence for the iso-1,1-EDB species is found, although studies of the matrix isolated 1,1-dibromo-2,2,2-trifluoroethane analogue show that the isomer is the dominant photoproduct. These results are examined in the light of theoretical studies that have characterized in detail the 1,1-EDB potential energy surface (PES). For Br2 elimination, a pathway from the isomer on the singlet PES is found which involves a simultaneous Br2 loss with 1,2-hydrogen shift; this pathway lies lower in energy than a concerted three-center elimination from the parent 1,1-EDB. For HBr elimination, our previous theoretical studies [Kalume, A.; George, L.; Cunningham, N.; Reid, S. A. Chem. Phys. Lett. 2013, 556, 35-38] have demonstrated the existence of concerted (single-step) and sequential pathways that involve coupled proton and electron transfer, with the sequential pathway involving the isomer as an intermediate. Here, more extensive computational results argue against a simple radical abstraction pathway for this process, and we compare experimental and computational results to prior results from the photolysis of the structural isomer, 1,2-EDB. These steady-state experiments set the stage for ultrafast studies of the dynamics of this system, which will be important in unraveling the complex photodecomposition pathways operative in condensed phases.

Photoinduced Electron Transfer in Donor–Acceptor Complexes of Ethylene with Molecular and Atomic Iodine

The photolysis products of dibromodifluoromethane (CF(2)Br(2)) were characterized by matrix isolation infrared and UV/Visible spectroscopy, supported by ab initio calculations. Photolysis at wavelengths of 240 and 266 nm of CF(2)Br(2):Ar samples (approximately 1:5000) held at approximately 5 K yielded iso-CF(2)Br(2) (F(2)CBrBr), a weakly bound isomer of CF(2)Br(2), which is characterized here for the first time. The observed infrared and UV/Visible absorptions of iso-CF(2)Br(2) are in excellent agreement with computational predictions at the B3LYP/aug-cc-pVTZ level. Single point energy calculations at the CCSD(T)/aug-cc-pVDZ level on the B3LYP optimized geometries suggest that the isoform is a minimum on the CF(2)Br(2) potential energy surface, lying some 55 kcal/mol above the CF(2)Br(2) ground state. The energies of various stationary points on the CF(2)Br(2) potential energy surface were characterized computationally; taken with our experimental results, these show that iso-CF(2)Br(2) is an intermediate in the Br+CF(2)Br-->CF(2)+Br(2) reaction. The photochemistry of the isoform was also investigated; excitation into the intense 359 nm absorption band resulted in isomerization to CF(2)Br(2). Our results are discussed in view of the rich literature on the gas-phase photochemistry of CF(2)Br(2), particularly with respect to the existence of a roaming atom pathway leading to molecular products.