TIME-RESOLVED RELAXATION DYNAMICS OF NEAR-INFRARED EXCITED ELECTRONIC STATES IN TRANSITION METAL COMPLEXES.

Sub-100 fs time-resolved, broadband transient absorption spectroscopy was employed to investigate ultrafast radiationless relaxation dynamics of near-infrared, metal-centered (MC), electronic excited states of several d$^{5}$ and d$^{9}$ transition metal complexes (e.g., \chem{CuCl_4}$^{2-}$, \chem{CuBr_4}$^{2-}$, \chem{IrBr_6}$^{2-}$, \chem{IrCl_6}$^{2-}$, etc.) in acetonitrile solution. The results yield insights into the topology of the involved potential energy surfaces, Jann-Teller distortions, and the dynamics through conical intersections connecting the first excited and ground electronic states (energy gap, less than 8000 \wn). Furthermore, it was found that the addition of water to the solutions efficiently quenches the MC excited states via energy transfer

Watching Ultrafast Barrierless Excited-state Isomerization Of Pseudocyanine In Real Time

The photoinduced excited-state processes in 1,1\u27-diethyl-2,2\u27-cyanine iodine are investigated using femtosecond time-resolved pump-probe spectroscopy. Using a broad range of probe wavelengths, the relaxation of the initially prepared excited-state wavepacket can be followed down to the sink region. The data directly visualize the directed downhill motion along the torsional reaction coordinate and suggest a barrierless excited-state isomerization in the short chain cyanine dye. Additionally, ultrafast ground-state hole and excited-state hole replica broadening is observed. While the narrow excited-state wavepacket broadens during pump-probe overlap, the ground-state hole burning dynamics takes place on a significantly longer time-scale. The experiment reported can be considered as a direct monitoring of the shape and the position of the photoprepared wavepacket on the excited-state potential energy surface

ULTRAFAST DYNAMICS OF DIBROMOCYCLOALKANES

Carbocyclic geminal dibromides are important intermediates in synthesis of complex heterocyclic molecules and natural products.\footnote{Ganesh, N. V.; Jayaraman, N. J. Org. Chem. 2007, 72, 5500-5504.} Ultrafast time-resolved techniques can help to obtain information about the electronic structure of the intermediates which appears in the chemistry and photochemistry of these molecules. Also, relaxation dynamics and reactivity of these intermediates in different solvents can be characterized. This information can be used for the design of different compounds with desired properties. In the current work, 1,1-dibromocycloalkanes with 3-, 4-, and 5-member rings were synthesized using previously described procedures.\footnote{Napolitano, E.; Fiachi, R.; Mastrorilli, E. Synt. Comm. 1986, 122-125.} \footnote{ingh, R. K.; Danishefsky, S. J.Org.Chem. 1975, 40, 2969-2970.} \footnote{Blankenship, C.; Paquette, L. A. Synt. Comm. 1984, 14, 983-987.} For all three samples, ultrafast time-resolved absorption experiments with UV-excitation were performed in acetonitrile and methylcyclohexane solvents. It was shown that excitation of dibromocycloalkane solutions with 250 nm short (40 fs) pulses forms excited state absorption (ESA) of parent molecules in the spectral range from 360 to 760 nm. Within 800 fs, ESA decays with beginning of formation product bands. Next within 50 ps, these broad bands reach their maximum intensity and form well-defined broad peaks centered at 550, 600 and 400 nm for 3-, 4-, and 5-member rings respectively. These product species are long-lived and begin to decay at 1 ns. Obtained results suggest the formation of isomer products \chem{(CH_2)\chem{n}-C-Br-Br} (n=1-3), similar to the isomeric species (HBrCBr-Br) observed in isomerization of bromoform.\footnote{Pal, S. K.; Mereshchenko, A. S.; Butaeva, E. V.; El-Khoury, P. Z.; Tarnovsky, A. N. J. Chem. Phys. 2013, 138, 124501.} \footnote{Mereshchenko, A. S.; Butaeva, E. V.; Borin, V. A.; Eyzips, A.; Tarnovsky, A. N. Nat. Chem. 2015, 7, 562-568.

Wavepacket Motion Via A Conical Intersection In The Photochemistry Of Aqueous Transition-metal Dianions

The photochemical reaction paths in aqueous PtBr(6)(2-) and OsBr(6)(2-) have been studied by femtosecond broad-band pump probe spectroscopy supported by CASPT2 and DFT/TDDFT calculations. These paths lead to the separation of negative charges and propagate through distortions of nascent, penta-coordinated metal fragments caused by Jahn-Teller C(4v) and D(3h) conical intersections (CIs), respectively. Within 150 fs following 420 nm excitation of PtBr(6)(2-), the molecule undergoes internal conversion and intersystem crossing into the dissociative lowest triplet excited (3)T(1g) state, loses a ligand, and relaxes via the C(4v) CI to the nearly trigonal bipyramid (3)PtBr(5)(-) product in the triplet state. Direct 530 nm excitation of PtBr(6)(2-) to (3)T(1g) yields. the same product. Oscillations observed in the bending and umbrella a(1) modes of (3)PtBr(5)(-) arise from impulsive excitation of, respectively, one of the reaction coordinate modes, which is parallel to the gradient difference vector of the C(4v) CI, and the spectator mode that preserves the electronic degeneracy

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 (F2 Cbr-Br): A Route to Br2 Formation in Cf2 Br2 Photolysis

The photolysis products of dibromodifluoromethane (CF2 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 CF2 Br2:Ar samples (∼1:5000) held at ∼5 K yielded iso- CF2 Br2 (F2 CBrBr), a weakly bound isomer of CF2 Br2, which is characterized here for the first time. The observed infrared and UV/Visible absorptions of iso- CF2 Br2 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 CF2 Br2 potential energy surface, lying some 55 kcal/mol above the CF2 Br2 ground state. The energies of various stationary points on the CF2 Br 2 potential energy surface were characterized computationally; taken with our experimental results, these show that iso- CF2 Br 2 is an intermediate in the Br+ CF2 Br→ CF 2 + Br2 reaction. The photochemistry of the isoform was also investigated; excitation into the intense 359 nm absorption band resulted in isomerization to CF2 Br2. Our results are discussed in view of the rich literature on the gas-phase photochemistry of CF2 Br2, particularly with respect to the existence of a roaming atom pathway leading to molecular products. © 2010 American Institute of Physics

Radiative Recombination Of Spatially Extended Excitons In (znse/cds)/cds Heterostructured Nanorods

We report on organometallic synthesis of luminescent (ZnSe/CdS)/CdS semiconductor heterostructured nanorods (hetero-NRs) that produce an efficient spatial separation of carriers along the main axis of the structure (type II carrier localization). Nanorods were fabricated using a seeded-type approach by nucleating the growth of 20-100 nm CdS extensions at [000 +/- 1] facets of wurtzite ZnSe/CdS core/shell nanocrystals. The difference in growth rates of CdS in each of the two directions ensures that the position of ZnSe/CdS seeds in the final structure is offset from the center of hetero-NRs, resulting in a spatially asymmetric distribution of carrier wave functions along the heterostructure. Present work demonstrates a number of unique properties of (ZnSe/CdS)/CdS hetero-NRs, including enhanced magnitude of quantum confined Stark effect and subnanosecond switching of absorption energies that can find practical applications in electroabsorption switches and ultrasensitive charge detectors

Structure Of The Photochemical Reaction Path Populated Via Promotion Of Cf2i2 Into Its First Excited State

The photochemical reaction path following the promotion of CF2I2 into its lowest-lying excited electronic singlet state has been modeled using ab initio multiconfigurational quantum chemical calculations. It is found that a conical intersection drives the electronically excited CF2I2* species either to the CF2I + I radical pair or back to the starting CF2I2 structure. The structures of the computed relaxation pathways explain the photoproduct selectivity previously observed in the gas phase. Furthermore, the results provide the basis for explaining the condensed-phase photochemistry of CF2I2

5-azido-2-aminopyridine, A New Nitrene/nitrenium Ion Photoaffinity Labeling Agent That Exhibits Reversible Intersystem Crossing Between Singlet And Triplet Nitrenes

The photochemistry of a new photoaffinity labeling (PAL) agent, 5-azido-2-(N,N-diethylamino)pyridine, was studied in aprotic and protic solvents using femtosecond-to-microsecond transient absorption and product analysis, in conjunction with ab initio multiconfigurational and multireference quantum chemical calculations. The excited singlet SI state is spectroscopically dark, whereas photoexcitation to higher-lying singlet excited S-2 and S-3 states drives the photochemical reaction toward a barrierless ultrafast relaxation path via two conical intersections to S-1, where N-2 elimination leads to the formation of the closed-shell singlet nitrene. The singlet nitrene undergoes intersystem crossing (ISC) to the triplet nitrene in aprotic and protic solvents as well as protonation to form the nitrenium ion. The ISC rate constants in aprotic solvents increase with solvent polarity, displaying a direct gap effect, whereas an inverse gap effect is observed in protic solvents. Transient absorption actinometry experiments suggest that a solvent-dependent fraction from 20% to 50% of nitrenium ions is generated on a time scale of a few tens of picoseconds. The closed-shell singlet and triplet nitrene are separated by a small energy gap in protic solvents. As a result, the unreactive triplet state nitrene undergoes delayed, thermally activated reverse ISC to reform the reactive closed-shell singlet nitrene, which subsequently protonates, forming the remaining fraction of nitrenium ions. The product studies demonstrate that the resulting nitrenium ion stabilized by the electron-donating 4-amino group yields the final cross-linked product with high, almost quantitative efficiency. The enhanced PAL function of this new azide with respect to the widely applied 4-amino-3-nitrophenyl azide is discussed

Probing Vibrationally Mediated Ultrafast Excited-state Reaction Dynamics With Multireference (caspt2) Trajectories

Excited-state trajectories computed at the complete active space second-order perturbation theory (CASPT2) reveal how vibrational excitation controls the molecular approach to the intersection space that drives the photodissociation of a prototypical halogenated methyl radical, namely CF2I. Translating the Franck-Condon structure along the ground-state CASPT2 vibrational modes in this system followed by propagating the displaced structures in the first excited doublet state simulates specific vibrational excitations and vibrationally mediated dynamics, respectively. Three distinct situations are encountered: the trajectories (i) converge to an energetically flat segment of the intersection space, (ii) locate a segment of the intersection space, and (iii) access a region where the intersection space degeneracy is lifted to form a ridge of avoided crossings. The computational protocol documented herein can be used as a tool to design control strategies based on selective excitation of vibrational modes, including adaptive feedback schemes using coherent light sources