In this Communication, the plus and minus signs of the circular dichroism (CD) spectra in Figures 2b and 4b were incorrect. The corrected Figures are shown below. Additionally,after further theoretical investigation, it was found that the signs of the rotatory strengths (R)for pseudoephedrine (pED) vary depending on the type of the density functionals used in the time-dependent density functional theory (TDDFT) calculations. This variation is due to small CD effects of the S 0-S 1 transition of pED and large error bars of the CD values predicted by theory.T able S1 in the Supporting Information lists the R values estimated using various density functionals. Figure 2. a) R2PI spectrum of S-pED near the origin band of the S 0-S 1 transition. The inset shows the structure of S-pED. The number of ions produced by as ingle-laser pulse at the origin bands was roughly estimated as about 900. b) R2PI CD spectra of S-(blue line) and R-pED (red line). The g values at the bands of AG(a), AG(b), and GG(a) of S-pED were measured as + + 0.026 AE 0.005, À0.025 AE 0.006, and + + 0.024 AE 0.005, respectively.c)Theoretical CD spectra of S-(blue line) and R-pED (red line) obtained with the rotatory strength, R,c alculated using TDDFT at the M06-2X/6-311 + ++ + G(d,p) level. Figure 4. a) R2PI spectrum of RED near the origin band of the S 0-S 1 transition. The inset shows the structure of RED. The discontinuous region between 37825 and 37855 cm À1 is where the grating order of the dye laser changes. b) R2PI CD spectrum of RED. The g values of 1-3 bands were measured as + + 0.030 AE 0.011, À0.091 AE 0.007,a nd + + 0.041 AE 0.013, respectively.
Anion chemical dynamics of autodetachment and fragmentation mediated by the dipole-bound state (DBS) have been thoroughly investigated in a state-specific way for the first time by employing the picosecond time-resolved or the nanosecond frequency-resolved spectroscopy combined with the cryogenically cooled ion trap and velocity-map imaging techniques. For the ortho-, meta-, or para-iodophenoxide anion (o-, m-, or p-IPhO -), the C-I bond rupture giving the anionic iodide (I -) fragment occurs via the nonadiabatic transition from the DBS to the nearby valence-bound states (VBS) of the anion where the vibronic coupling into the S1 (πσ*) state (which is repulsive along the C-I bond extension coordinate) should be largely responsible. The dynamic details are governed by the isomer-specific nature of the potential energy surfaces in the vicinity of the DBS-VBS curve crossings, as manifested in the huge different chemical reactivity of o-, m-, or p-IPhO -. It is confirmed here that the C-I bond dissociation is mediated by DBS resonances, providing the foremost evidence that the metastable DBS plays the essential role as the doorway into the anion chemistry especially of the dissociative electron attachment (DEA). The fragmentation channel is dominant when it is mediated by the DBS resonances located below the electron-affinity (EA) threshold, whereas it is kinetically adjusted by the competitive autodetachment process when the DBS resonances lying above EA convey the electron to the valence orbitals. The product yield of the C-I bond cleavage is strongly mode-dependent as the rate of the concomitant autodetachment is much influenced by the characteristics of the individual vibrational modes, paving a new way of the reaction control of the anion chemistry.
Conspectus Nonvalence bound states (NBS) are anionic states where the excess electron is extremely loosely bound to the neutral core through long-range potentials. In contrast to the valence orbitals of which the electron occupancy determines the molecular structure, as well as the chemical reactivity, the nonvalence orbital is quite diffuse and located far from the neutral core. The NBS can be classified into the dipole-bound state (DBS), quadruple-bound state (QBS), or correlation-bound state (CBS) according to the nature of the electron-neutral interaction, although their interaction potentials may cooperatively contribute. The NBS is ubiquitous in nature and has the strong implications in atmospheric, interstellar, or biological chemistry. Accordingly, NBS has long been conceived to play the role of the doorway into the formation of a stable anion or dissociative electron attachment (DEA). Despite intensive and extensive studies, however, the quantum-mechanical nature of NBS is still far from being thorough understanding. Herein, we describe a new aspect of state-specific NBS-mediated chemical dynamics, which has been revealed through a series of recent studies by our group. We have employed picosecond time–resolved pump–probe spectroscopy combined with cryogenically cooled ion trap and velocity-map imaging techniques to study closed-shell anions generated by electrospray ionization. DBS vibrational Feshbach resonances are prepared by the optical excitation of phenoxide, for instance, and their individual lifetimes have been precisely measured in a state-specific manner to reveal the strong mode-dependency of the autodetachment rate. Fermi’s golden rule turns out to be extremely useful for a rational explanation of the experiment, although the more sophisticated theoretical model is desirable for the more quantitative analysis. For the DBS of para-chlorophenoxide or para-bromophenoxide where the polarizability of neutral core is substantial, the Fermi’s golden rule based on the charge-dipole potential needs to be significantly modified to include the correlation effects to explain the exceptionally slow autodetachment rates. For the QBS of 4-cyanophenoxide, the mode-specific behavior of the quadrupole ellipsoid tensor explains the strong mode-dependent autodetachment rate. Meanwhile, the nonadiabatic transition of the excess electron into the valence orbital can result in stable anion formation or immediate chemical bond rupture. In the DBS of ortho-, meta-, or para-iodophenoxide, the transformation of the loosely bound excess electron into the πσ* antibonding orbital occurs to give I– as a final fragment. The fragmentation mediated by DBS occurs competitively with the concomitant autodetachment, paving a new way of the reaction control by tuning the quantum-mechanical nature of the DBS Feshbach resonance. This experimental observation provides the foremost evidence for the dynamic role of the DBS as a doorway into anion chemistry, such as DEA. The ponderomotive force on the electron in the nonvalence orbital...
Circular dichroism (CD) spectra contain information about absolute configurations and conformations of chiral compounds. However, extracting this information from CD spectra in solution is challenging, because the spectra exhibit only the averaged CD values of all different conformers. CD spectroscopy of jet-cooled molecules can provide conformation-specific CD spectra, but its application to biomolecules has been limited due to the difficulty of their production in the gas phase. Here, we obtained the first CD spectra of chiral molecular ions produced by electrospray ionization (ESI) using cold ion CD spectroscopy. Protonated L-or D-phenylalanine ions produced by ESI were stored in a cold quadrupole ion trap and irradiated by multiple laser pulses with left or right circular polarization. The CD spectra exhibited well-resolved CD bands of two conformers, whose signs were opposite to each other. This study will broaden the scope of conformation-resolved CD spectroscopy to large molecular ions without size limitations.
Circular dichroism (CD) spectroscopy of jet-cooled molecules provides conformation-specific CD spectra. However, its widespread utilization has been limited by the weak CD effects and the low density of gas-phase molecules. Here, we developed a dual-beam method to improve the sensitivity and accuracy of gas-phase CD measurements. Circularly and linearly polarized pulses were generated from a single laser pulse and used to irradiate a single molecular-beam pulse to produce two ion peaks. The ion peaks induced by linearly polarized pulses were subtracted from those induced by circularly polarized pulses to correct the CD values for the pulse-to-pulse fluctuations in laser power and gas density. The resonant two-photon ionization CD spectrum of (1R,2R)-(−)-pseudoephedrine revealed that the standard deviations of CD values measured using the dual-beam method were three times lower than those measured using a single-beam method. The dual-beam method provides an effective, accurate, and easy-to-use tool to obtain gas-phase CD spectra.
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