In our experiment, a trace amount of an organic molecule (M = 1H-phenalen-1-one, 9-fluorenone, pyridine, or acridine) was seeded into a gas mix consisting of 3% O2 with a rare gas buffer (He or Ar) and then supersonically expanded. We excited the resulting molecular beam with ultraviolet light at either 355 nm (1H-phenalen-1-one, 9-fluorenone, or acridine) or 266 nm (pyridine) and used resonance enhanced multiphoton ionization (REMPI) spectroscopy to probe for formation of O2 in the a 1Δg state, 1O2. For all systems, the REMPI spectra demonstrates that ultraviolet excitation results in formation of 1O2 and the oxygen product is confirmed to be in the ground vibrational state and with an effective rotational temperature below 80 K. We then recorded the velocity map ion image of the 1O2 product. From the ion images we determined the center-of-mass translational energy distribution, P(ET), assuming photodissociation of a bimolecular M-O2 complex. We also report results from electronic structure calculations that allow for a determination of the M-O2 ground state binding energy. We use the complex binding energy, the energy to form 1O2, and the adiabatic triplet energy for each organic molecule to determine the available energy following photodissociation. For dissociation of a bimolecular complex, this available energy may be partitioned into either center-of-mass recoil or internal degrees of freedom of the organic moiety. We use the available energy to generate a Prior distribution, which predicts statistical energy partitioning during dissociation. For low available energies, less than 0.2 eV, we find the statistical prediction is in reasonable agreement with the experimental observations. However, at higher available energies the experimental distribution is biased to lower center-of-mass kinetic energies compared with the statistical prediction, which suggests the complex undergoes vibrational predissociation.
more »
« less
Singlet O 2 from Ultraviolet Excitation of the Quinoline-O 2 Complex
We report results from experiments with the quinoline-O2 complex, which was photodissociated using light near 312 nm. Photodissociation resulted in formation of the lowest excited state of oxygen, O2 a 1Δg, which we detected using resonance enhanced multiphoton ionization and velocity map ion imaging. The O2+ ion image allowed for a determination of the center-of-mass translational energy distribution, P(ET), following complex dissociation. We also report results of electronic structure calculations for the quinoline singlet ground state and lowest energy triplet state. From the CCSD/aug-cc-pVDZ//(U)MP2/cc-pVDZ calculations, we determined the lowest energy triplet state to have ππ* electronic character and to be 2.69 eV above the ground state. We also used electronic structure calculations to determine the geometry and binding energy for several quinoline-O2 complexes. The calculations indicated that the most strongly bound complex has a well depth of about 0.11 eV and places the O2 moiety above and approximately parallel to the quinoline ring system. By comparing the experimental P(ET) with the energy for the singlet ground state and the lowest energy triplet state, we concluded that the quinoline product was formed in the lowest energy triplet state. Finally, we found the experimental P(ET) to be in agreement with a Prior translational energy distribution, which suggests a statistical dissociation for the complex.
more »
« less
- Award ID(s):
- 2150871
- NSF-PAR ID:
- 10503670
- Publisher / Repository:
- Journal of Physical Chemistry A
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry A
- Volume:
- 127
- Issue:
- 23
- ISSN:
- 1089-5639
- Page Range / eLocation ID:
- 4957 to 4963
- Subject(s) / Keyword(s):
- singlet oxygen resonance enhanced multiphoton ionization REMPI velocity map ion imaging VMI
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract Little attention has been focused on diradical and zwitterionic photoperoxides formed from nitrosamine compounds. Here, an attempt is made to probe the electronic character of the nitrooxide intermediate formed in photochemical reactions with triplet oxygen (3O2). Theoretical studies have been conducted to screen
para ‐substituted phenyl nitrosamines. In particular, we find that electron‐withdrawing substituents produce low‐lying triplet nitrooxide diradicals. A clear electronic dependence in theS 0– T S 0– S 1energy gaps of nitrooxides was found using Hammett plots. Computed geometries show a twisted diradical triplet nitrooxide moiety, which contrasts to the nearly flat singlet zwitterionic ground state nitrooxide moiety; analyses of charges (natural bond order), molecular orbitals (HOMO /LUMO ) and spin densities enable these assignments. Calculations predict the former triplet species is photogenerated initially from nitrosamine with O2. The conversion of the triplet nitrooxide diradical to the singlet ground state is an example where longer‐lived zwitterionic nitrooxide structures become possible. The reaction mechanism is consistent with a zwitterionic ground state nitrooxide playing an important role in the bimolecular oxygen‐transfer reaction with phosphine and phosphite trapping agents as has been observed experimentally. -
more » « less
Abstract The structures of zinc carbene ZnCH2and zinc carbyne HZnCH, and the conversion transition states between them are optimized at B3LYP/aug‐cc‐pVTZ, MP2/aug‐cc‐pVTZ, and CCSD/aug‐cc‐pVTZ levels of theory. The thermodynamic energies with CCSD(T) method are further extrapolated to basis set limit through a series of basis sets of aug‐cc‐pVXZ (X=D, T, Q, 5). The Zn−C bonding characteristics are interpreted by molecular plots, Laplacian of density plots, the integrated delocalization indices, net atomic charges, and derived atomic hardness. On the one hand, the studies demonstrated the efficiency of DFT method in structure optimizations and the accuracy of CBS method in obtaining thermodynamic energies; On the other hand, the density analysis of CCSD/aug‐cc‐pVDZ density demonstrates that both the sharing interaction and ionic interaction are important in ZnCH2ad HZnCH. The3B1state of ZnCH2is the global minimum and formed in visible light, but its small bond dissociation energy (47.0 kcal/mol) cannot keep the complex intact under UV light (79.4–102.1 kcal/mol). However, the3Σ−state of HZnCH can survive the UV light due to the greater Zn−C dissociation energy (100.7 kcal/mol). The delocalization indices of Zn…C in both3B1of ZnCH2(0.777) and the3Σ−state of HZnCH (0.785) are close to the delocalization index of the single C−C bond of ethane (0.841), i. e. the nomenclature of Zinc carbene and Zinc carbyne is incorrect. The stronger Zn−C bond in the3Σ−state of HZnCH than in the3B1state of ZnCH2can be attributed to the larger charge separation in the former. It was found that the Zn−C bonds in related Zinc organic compounds were also single bonds no matter whether the organic groups are CR, CR2, or CR3. The ionic interactions were discussed in terms of the atomic hardness that were in turn related to ionization energy and electron affinity. The unique combination of covalent and ionic characteristics in the Zn−C bonds of organic Zinc compounds could be the origin of many interesting applications of organic Zinc reagents.
-
more » « less
Abstract Pnictinidenes are an increasingly relevant species in main group chemistry and generally exhibit proclivity for the triplet electronic ground state. However, the elusive singlet electronic states are often desired for chemical applications. We predict the singlet‐triplet energy differences (ΔEST=ESinglet−ETriplet) of simple group 15 and 16 substituted pnictinidenes (Pn−R; Pn=P, As, Sb, or Bi) with highly reliable focal‐point analyses targeting the CCSDTQ/CBS level of theory. The only cases we predict to have favorable singlet states are P−PH2(−3.2 kcal mol−1) and P−NH2(−0.2 kcal mol−1). ΔESTtrends are discussed in light of the geometric predictions as well as qualitative natural bond order analysis to elucidate some of the important electronic structure features. Our work provides a rigorous benchmark for the ΔESTof fundamental Pn−R moieties and provides a firm foundation for the continued study of heavier pnictinidenes.
-
more » « less
The dissociation of the CNHicomplex in GaN is studied in detail using photoluminescence measurements and first‐principles calculations. The blue luminescence (BL2) band with a maximum at 3.0 eV is caused by electron transitions from an excited state located at 0.02 eV below the conduction band to the ground state of the CNHidonor with the 0/+ level 0.15 eV above the valence band. The dissociation releases hydrogen atom, and the remaining CNdefect with the −/0 state at 0.92 eV above the valence band is responsible for the yellow band (YL1) with a maximum at about 2.2 eV. The dissociation of the CNHicomplex can be caused by the photoinduced defect reaction mechanism under UV illumination at low temperature (≈20 K), leading to the bleaching of the BL2 band and simultaneous rise in the YL1 band. The bleaching is reversible. Alternatively, the complex dissociates after annealing at temperatures above 600 °C. The activation energy of this process (3–4 eV, depending on the annealing geometry) corresponds to the removal of hydrogen from the sample and not to the dissociation of the complex itself.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.jpca.3c02024
